WO2011030688A1 - 共重合体を含有する感光性樹脂組成物 - Google Patents
共重合体を含有する感光性樹脂組成物 Download PDFInfo
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- WO2011030688A1 WO2011030688A1 PCT/JP2010/064717 JP2010064717W WO2011030688A1 WO 2011030688 A1 WO2011030688 A1 WO 2011030688A1 JP 2010064717 W JP2010064717 W JP 2010064717W WO 2011030688 A1 WO2011030688 A1 WO 2011030688A1
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- photosensitive resin
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- 0 CCC(C(C*)C(N1)=O)C1=O Chemical compound CCC(C(C*)C(N1)=O)C1=O 0.000 description 1
- MUHKUHRAFSNYKF-UHFFFAOYSA-N CCC(C(CC)C(N1C2CC=CCC2)=O)C1=O Chemical compound CCC(C(CC)C(N1C2CC=CCC2)=O)C1=O MUHKUHRAFSNYKF-UHFFFAOYSA-N 0.000 description 1
Classifications
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/36—Amides or imides
- C08F222/40—Imides, e.g. cyclic imides
- C08F222/402—Alkyl substituted imides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/02—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/041—Lenses
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- 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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- 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
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
- G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- 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
- G03F7/40—Treatment after imagewise removal, e.g. baking
Definitions
- the present invention relates to a copolymer using allyl isocyanuric acid as a raw material and a photosensitive resin composition containing the copolymer.
- the present invention also relates to a photosensitive resin composition capable of remarkably improving light resistance, transparency, heat resistance, heat discoloration resistance, solvent resistance, crack resistance and the like for the film formed therefrom.
- polyhydroxystyrene is known as a material for forming a microlens.
- the polyhydroxystyrene is used as a microlens forming material, the hemispherical shape of the microlens is easily changed by heating at a high temperature, and it is difficult to form a microlens having a stable shape.
- polyhydroxystyrene is easily colored by heat treatment and tends to deteriorate transparency, and coloring may be observed when the microlens is used.
- Patent Document 1 An antireflection film-forming composition containing a polymer having a triazine trione structure has been proposed (Patent Document 1).
- Patent Documents 2 to 4 A photoresist composition containing a maleimide copolymer, for forming a resist protective film for immersion lithography. Materials and the like have been proposed (Patent Documents 2 to 4).
- an alkali-soluble copolymer composed of indene, maleimide and N-substituted maleimide, a 1,2-naphthoquinonediazide compound for the purpose of developing an insulating film of a display device such as a liquid crystal display (LCD) or an organic electroluminescence display
- an alkali-soluble copolymer composed of indene, maleimide and N-substituted maleimide, a 1,2-naphthoquinonediazide compound and A method for forming an insulating film for a display device, which uses a radiation-sensitive resin composition containing a crosslinking agent, has been proposed (Patent Document 5).
- Patent Document 5 proposes very excellent in compatibility with polyfunctional (meth) acrylates, and also has good alkali solubility.
- a maleimide copolymer characterized by containing a monomer structural unit derived from styrene, a monomer structural unit derived from styrenes, and a monomer structure derived from (meth) acrylic acid has been proposed ( Patent Document 6).
- Japanese Patent No. 4126556 US Pat. No. 6,586,560 (B1) Japanese Patent Publication No. 6-23842 JP 2008-303315 A JP 2003-131375 A JP 2004-224894 A JP 2001-354822 A
- the present invention has been made based on the above circumstances, and the problems to be solved are significantly improved in light resistance, transparency, heat resistance, heat discoloration resistance, solvent resistance, patterning property and crack resistance. It is providing the photosensitive resin composition which can do. Moreover, the subject of this invention is providing the cured film and microlens which were formed from the photosensitive resin composition and excellent in the said characteristic.
- (A) component the copolymer which has a structural unit represented by following formula (1)
- (B) component The photosensitive resin composition containing a photosensitive agent.
- two X's each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 or 6 carbon atoms, a phenyl group or a benzyl group, provided that the alkyl group, (In the cycloalkyl group, the phenyl group and the benzyl group, part or all of the hydrogen atoms may be substituted with a halogen atom, a carboxyl group, a hydroxyl group, an amino group or a nitro group.)
- the component (A) is a copolymer having at least one maleimide structural unit represented by the following formula (2) in addition to the structural unit represented by the formula (1).
- the photosensitive resin composition as described.
- Y represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 or 6 carbon atoms, a phenyl group or a benzyl group, provided that the alkyl group, the cycloalkyl group, In the phenyl group and the benzyl group, part or all of the hydrogen atoms may be substituted with a halogen atom, a carboxyl group, a hydroxyl group, an amino group, or a nitro group.
- the photosensitive resin composition according to the first aspect wherein the copolymer has a weight average molecular weight of 1,000 to 30,000.
- the photosensitive resin composition as described in the 1st viewpoint or 2nd viewpoint which contains the crosslinking agent which is (C) component further.
- the film formed from the photosensitive resin composition of the present invention can have excellent light resistance, transparency, heat resistance, heat discoloration resistance, solvent resistance and crack resistance.
- the pattern formed from the photosensitive resin composition of this invention can also have the outstanding heat resistance, solvent resistance, etc.
- various microlenses having different refractive indexes are formed from the composition by changing the type of maleimide used when synthesizing the copolymer. can do.
- the copolymerization of unsubstituted maleimide and / or N-substituted maleimide and allyl isocyanuric acid so as to obtain an alternating copolymer is more preferable than the polymerization of allyl isocyanuric acid with each other (yield 10% or less).
- the desired copolymer can be obtained with a high yield.
- the film formed from the photosensitive resin composition of the present invention is colored by a microlens when heat treatment is performed at a high temperature in the formation process or the formation process of peripheral devices such as wiring. The possibility of shape deformation can be significantly reduced.
- the photosensitive resin composition of the present invention is suitable as a material for forming a microlens.
- the present invention is a photosensitive resin composition containing the component (A) and the component (B).
- the solid content obtained by removing the solvent from the photosensitive resin composition of the present invention is usually 1 to 50% by mass.
- the component (A) of the present invention is a copolymer having at least a structural unit represented by the following formula (1).
- two X's each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 or 6 carbon atoms, a phenyl group or a benzyl group, provided that the alkyl group,
- the cycloalkyl group, the phenyl group and the benzyl group, part or all of the hydrogen atoms may be substituted with a halogen atom, a carboxyl group, a hydroxyl group, an amino group or a nitro group.
- the component (A) of the present invention is a copolymer having one or more maleimide structural units represented by the following formula (2) as structural units other than the structural unit represented by the above formula (1). It is a polymer.
- Y represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 or 6 carbon atoms, a phenyl group or a benzyl group, provided that the alkyl group, the cycloalkyl group, In the phenyl group and the benzyl group, part or all of the hydrogen atoms may be substituted with a halogen atom, a carboxyl group, a hydroxyl group, an amino group, or a nitro group.
- (A) component of this invention replaces with the structural unit represented by the said Formula (2) as structural units other than the structural unit represented by the said Formula (1), or is the said Formula (2).
- Z represents a phenyl group, a naphthyl group, an anthracenyl group, a biphenylyl group, a carbazole group or an alkoxy group having 1 to 8 carbon atoms, provided that the phenyl group, the naphthyl group, the anthracenyl group, the biphenylyl group
- the carbazole group part or all of the hydrogen atoms may be substituted with a halogen atom, a carboxyl group, a hydroxyl group, an amino group, or a nitro group.
- the copolymer of the component (A) is a copolymer having a structural unit represented by the above formula (2) and / or the above formula (3) other than the structural unit represented by the above formula (1).
- the molar ratio of the above formula (1) to the above formula (2) and / or the above formula (3) is usually 10 to 90:90 to 10, preferably 20 to 70:80 to 30.
- the weight average molecular weight of the polymer is usually 1000 to 30000, preferably 1500 to 20000.
- the weight average molecular weight is a value obtained by using gel as a standard sample by gel permeation chromatography (GPC).
- the content of the component (A) in the photosensitive resin composition of the present invention is usually 1 to 99% by mass based on the content in the solid content of the photosensitive resin composition, preferably 10 to 95% by mass.
- the method is not particularly limited, but it is generally obtained by polymerizing a monomer mixture containing the monomer species used for obtaining the above-mentioned copolymer in a solvent at a temperature of usually 50 to 110 ° C.
- the photosensitive agent which is the component (B) of the present invention is not particularly limited as long as it is a compound that can be used as a photosensitive component, but a 1,2-naphthoquinonediazide compound is preferable.
- the 1,2-naphthoquinonediazide compound is a compound having a hydroxyl group, and among these hydroxyl groups, 10 to 100 mol%, preferably 20 to 95 mol% is 1,2-naphthoquinonediazidesulfonic acid ester. Compound can be used.
- Examples of the compound having a hydroxyl group include phenol, o-cresol, m-cresol, p-cresol, hydroquinone, resorcinol, catechol, methyl gallate, ethyl gallate, 1,3,3-tris (4-hydroxy Phenyl) butane, 4,4-isopropylidene diphenol, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxyphenylsulfone, 4, 4-hexafluoroisopropylidenediphenol, 4,4 ′, 4 ′′ -trishydroxyphenylethane, 1,1,1-trishydroxyphenylethane, 4,4 ′-[1- [4- [1- (4 -Hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bi Sphenol, 2,4-dihydroxybenzophenone, 2,3,4-tri
- These photosensitizers can be used alone or in combination of two or more.
- the content of the component (B) in the photosensitive resin composition of the present invention is usually 1 to 50% by mass based on the content in the solid content of the photosensitive resin composition.
- the crosslinking agent which is (C) component
- the crosslinking agent is a compound which forms the coupling
- the crosslinking agent include polyfunctional (meth) acrylate compounds, epoxy compounds, hydroxymethyl group-substituted phenol compounds, and compounds having an alkoxyalkylated amino group. These crosslinking agents can be used alone or in combination of two or more.
- polyfunctional (meth) acrylate compound examples include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol.
- epoxy compound examples include novolac type epoxy resins, bisphenol type epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins.
- hydroxymethyl group-substituted phenol compound examples include 2-hydroxymethyl-4,6-dimethylphenol, 1,3,5-trihydroxymethylbenzene, and 3,5-dihydroxymethyl-4-methoxytoluene [2, 6-bis (hydroxymethyl) -p-cresol] and the like.
- Examples of the compound having an alkoxyalkylated amino group include, for example, (poly) methylolated melamine, (poly) methylolated glycoluril, (poly) methylolated benzoguanamine, (poly) methylolated urea, A nitrogen-containing compound having a plurality of active methylol groups, wherein at least one of the hydroxyl groups of the methylol group is substituted with an alkyl group such as a methyl group or a butyl group. .
- the compound having an alkoxyalkylated amino group may be a mixture of a plurality of substituted compounds, and some of them contain an oligomer component formed by self-condensation, but these can also be used. . More specifically, for example, hexamethoxymethyl melamine ("CYMEL (registered trademark) 303" manufactured by Nippon Cytec Industries Co., Ltd.), tetrabutoxymethyl glycoluril (“CYMEL (registered trademark) 1170 manufactured by Nippon Cytec Industries, Inc.). )), Tetramethoxymethylbenzoguanamine (“CYMEL (registered trademark) 1123" manufactured by Nippon Cytec Industries Co., Ltd.), and the like. Of the compounds having an alkoxyalkylated amino group, hexamethoxymethylmelamine represented by the following formula (7) is preferable.
- the content of the component (C) in the photosensitive resin composition of the present invention is usually 1 to 50% by mass based on the content in the solid content of the photosensitive resin composition.
- the method for preparing the photosensitive resin composition of the present invention is not particularly limited.
- the copolymer as component (A) is dissolved in a solvent, and the photosensitive agent as component (B) and (C) are dissolved in this solution.
- a method of mixing a cross-linking agent as a component at a predetermined ratio to obtain a uniform solution can be mentioned.
- a method in which other additives are further added and mixed as necessary may be mentioned.
- the solvent is not particularly limited as long as it can dissolve the components (A) to (C).
- solvents 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, propylene glycol monomethyl ether acetate.
- solvents can be used alone or in combination of two or more.
- propylene glycol monomethyl ether propylene glycol monomethyl ether acetate, 2-heptanone, ethyl lactate, butyl lactate and cyclohexanone are preferable from the viewpoint of improving the leveling property of the coating film.
- the photosensitive resin composition of this invention can also contain surfactant for the purpose of improving applicability
- the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, polyoxyethylene Polyoxyethylene alkyl allyl ethers such as nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate Sorbitan fatty acid esters such as rate, polyoxyethylene sorbitan monolaurate, polyoxyethylene Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as sorbitan monopalmitate, polyoxyethylene sorbitan
- the above surfactants can be used alone or in combination of two or more.
- the content in the photosensitive resin composition of the present invention is 3% by mass or less based on the content in the solid content of the photosensitive resin composition, preferably Is 1% by mass or less, more preferably 0.5% by mass or less.
- the resin composition of the present invention may be added with a curing aid, an ultraviolet absorber, a sensitizer, a plasticizer, an antioxidant, an adhesion aid, etc., as necessary, as long as the effects of the present invention are not impaired.
- An agent can be included.
- Substrate for example, a semiconductor substrate such as silicon covered with a silicon oxide film, a semiconductor substrate such as silicon covered with a silicon nitride film or a silicon oxynitride film, a silicon nitride substrate, a quartz substrate, a glass substrate (non-alkali glass, low (Including alkali glass, crystallized glass), glass substrate on which an ITO film is formed, etc. ⁇ , the photosensitive resin composition of the present invention is applied by an appropriate application method such as a spin coater. A coating film is formed by pre-baking using a heating means.
- the pre-bake conditions are appropriately selected from a baking temperature of 80 to 250 ° C. and a baking time of 0.3 to 60 minutes, preferably a baking temperature of 80 to 150 ° C. and a baking time of 0.5 to 5 minutes.
- the film thickness of the film formed from the photosensitive resin composition of the present invention is 0.005 to 3.0 ⁇ m, preferably 0.01 to 1.0 ⁇ m.
- exposure is performed through a mask (reticle) for forming a predetermined pattern on the film obtained above.
- a mask for forming a predetermined pattern on the film obtained above.
- ultraviolet rays such as g-line and i-line and far-infrared rays such as KrF excimer laser can be used.
- post-exposure heating Post Exposure Bake
- the conditions for the post-exposure heating are appropriately selected from heating temperatures of 80 to 150 ° C. and heating times of 0.3 to 60 minutes. Then, it is developed with an alkaline developer.
- alkaline developer examples include aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline, and ethanolamine. And alkaline aqueous solutions such as amine aqueous solutions such as propylamine and ethylenediamine. Further, a surfactant or the like can be added to these developers.
- alkali metal hydroxides such as potassium hydroxide and sodium hydroxide
- quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline
- alkaline aqueous solutions such as amine aqueous solutions such as propylamine and ethylenediamine.
- a surfactant or the like can be added to these developers.
- the development conditions are appropriately selected from a development temperature of 5 to 50 ° C. and a development time of 10 to 300 seconds.
- the film formed from the photosensitive resin composition of the present invention can be easily developed at room temperature using a tetramethylammonium hydroxide aqueous solution (TMAH aqueous solution). After development, rinsing is performed using ultrapure water or the like.
- TMAH aqueous solution tetramethylammonium hydroxide aqueous solution
- the entire surface of the substrate is exposed using ultraviolet rays such as g-line and i-line, KrF excimer laser, or the like.
- post-baking is performed using a heating means such as a hot plate.
- the post-baking conditions are appropriately selected from a baking temperature of 100 to 250 ° C. and a baking time of 0.5 to 60 minutes.
- Examples 1 and 2 3 g of the polymers obtained in Synthesis Examples 1 and 2, 0.9 g of P-150 (manufactured by Toyo Gosei Kogyo Co., Ltd.) as a photosensitizer, CYMEL (registered trademark) 303 (Nippon Cytec Industries Co., Ltd.) as a cross-linking agent 95 g and 0.01 g of Megafac (registered trademark) R-30 (manufactured by DIC Corporation) as a surfactant were dissolved in 12.0 g of propylene glycol monomethyl ether and 12.0 g of propylene glycol monomethyl ether acetate to obtain a solution. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and prepared the photosensitive resin composition (solution).
- a solution was prepared by dissolving in 7 g. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and prepared the photosensitive resin composition (solution).
- the film formed from the photosensitive resin composition of the present invention had high light resistance and was difficult to be colored.
- the transmittance of the film decreased to 90% after the light resistance test.
- the film formed from the photosensitive resin composition of the present invention had high heat resistance and hardly colored even after heating at 260 ° C.
- the film permeability was 95% after post-baking at 200 ° C. for 5 minutes, but when the film was further heated at 260 ° C. for 3 minutes, the film permeability was reduced to 78%.
- TMAH TMAH aqueous solution
- ultrapure water for 20 seconds
- drying a 2 ⁇ m ⁇ 2 ⁇ m dot pattern Formed.
- the entire surface was irradiated with 500 mJ / cm 2 of i-line (photo bleaching), and post-baked on a hot plate at 200 ° C. for 5 minutes. Further, these films were heated at 260 ° C. for 3 minutes.
- the pattern formed using the photosensitive resin composition of the present invention had high heat resistance, and the pattern did not reflow under any conditions of 200 ° C. and 260 ° C.
Abstract
Description
また、液晶ディスプレイ(LCD)、有機エレクトロルミネッセンスディスプレイ等のディスプレイ装置の絶縁膜の開発を目的に、インデンとマレイミドとN-置換マレイミドからなるアルカリ可溶性共重合体、1,2-ナフトキノンジアジド化合物、及び架橋剤を含有する感放射線性樹脂組成物を用いることを特徴とするディスプレイ装置の絶縁膜形成方法が提案されている(特許文献5)。
さらに、多官能(メタ)アクリレートとの相溶性に非常に優れ、また、アルカリ可溶性も良好であり、したがって、このような特徴が要求される各種用途に好適に用いることを目的に、無置換マレイミド由来の単量体構造単位、スチレン類由来の単量体構造単位、及び(メタ)アクリル酸由来の単量体構造を含有することを特徴とする、マレイミド系共重合体が提案されている(特許文献6)。
また、本発明の課題は、その感光性樹脂組成物から形成される、上記特性に優れた硬化膜及びマイクロレンズを提供することである。
すなわち、第1観点として、
(A)成分:下記式(1)で表される構造単位を有する共重合体、及び
(B)成分:感光剤を含有する感光性樹脂組成物。
第3観点として、前記(A)成分及び前記(B)成分に加え、さらに(C)成分である架橋剤を含有する第1観点又は第2観点に記載の感光性樹脂組成物。
第4観点として、第1観点乃至第3観点のうちいずれかに記載の感光性樹脂組成物から得られる硬化膜。
第5観点として、第1観点乃至第3観点のうちいずれかに記載の感光性樹脂組成物から作製されるマイクロレンズ。
また、本発明の感光性樹脂組成物から形成されたパターンも優れた耐熱性及び耐溶剤性等を有することが可能である。
さらに本発明の感光性樹脂組成物に含有される共重合体において、当該共重合体を合成する際に用いるマレイミドの種類を変えることで、当該組成物から屈折率が異なる様々なマイクロレンズを形成することができる。しかも、無置換マレイミド及び/又はN-置換マレイミドとアリルイソシアヌル酸とを、交互共重合体が得られるように共重合させる方が、アリルイソシアヌル酸同士を重合させる(収率10%以下)よりも、高い収率で目的の共重合体を得ることができる。
以上より、本発明の感光性樹脂組成物から形成される膜は、その形成工程、または配線等の周辺装置の形成工程において、高温での加熱処理が行われる場合にマイクロレンズが着色し、レンズ形状が変形する可能性を著しく減少できる。また、マイクロレンズ形成後に電極、配線形成工程が行われる場合には、有機溶剤によるマイクロレンズの変形、剥離といった問題も著しく減少できる。
したがって、本発明の感光性樹脂組成物は、マイクロレンズを形成する材料として好適である。
本発明の感光性樹脂組成物から溶剤を除いた固形分は通常、1乃至50質量%である。
本発明の(A)成分は、少なくとも下記式(1)で表される構造単位を有する共重合体である。
本発明の(B)成分である感光剤としては、感光成分として使用できる化合物であれば、特に限定されるものでないが、1,2-ナフトキノンジアジド化合物が好ましい。
前記1,2-ナフトキノンジアジド化合物としては、ヒドロキシル基を有する化合物であって、これらのヒドロキシル基のうち、10乃至100モル%、好ましくは20乃至95モル%が1,2-ナフトキノンジアジドスルホン酸エステル化された化合物を用いることができる。
本発明が(C)成分である架橋剤を含む場合、その架橋剤は、熱や酸の作用により、樹脂等の配合組成物や他の架橋剤分子との結合を形成する化合物である。当該架橋剤としては、例えば、多官能(メタ)アクリレート化合物、エポキシ化合物、ヒドロキシメチル基置換フェノール化合物、及びアルコキシアルキル化されたアミノ基を有する化合物等を挙げることができる。
これらの架橋剤は、単独で又は二種以上を組み合わせて用いることができる。
アルコキシアルキル化されたアミノ基を有する化合物のうち、下記式(7)で表されるヘキサメトキシメチルメラミンが好ましい。
当該界面活性剤としては、例えば、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンセチルエーテル、ポリオキシエチレンオレイルエーテル等のポリオキシエチレンアルキルエーテル類、ポリオキシエチレンオクチルフェノールエーテル、ポリオキシエチレンノニルフェノールエーテル等のポリオキシエチレンアルキルアリルエーテル類、ポリオキシエチレン・ポリオキシプロピレンブロックコポリマー類、ソルビタンモノラウレート、ソルビタンモノパルミテート、ソルビタンモノステアレート、ソルビタンモノオレエート、ソルビタントリオレエート、ソルビタントリステアレート等のソルビタン脂肪酸エステル類、ポリオキシエチレンソルビタンモノラウレート、ポリオキシエチレンソルビタンモノパルミテート、ポリオキシエチレンソルビタンモノステアレート、ポリオキシエチレンソルビタントリオレエート、ポリオキシエチレンソルビタントリステアレート等のポリオキシエチレンソルビタン脂肪酸エステル類等のノニオン系界面活性剤、エフトップ〔登録商標〕EF301、EF303、EF352(三菱マテリアル電子化成株式会社(旧(株)ジェムコ)製)、メガファック〔登録商標〕F171、F173、R30(DIC株式会社(旧大日本インキ化学工業(株))製)、フロラードFC430、FC431(住友スリーエム(株)製)、アサヒガード〔登録商標〕AG710、サーフロン〔登録商標〕S-382、SC101、SC102、SC103、SC104、SC105、SC106(旭硝子(株)製)等のフッ素系界面活性剤、オルガノシロキサンポリマーKP341(信越化学工業(株)製)等を挙げることができる。
さらに、これらの現像液に界面活性剤等を加えることもできる。
[下記合成例で得られたポリマーの重量平均分子量の測定]
装置:日本分光(株)製GPCシステム
カラム:Shodex〔登録商標〕KL-804L及び803L
カラムオーブン:40℃
流量:1ml/分
溶離液:テトラヒドロフラン
<合成例1>
モノアリルイソシアヌル酸33g、N-シクロヘキシルマレイミド15g、1,4-ジオキサン88gをフラスコに入れ、容器内を70℃にし、溶解させた。その後、2,2’-アゾビス(イソ酪酸)ジメチル2.4gと1,4-ジオキサン30gの溶液をそのフラスコ中に1時間かけて滴下した。その後8時間加熱還流した後、室温に戻し、得られた溶液をメタノールに加え、下記式(8)で表される構造単位を有するポリマー(共重合体)を、白色粉末として21g得た。反応生成物のGPC分析を行ったところ、標準ポリスチレン換算にて重量平均分子量は8,400であった。
モノアリルイソシアヌル酸13g、N-シクロヘキシルマレイミド15g、マレイミド5g、1,4-ジオキサン50gをフラスコに入れ、加熱還流させた。その後、2,2’-アゾビス(イソ酪酸)ジメチル1.6gと1,4-ジオキサン30gの溶液をそのフラスコ中に1時間かけて滴下した。その後10時間加熱還流した後、室温に戻し、得られた溶液をメタノールに加え、下記式(9)で表される構造単位を有するポリマー(共重合体)を、白色粉末として12g得た。反応生成物のGPC分析を行ったところ、標準ポリスチレン換算にて重量平均分子量は12,900であった。
マレイミド9.6g、N-シクロヘキシルマレイミド20g、2,2’-アゾビス(イソ酪酸)ジメチル1.8gを2-ブタノン47.1gに溶解させた後、その溶液を2-ブタノン78.5gが加熱還流されているフラスコ中に4時間かけて滴下した。滴下終了後、4時間反応させた。この反応溶液を室温に冷却後、ヘキサン/ジエチルエーテル混合溶媒に投入してポリマーを再沈殿させ、減圧乾燥して、下記式(10)で表される構造単位を有するポリマー(共重合体)を得た。反応生成物のGPC分析を行ったところ、標準ポリスチレン換算にて重量平均分子量は10,400であった。
合成例1,2で得られたポリマー3g、感光剤としてP-150(東洋合成工業(株)製)0.9g、架橋剤としてCYMEL(登録商標)303(日本サイテックインダストリーズ(株))0.95g、界面活性剤としてメガファック(登録商標)R-30(DIC(株)製)0.01gをプロピレングリコールモノメチルエーテル12.0g及びプロピレングリコールモノメチルエーテルアセテート12.0gに溶解させ溶液とした。その後、孔径0.10μmのポリエチレン製ミクロフィルターを用いてろ過して感光性樹脂組成物(溶液)を調製した。
合成例3で得られたポリマー3g、感光剤としてP-200(東洋合成工業(株)製)2.7g、架橋剤としてCYMEL(登録商標)303(日本サイテックインダストリーズ(株))2.7g、界面活性剤としてメガファック(登録商標)R-30(DIC(株)製)0.03gをプロピレングリコールモノメチルエーテル46.0g及び乳酸エチル19.7gに溶解させ溶液とした。その後、孔径0.10μmのポリエチレン製ミクロフィルターを用いてろ過して感光性樹脂組成物(溶液)を調製した。
ポリ(4-ビニルフェノール)(シグマアルドリッチジャパン(株)製、重量平均分子量20,000)9g、感光剤としてP-200(東洋合成工業(株)製)2.7g、架橋剤としてCYMEL(登録商標)303(日本サイテックインダストリーズ株式会社)2.7g、界面活性剤としてメガファック(登録商標)R-30(DIC(株)製)0.03gをプロピレングリコールモノメチルエーテル46.0g及び乳酸エチル19.7gに溶解させ溶液とした。その後、孔径0.10μmのポリエチレン製ミクロフィルターを用いてろ過して感光性樹脂組成物(溶液)を調製した。
実施例1、実施例2、参考例1及び比較例1で調製した感光性樹脂組成物をそれぞれ、石英基板上にスピンコーターにより塗布し、ホットプレート上において100℃で2分間プリベークし、膜厚1μmの感光性樹脂膜を形成した。その後、現像液(0.1質量%TMAH水溶液)に1分間浸漬し、水で20秒間リンスした。さらに500mJ/cm2のi線を全面照射し(フォトブリーチング)、ホットプレート上において200℃で5分間ポストベークした。そして、これらの膜をキセノンアークランプによる耐光性試験(JIS B7754)を24時間行い、当該膜を紫外線可視分光光度計UV-2550((株)島津製作所製)を用いて波長400nmの透過率(%)を測定した。評価の結果を下記表1に示す。
実施例1、実施例2、参考例1及び比較例1で調製した感光性樹脂組成物をそれぞれ、石英基板上にスピンコーターを用いて塗布し、ホットプレート上において100℃で2分間プリベークした。次いで、紫外線照射装置PLA-501(F)(キャノン(株)製)により、365nmにおける照射量が500mJ/cm2の紫外線を全面照射した(フォトブリーチング)。次いで、ホットプレート上において200℃で5分間ポストベークを行い、膜厚1μmの膜を形成した。これらの膜を紫外線可視分光光度計UV-2550((株)島津製作所製)を用いて波長400nmの透過率を測定した。さらにこの膜を260℃で3分間加熱した後、波長400nmの透過率(%)を測定した。評価の結果を下記表2に示す。
実施例1、実施例2、参考例1及び比較例1で調製した感光性樹脂組成物をそれぞれ、シリコンウェハー上にスピンコーターを用いて塗布し、ホットプレート上において100℃で2分間プリベークして、膜厚1μmの感光性樹脂膜を形成した。次いで、i線ステッパーNSR-2205i12D(NA=0.63)((株)ニコン製)を用いて、マスクを介して露光した。次いで、ホットプレート上において、100℃で2分間露光後ベーク(PEB)し、0.2質量%TMAH水溶液で1分間現像し、超純水で20秒間リンス、乾燥して2μm×2μmのドットパターンを形成した。さらに、前記i線ステッパーを用いて、500mJ/cm2のi線を全面照射し(フォトブリーチング)、ホットプレート上において200℃で5分間ポストベークを行った。さらに、これらの膜を260℃で3分間加熱した。走査型電子顕微鏡S-4800((株)日立ハイテクノロジーズ製)を用いて、現像・リンス・乾燥後、200℃でポストベーク後、及び260℃で加熱後のパターンの観察を行った。評価の結果を下記表3に示す。
実施例1、実施例2、参考例1及び比較例1で調製した感光性樹脂組成物をそれぞれ、シリコンウェハー上にスピンコーターを用いて塗布し、ホットプレート上において100℃で2分間プリベークした。次いで、紫外線照射装置PLA-501(F)(キャノン(株)製)により、365nmにおける照射量が500mJ/cm2の紫外線を全面照射した(フォトブリーチング)。次いで、ホットプレート上において200℃で5分間ポストベークを行い、膜厚1μmの膜を形成した。これらの膜を、アセトン、N-メチルピロリドン、2-プロパノール、及び2-ヘプタノンに、それぞれ23℃にて10分間浸漬した。いずれも、浸漬前後での膜厚変化が5%以下であることを確認した。
実施例1、実施例2、及び参考例1で調製した感光性樹脂組成物をそれぞれ、シリコンウェハー上にスピンコーターを用いて塗布し、ホットプレート上において100℃で2分間プリベークして、膜厚1μmの感光性樹脂膜を形成した。次いで、ホットプレート上において、100℃で2分間ベークし、0.2質量%TMAH水溶液で1分間現像し、超純水で20秒間リンス、乾燥した。さらに、前記i線ステッパーを用いて、500mJ/cm2のi線を全面照射し(フォトブリーチング)、ホットプレート上において200℃で5分間ポストベークを行った。得られたウェハー切片に対して、恒温恒湿試験(85℃、85%)を1週間行った。目視にて、これらウェハー上の膜にクラックが見られるかを確認した。クラックがない場合を「○」、クラックが発生した場合を「×」として評価を行った。評価の結果を下記表4に示す。
Claims (5)
- (A)成分:下記式(1)で表される構造単位、及び下記式(2)で表される少なくとも1種の構造単位を有する共重合体、並びに
(B)成分:感光剤を含有する感光性樹脂組成物。
- 前記共重合体の重量平均分子量が1000乃至30000である、請求項1に記載の感光性樹脂組成物。
- さらに(C)成分である架橋剤を含有する請求項1又は請求項2に記載の感光性樹脂組成物。
- 請求項1乃至請求項3のいずれか一項に記載の感光性樹脂組成物から得られる硬化膜。
- 請求項1乃至請求項3のいずれか一項に記載の感光性樹脂組成物から作製されるマイクロレンズ。
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US13/395,336 US8674043B2 (en) | 2009-09-14 | 2010-08-30 | Photosensitive resin composition containing copolymer |
JP2011530808A JP5574124B2 (ja) | 2009-09-14 | 2010-08-30 | 共重合体を含有する感光性樹脂組成物 |
EP10815285.1A EP2479612B1 (en) | 2009-09-14 | 2010-08-30 | Photosensitive resin composition containing copolymer |
CN2010800380246A CN102483570B (zh) | 2009-09-14 | 2010-08-30 | 含有共聚物的感光性树脂组合物以及固化膜、微透镜 |
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JP6764134B2 (ja) * | 2016-08-30 | 2020-09-30 | 日産化学株式会社 | 感光性接着剤組成物 |
JP7127635B2 (ja) * | 2017-02-21 | 2022-08-30 | 日本ゼオン株式会社 | 感光性樹脂組成物 |
CN110407978B (zh) * | 2019-08-31 | 2021-04-13 | 贵州大学 | 一种可辐照交联n-(氟基苯基)马来酰亚胺共聚组合物及其尼龙6复合材料制备方法 |
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- 2010-08-30 WO PCT/JP2010/064717 patent/WO2011030688A1/ja active Application Filing
- 2010-08-30 US US13/395,336 patent/US8674043B2/en not_active Expired - Fee Related
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JP5574124B2 (ja) | 2014-08-20 |
US8674043B2 (en) | 2014-03-18 |
EP2479612A4 (en) | 2015-10-14 |
KR20120074286A (ko) | 2012-07-05 |
KR101626493B1 (ko) | 2016-06-01 |
EP2479612A1 (en) | 2012-07-25 |
TW201124796A (en) | 2011-07-16 |
EP2479612B1 (en) | 2016-12-07 |
JPWO2011030688A1 (ja) | 2013-02-07 |
CN102483570B (zh) | 2013-10-23 |
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