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WO2008007764A1 - Composition de résine photosensible, produit stratifié en cette composition, objet durci en cette composition, et procédé de traçage de motif à partir de cette composition - Google Patents

Composition de résine photosensible, produit stratifié en cette composition, objet durci en cette composition, et procédé de traçage de motif à partir de cette composition Download PDF

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Publication number
WO2008007764A1
WO2008007764A1 PCT/JP2007/063956 JP2007063956W WO2008007764A1 WO 2008007764 A1 WO2008007764 A1 WO 2008007764A1 JP 2007063956 W JP2007063956 W JP 2007063956W WO 2008007764 A1 WO2008007764 A1 WO 2008007764A1
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WIPO (PCT)
Prior art keywords
resin composition
photosensitive resin
pattern
composition according
composition
Prior art date
Application number
PCT/JP2007/063956
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English (en)
Japanese (ja)
Inventor
Nao Honda
Naoko Imaizumi
Donald Johnson
Original Assignee
Nippon Kayaku Kabushiki Kaisha
Microchem Corp.
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Publication date
Application filed by Nippon Kayaku Kabushiki Kaisha, Microchem Corp. filed Critical Nippon Kayaku Kabushiki Kaisha
Priority to JP2008524851A priority Critical patent/JP4913142B2/ja
Publication of WO2008007764A1 publication Critical patent/WO2008007764A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates 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
    • C08G59/18—Macromolecules 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
    • C08G59/68—Macromolecules 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
    • C08G59/687—Macromolecules 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 containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates 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
    • C08G59/18—Macromolecules 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
    • C08G59/20—Macromolecules 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 epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/3218—Carbocyclic compounds
    • 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
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0385—Macromolecular compounds which are rendered insoluble or differentially wettable using epoxidised novolak resin

Definitions

  • Photosensitive resin composition laminate thereof, cured product thereof, and pattern formation method using the composition (3)
  • the present invention is capable of forming a high-resolution, high-aspect-ratio pattern and having high sensitivity, a photosensitive resin composition, a laminate thereof, a cured product thereof, and pattern formation using the composition Concerning the method.
  • Photolithographic resists have recently been widely used in semiconductor and MEMS (microelectron force-cal system) applications.
  • photolithography is performed by patterning exposure on a substrate, and then it is achieved by selectively removing an exposed area or a non-exposed area by developing with a developer.
  • Resist that can be photolithographically processed is either positive or negative type, and those that dissolve in the developer upon exposure are positive types and those that become insoluble are negative types.
  • High-aspect ratios are required for leading-edge electoric package applications, while in MEMS applications, the ability to form a uniform spin-coating film, a straight shape with a thickness of 100 m or more, and high-aspect ratio photo Lithographic resist is required.
  • the aspect ratio is an important characteristic expressed by resist film thickness Z pattern line width and showing the performance of photolithography.
  • the top force of the film due to light absorption The force that reduces the irradiation intensity toward the bottom Such light absorption is too high.
  • the bottom of the resist is underexposed compared to the top, so the side wall shape becomes a slope shape or a distorted shape.
  • Negative type chemically amplified thick film photolithography processable yarns and composites are known to have very low light absorption in the 350-450 nm wavelength region, and the composition of this resist is multifunctional.
  • Photopower thione polymerization initiators such as bisphenol A novolac epoxy resin (Resolution 'Performance' EPON SU-8 Resin made by Pukko Daku, CYRACURE UVI-6974 made by Dow Chemical) Aromatic sulfone-hexafluoroantimonate in propylene carbonate solution).
  • This photoresist composition is spin-coated or curtain-coated on various substrates, then the solvent is volatilized by baking to form a solid photoresist layer having a thickness of 100 m or more, contact exposure, Photolithography is performed by irradiating near ultraviolet light through a photomask using various exposure methods such as proximity exposure and projection exposure. Then, it is immersed in a developing solution, the non-exposed area is dissolved, and a high-resolution photomask negative image is formed on the substrate.
  • EPON SU-8 resin is a low molecular weight epoxy oligomer having superior characteristics in photolithography processing with a high aspect ratio in a thick film. Its superior features are (i) high epoxy functionality, (ii) high degree of branching, (iii) high transmittance at 350-450 nm, and (iv) low molecular weight necessary and sufficient to form solids. is there. High number of epoxy functional groups and high degree of branching cause sufficient cross-linking under strong acid catalyst, and high transmittance is uniformly irradiated through the thick film, forming a pattern with an aspect ratio of 10 or more with a thick film of 100 m or more. Has resist performance.
  • the selection of a resin having a high number of epoxy functional groups and a high degree of branching is an important item for forming a high aspect ratio structure with straight sidewalls.
  • the selection of a low molecular weight resin allows a solid layer of thick film photoresist to be performed with a minimum number of coating steps to form a solid layer on the substrate.
  • Light-power thione polymerization initiators based on sulfo-um salt or ododonium salt are well known, and useful light-power thione polymerization initiators having appropriate absorbance have been disclosed.
  • p-Phenol-lentioether is contained (Patent Documents 1 and 2).
  • 2 alkyl 9, 10 dimethoxyanthracene or other anthracene, naphthalene It is also possible to arrange a sensitizer such as a ril or pyrilil compound, and it can be introduced into a photopower thione polymerization initiator (Patent Document 3).
  • Negative resists based on the disclosed compounds as described above, suitable for spin coating, are sold by MicroChem and are used commercially, especially in MEMS device components.
  • the “SU-8 Series” provided by Micro-Chem is spin-coated at 1000-3000 rpm to form a film with a thickness of 30-100 ⁇ m, and then exposed to 100 m or more after imaging.
  • a pattern with an aspect ratio of 10 or more can be formed.
  • Patent Document 4 An application such as a dry film resist coated on a substrate such as a polyester film is also disclosed (Patent Document 4).
  • a photoimageable cationic polymerizable flame retardant composition suitable for use as a solder mask has been disclosed (Patent Documents 5, 6, and 7).
  • This bisphenol A and the condensation product of Epiku port Ruhidorin consists of a mixture containing 10 to 80 wt 0/0, bisphenol A climb Kkuepokishi ⁇ 20 to 90 weight 0/0, epoxidized tetrabromobisphenol bisphenol A
  • a compositional power containing 35 to 50% by weight and 0.1 to 15% by weight of a light power thione polymerization initiator is also obtained.
  • a photopolymerizable compound based on a hydroxyl group-containing additive, a light-power thione polymerization initiator, and an epoxy resin having a functional group number of 1.5 or more is also disclosed.
  • Hydroxyl-containing additives have been reported to increase flexibility and reduce stress in thick films of 100 ⁇ m or more (Patent Document 8).
  • Patent Document 9 discloses a method of producing a hard epoxy resin system in an EB curable application.
  • the main improvement here is the brittleness of the radiation-cured epoxy resin.
  • Many structural and consumer resins epoxy resins
  • a wide range of tough materials including SU-8 resin is disclosed herein.
  • the effectiveness of the invention described in Patent Document 9 is shown by fracture toughness and flexural modulus.
  • the tough material described in Patent Document 9 also has various thermoplastics, hydroxyl group-containing thermoplastic oligomers, epoxy-containing thermoplastic oligomers, reactive flexible materials, elastomers, rubbers, and mixtures thereof.
  • composition described in Patent Document 9 is a composition applied to a film imaged by non-patterned EB irradiation. Therefore, the characteristics of these compositions do not serve as a reference for photoimaging applications when they are subjected to patterning exposure by UV, X-ray and EB irradiation.
  • Patent Document 10 Many proposals have been made regarding a photoresist composition containing an epoxy (Patent Document 10).
  • the composition here needs to have a sufficient transmittance for exposure irradiation that photodegrades the photoinitiator through the film thickness.
  • the photoresist composition must have appropriate physical and chemical properties such as solder resistance or ink resistance or strength, significant deterioration, and poor adhesion to withstand various applications. Don't be. If this photoresist composition is used for other applications, such as a photoresist for etching, other properties are required. However, there are currently no specific epoxy resins that satisfy all of the various requirements.
  • Patent Document 1 USP5502083
  • Patent Document 2 USP6368769
  • Patent Document 3 USP5102772
  • Patent Document 4 USP4882245
  • Patent Document 5 USP5026624
  • Patent Document 6 USP5278010
  • Patent Document 7 USP5304457
  • Patent Document 8 USP4256828
  • Patent Document 9 USP5726216
  • Patent Document 10 USP5264325
  • the present invention has been made in view of the above-described conventional circumstances, and the problem is that a photosensitive resin composition that can form a pattern with high resolution and high aspect ratio and has high sensitivity. Is to provide.
  • the present inventors have intensively conducted experiments and examinations regarding high sensitivity and high resolution in a photosensitive resin composition, and as a result, specific polyfunctional epoxy resin. And a specific photoactive thione polymerization initiator are combined to prepare a photosensitive resin composition, and using this photosensitive resin composition, a resin pattern is formed.
  • the present inventors have found that a greaves pattern with a high ratio can be formed. That is, the present invention relates to (1) a photothion polymerization initiator (A) which is sulfo-umtris (pentafluoroethyl) trifluorophosphate and a polyfunctional epoxy resin represented by the following general formula (1).
  • Fat (B) is sulfo-umtris (pentafluoroethyl) trifluorophosphate
  • the epoxy group in the formula may be a bisphenol A type epoxy resin or a polymer polymerized with a bisphenol A novolak type epoxy resin.
  • N represents an average value and is an integer of 0 to 30.
  • a photosensitive resin composition comprising
  • the solid content concentration is 5 to 95 times.
  • a photosensitive resin composition laminate in which the photosensitive resin composition according to any one of (1) to (4) is sandwiched between substrates,
  • a cured product comprising the photosensitive resin composition according to any one of (1) to (4) above.
  • a photosensitive resin composition layer obtained by coating the photosensitive resin composition according to any one of the above (1) to (4) on a desired support is dried, and then predetermined.
  • No pattern forming method comprising: exposing the pattern to a beta after the exposure, developing the resin composition layer, and heat-treating the obtained resin pattern to obtain a cured resin pattern having a predetermined shape.
  • the photosensitive resin composition of the present invention comprises a photoactive thione polymerization initiator (A) that is sulfoyulium tris (pentafluoroethyl) trifluorophosphate and a multi-function represented by the general formula (1). It is characterized by containing epoxy resin (B), and can form a high-sensitivity and high aspect ratio resin pattern. Furthermore, it is possible to impart a characteristic that can be exhibited over a long period of time without deteriorating the ability to form the above-mentioned grease pattern.
  • A photoactive thione polymerization initiator
  • B epoxy resin
  • the photopower thione polymerization initiator in the present invention generates cations upon irradiation with excimer lasers such as ultraviolet rays, far ultraviolet rays, KrF and ArF, X-rays and electron beams, and the cations are generated. It is a compound that can be a polymerization initiator.
  • the light-power thione polymerization initiator (A) is sulfoyulium tris (pentafluoroethyl) trifluorophosphate.
  • Examples of the sulfone of the photopower thione polymerization initiator include triphenyl sulfone, tri-p-tolyl sulfone, tri-o-tolyl sulfone, and tris (4-methoxyphenol) sulphonol.
  • triphenyl sulfone and 4 (phenylthio) phenyl disulfol sulfome are more preferred, represented by the following formula (2): The most preferred is 4 (Fuerthio) Fuel Disulfosulfum (A-1) as shown!
  • the bisphenol A novolak type polyfunctional epoxy resin (B) in the present invention is a bisphenol A novolak type polyfunctional epoxy resin containing a sufficient amount of epoxy groups in one molecule to form a film pattern. Any epoxy resin may be used as long as it is an epoxy resin.
  • Specific examples of bisphenol A novolac-type polyfunctional epoxy resin include EPON SU-8 (Resolution 'Performance' Products), Epicoat 157S70, Epicoat 157S65 (Japan Epoxy Resin), YD-128 (Tokyo) Chemicals), Epiclone N-885, Epiclone N-865, Epiclone 2055 (Dainippon Ink Chemical Co., Ltd.).
  • the epoxy equivalent of these bisphenol A novolac type polyfunctional epoxy resins is preferably 150 to 400, and the epoxy equivalent is smaller than this range. This is not preferable. On the other hand, if it is larger than this range, the crosslinking density becomes small, and the strength of the cured film is not preferred because the chemical resistance, heat resistance and crack resistance are poor.
  • n in the general formula (1) represents a repeating unit, and when n is smaller than this range, 3 to 30 is generally preferable, it is in a liquid state and has poor curability and cannot be used. On the other hand, if it is larger than this range, developability and transferability are deteriorated.
  • n is a value obtained by dividing the number average molecular weight measured by gel permeation chromatography (GPC) by the molecular weight of the repeating unit.
  • GPC gel permeation chromatography
  • n is smaller than this range, which is preferably 0 to 30, it is generally liquid and has poor curing properties and cannot be used. On the other hand, if it is larger than this range, the developability and transferability are poor.
  • EPON SU-8 Resolution “Performance” products
  • Nyapicoat 157S70 Japan Epoxy Resins
  • the polyfunctional epoxy resin (B) is represented by the following general formula (1).
  • the epoxy group in the formula may be a bisphenol A type epoxy resin or a polymer polymerized with a bisphenol A nopolak type epoxy resin.
  • N represents an average value and is an integer of 0 to 30. is there. )
  • the soft spot of the polyfunctional epoxy resin (B) is low, As soon as scratching occurs, it is not preferable because it softens at room temperature when used as a dry film resist.
  • the soft point of the polyfunctional epoxy resin (B) is high, the dry film resist is preferably softened when laminating the substrate to the substrate ⁇ , because the bonding property to the substrate becomes worse. Absent.
  • the preferred softening point of the polyfunctional epoxy resin is 40 to 120 ° C, more preferably 50 to 100 ° C.
  • the use of the light-powered thione polymerization initiator (A) and the bisphenol A novolac type polyfunctional epoxy resin (B) is preferred, preferably 0.1 to 99.9 to 15:85. More preferably, ⁇ 0.5: 99. 5: LO: 90.
  • a miscible reactive epoxy monomer (C) may be further added to improve the pattern performance.
  • a glycidyl ether compound can be used.
  • the reactive epoxy monomer (C) component is used for the purpose of improving the reactivity of the resist and the physical properties of the cured film.
  • the reactive epoxy monomer component is mostly liquid and is 20% by weight when the component is liquid. If it is added in excess of%, the film after solvent removal tends to be sticky and mask sticking tends to occur. From this point, when the monomer component is blended, the blending ratio is such that the total of the component (A), the component (B) and the component (C) is the solid content of the resist. 1 to LO weight% is preferred with respect to the solid content, especially 2 to 7 weight% is preferred.
  • a solvent (D) can be used to lower the viscosity of the photosensitive resin composition of the present invention and improve the coating properties.
  • the solvent (D) any commonly used organic solvent that can dissolve each component can be used. Examples of such organic solvents include ketones such as acetone, ethyl methyl ketone, and cyclohexanone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, dipropylene glycol dimethyl ether, and dipropylene glycol jetyl ether.
  • Glycol ethers ethyl acetate, butyl acetate, butylcetosolve acetate, carbitol acetate, propylene glycol monomethyl ether acetate, esters such as butyrolatataton, alcohols such as methanol, ethanol, ceresolve, methyl ceresolve, octane, Examples thereof include aliphatic hydrocarbons such as decane, organic solvents such as petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha.
  • solvents may be used alone or in combination of two or more.
  • the solvent component is added for the purpose of adjusting the film thickness and applicability when applied to the base material, and in order to maintain the solubility of the main component, the volatility of the component, and the liquid viscosity of the composition properly. Further, it is preferably 5 to 95% by weight based on the photosensitive resin composition, particularly preferably 10 to 90% by weight.
  • a miscible adhesion-imparting agent may be used for the purpose of further improving the adhesion of the composition to the substrate.
  • a coupling agent such as a coupling agent silane coupling agent or a titanium coupling agent can be used, and a silane coupling agent is preferable.
  • silane coupling agent examples include 3-chloropropyltrimethoxysilane, butyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyl'tris (2-methoxyethoxy) silane, and 3-methacryloxypropinoretrie.
  • adhesion promoters can be used alone or in combination of two or more. Since the adhesion-imparting agent is non-reactive with the main component, components other than those that act at the substrate interface are present as residual components after curing, and if used in large amounts, adverse effects such as deterioration of physical properties will occur. Depending on the base material, it can be used within a range that does not adversely affect the effect even in a small amount, and the use ratio is preferably 15% by weight or less based on the photosensitive resin composition. Particularly preferred is 5% by weight or less.
  • a sensitizer may be further used to absorb ultraviolet light and to supply the absorbed light energy to the photothion polymerization initiator.
  • anthracene compounds having an alkoxyl group at the 9th and 10th positions (9, 10 dialkoxyanthracene derivatives) are preferable.
  • the alkoxyl group include C1-C4 alkoxyl groups such as a methoxy group, an ethoxy group, and a propoxy group.
  • the 9, 10 dialkoxyanthracene derivative may further have a substituent.
  • substituents examples include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, C1-C4 alkyl group such as methyl group, ethyl group and propyl group, sulfonic acid alkyl ester group, and carboxylic acid alkyl ester group.
  • halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom
  • C1-C4 alkyl group such as methyl group, ethyl group and propyl group
  • alkyl in the sulfonic acid alkyl ester group and the carboxylic acid alkyl ester examples include C1-C4 alkyl such as methyl, ethyl and propyl.
  • the substitution position of these substituents is preferably the 2-position.
  • Examples of the 9, 10 dialkoxyanthracene derivatives include 9, 10 dimethoxyanthracene, 9, 10 jetoxyanthracene, 9,10 dipropoxyanthracene, 9,10 dimethoxy-2-ethylanthracene, 9,10 diethoxy-2 Ethylanthracene, 9,10 Dipropoxy-2 Ethylanthracene, 9,10 Dimethoxy-2 chloroanthracene, 9,10 Dimethoxyanthracene 2-sulfonic acid methyl ester, 9, 10 Jetxanthracene mono-2-sulfonic acid methyl ester, 9, 10 Dimethoxyanthracene 2-carboxylic acid methyl ester.
  • the sensitizer component is effective in a small amount, the use ratio is particularly preferably 3% by weight or less based on the component (A) of the light power thione polymerization initiator. Is less than 1% by weight.
  • trismethoxyaluminum when it is necessary to reduce the adverse effects of the ions derived from the light-powered thione polymerization initiator (A), trismethoxyaluminum, trisethoxyloxyaluminum, trisisopropoxyaluminum, Alkoxyaluminum such as propoxydiethoxyaluminum and trisbutoxyaluminum, phenoxyaluminum such as trisphenoxyaluminum and trisparamethylphenoxyaluminum, trisacetoxyaluminum, tristearate aluminum and trisbutyrato Aluminum, Trisp ported pionato aluminum, Triacetyl acetonato aluminum, Tristrifluoroacetyl acetonate aluminum, Tri cetyl acetoacetate aluminum, Dicetyl acetonate dipivaloylmethanato These components, which may contain ion catchers such as organoaluminum compounds such as aluminum and diisoprop
  • thermoplastic rosin examples include polyethersulfone, polystyrene, and polycarbonate.
  • the colorant examples include phthalocyanine blue, phthalocyanine green, iodine 'green, crystal violet, titanium oxide, carbon black, and naphthalene black.
  • the thickener examples include olven, benton, and montmorillonite.
  • the antifoaming agent examples include antifoaming agents such as silicone, fluorine, and polymer.
  • barium sulfate, barium titanate, silicon oxide, amorphous silica, talc, clay, magnesium carbonate, calcium carbonate, acid aluminum, hydroxide aluminum aluminum, mica powder Inorganic fillers such as the above can be used, and the blending ratio is 0 to 60% by weight in the composition.
  • the photosensitive resin composition of the present invention is preferably blended in the proportions shown in Table 1 below, if necessary.
  • the adhesion-imparting agent, sensitizer, ion catcher, thermoplastic resin, colorant, thickener, antifoaming agent, leveling agent and inorganic filler may be added.
  • a disperser such as a dissolver, a homogenizer, or a three-roll mill if necessary.
  • filter with a mesh or membrane filter is also be used.
  • the photosensitive resin composition of the present invention is preferably used in liquid form.
  • it is applied onto a substrate such as silicon wafer or glass using a spin coater or the like at a thickness of 0.1 to LOO of 0 ⁇ m, and 60 to 130 Then, heat treatment is performed for about 5 to 60 minutes to remove the solvent and form a photosensitive resin composition layer.
  • a mask having a predetermined pattern is placed and irradiated with ultraviolet rays, and at 50 to 130 ° C, 1 to After heat treatment for about 50 minutes, the unexposed part is developed with a developer at room temperature to 50 ° C for about 1 to 180 minutes to form a pattern, and then heated at 130 to 200 ° C.
  • a permanent protective film that satisfies various properties can be obtained.
  • the developer for example, an organic solvent such as ⁇ -petit-mouth rataton, triethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, or a mixed solution of the organic solvent and water can be used.
  • a paddle type, spray type, shower type, or other developing device may be used, and ultrasonic irradiation may be performed as necessary.
  • the resin composition of the present invention is obtained by applying the yarn composition on a base film using a roll coater, die coater, knife coater, bar coater, gravure coater, etc., and then 45 to 100 ° C. It can be made into a dry film resist by drying in a drying oven set to, removing a predetermined amount of solvent, and laminating a cover film or the like as necessary. At this time, the thickness of the resist on the base film is adjusted to 2 to: LOO / zm.
  • base film and cover film include polyester, polypropylene, and polyethylene. Films such as TAC and polyimide are used.
  • these films may be processed with a release agent such as a silicon release treatment agent or a non-silicon release treatment agent.
  • a release agent such as a silicon release treatment agent or a non-silicon release treatment agent.
  • the cover film is peeled off, transferred to a substrate at a temperature of 40 ° C. to 100 ° C. and a pressure of 0.05 to 2 MPa by a hand roll, a laminator, etc.
  • Exposure, post-exposure beta, development, and heat treatment may be carried out in the same manner as the photosensitive resin composition described in 1.
  • the photosensitive resin composition is supplied as a film as described above, the steps of coating on the support and drying can be omitted, and the photosensitive resin of the present invention can be more simply used. Pattern formation using an oil composition is possible.
  • the cured product of the resin composition of the present invention obtained by the above method is used, for example, as a permanent resist film, for example, for MEMS parts such as an inkjet recording head.
  • This photosensitive resin composition was coated on a silicon wafer with a spin coater and dried to obtain a photosensitive resin composition layer having a thickness of 80 ⁇ m.
  • This photosensitive resin composition layer was prebetated on a hot plate at 65 ° C for 5 minutes and at 95 ° C for 20 minutes. After that, pattern exposure (soft contact, i-line) is performed using an i-line exposure system (mask aligner: manufactured by Usio Electric Co., Ltd.), and after exposure, beta (PEB) is performed at 95 ° C for 6 minutes. Then, development processing was performed at 23 ° C. for 7 minutes by an immersion method using propylene glycol monomethyl ether acetate to obtain a cured resin pattern on the substrate. [0053] (Evaluation of photosensitive resin composition)
  • Optimum exposure amount exposure amount with the best mask transfer accuracy
  • Photosensitive resin composition 100 parts by weight of bisphenol A novolac type polyfunctional epoxy resin (trade name: EPON SU-8 Resolution Solution “Products”) and photo-thion polymerization initiator (trade name: CPI—210S Sanpapro) 2.
  • a photosensitive composition was obtained by mixing 3 parts by weight, 4 parts by weight of a reactive epoxy monomer (trade name: ED506 manufactured by Asahi Denka Kogyo Co., Ltd.), and 40 parts by weight of MEK.
  • This photosensitive resin composition is uniformly applied onto a polypropylene (PP) film (base film, manufactured by Toray Industries, Inc.) having a film thickness of 60 ⁇ m, and heated at 65 ° C for 10 minutes and 80 ° C using a hot air convection dryer. After drying at C for 15 minutes, a 60 ⁇ m-thick PP film (cover film) was laminated on the exposed surface to form a photosensitive resin composition laminate having a thickness of 40 m.
  • PP polypropylene
  • the cover film of the photosensitive resin composition laminate was peeled off, laminated on a silicon wafer at a roll temperature of 70 ° C, an air pressure of 0.2 MPa, and a speed of 0.5 mZmin, and this was repeated once.
  • a photosensitive resin composition layer having a thickness of 80 m was obtained.
  • the photosensitive resin composition layer was subjected to pattern exposure (soft contact, i-line) using an i-line exposure apparatus (mask aligner: manufactured by Usio Electric Co., Ltd.). Thereafter, PEB was performed for 4 minutes at 95 ° C using a hot plate, and development processing was performed for 4 minutes at 23 ° C by immersion using PGMEA to obtain a cured resin pattern on the substrate.
  • Optimum exposure 300miZcm 2 Aspect ratio 5.5 and good results were obtained.
  • the photosensitive resin composition useful in the present invention is useful for forming a resin pattern having a high aspect profile, and is particularly dimensionally stable in fine-sized electronic devices. Suitable for high-performance resin molding.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials For Photolithography (AREA)
  • Epoxy Resins (AREA)

Abstract

La présente invention concerne une composition de résine photosensible qui permet de tracer un motif à haute résolution et à fort rapport longueur-largeur et présentant une sensibilité élevée. La composition de résine photosensible comprend un initiateur de photopolymérisation cationique (A) qui est un tris(pentafluoroéthyl)trifluorophosphate de sulfonium et une résine époxy polyfonctionnelle (B).
PCT/JP2007/063956 2006-07-14 2007-07-13 Composition de résine photosensible, produit stratifié en cette composition, objet durci en cette composition, et procédé de traçage de motif à partir de cette composition WO2008007764A1 (fr)

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US7977030B2 (en) * 2007-06-15 2011-07-12 Tokyo Ohka Kogyo Co., Ltd. Photosensitive resin composition, photosensitive resin laminate, and method for pattern forming
KR20140117512A (ko) 2012-01-19 2014-10-07 닛산 가가쿠 고교 가부시키 가이샤 네가티브형 감광성 수지 조성물
KR20150067236A (ko) 2012-10-02 2015-06-17 닛산 가가쿠 고교 가부시키 가이샤 네가티브형 감광성 수지조성물
KR20160075566A (ko) 2013-10-21 2016-06-29 닛산 가가쿠 고교 가부시키 가이샤 네가티브형 감광성 수지 조성물
JP2018036533A (ja) * 2016-08-31 2018-03-08 東京応化工業株式会社 ネガ型感光性樹脂組成物、感光性レジストフィルム、パターン形成方法、硬化膜、硬化膜の製造方法
WO2021059843A1 (fr) 2019-09-24 2021-04-01 東レ株式会社 Composition de résine, film de composition de résine, film durci, structure creuse utilisant ce dernier et dispositif semi-conducteur
WO2022202486A1 (fr) 2021-03-23 2022-09-29 東レ株式会社 Composition de résine photosensible négative, film de composition de résine photosensible négative, produit durci, procédé de préparation de produit durci, structure creuse et composant électronique
WO2023162718A1 (fr) 2022-02-24 2023-08-31 東レ株式会社 Composition de résine, film de revêtement de composition de résine, film de composition de résine, film durci et dispositif à semi-conducteur utilisant ces produits

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JP2005055865A (ja) * 2003-07-24 2005-03-03 Tokyo Ohka Kogyo Co Ltd 感光性樹脂組成物および該組成物を用いたパターン形成方法
WO2005079330A2 (fr) * 2004-02-13 2005-09-01 Microchem Corp. Composition de resist permanente, produit durci a partir de cette composition, et utilisation correspondante
WO2005116038A1 (fr) * 2004-05-28 2005-12-08 San-Apro Limited Nouveau sel d'onium et de complexe de métal de transition d'un acide alkylfluorophosphorique fluoré

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WO2005093514A1 (fr) * 2004-03-26 2005-10-06 Tokyo Ohka Kogyo Co., Ltd. Composition à base de résine photosensible et procédé de formation d'un modèle avec la composition

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JP2005055865A (ja) * 2003-07-24 2005-03-03 Tokyo Ohka Kogyo Co Ltd 感光性樹脂組成物および該組成物を用いたパターン形成方法
WO2005079330A2 (fr) * 2004-02-13 2005-09-01 Microchem Corp. Composition de resist permanente, produit durci a partir de cette composition, et utilisation correspondante
WO2005116038A1 (fr) * 2004-05-28 2005-12-08 San-Apro Limited Nouveau sel d'onium et de complexe de métal de transition d'un acide alkylfluorophosphorique fluoré

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7977030B2 (en) * 2007-06-15 2011-07-12 Tokyo Ohka Kogyo Co., Ltd. Photosensitive resin composition, photosensitive resin laminate, and method for pattern forming
KR20140117512A (ko) 2012-01-19 2014-10-07 닛산 가가쿠 고교 가부시키 가이샤 네가티브형 감광성 수지 조성물
KR20150067236A (ko) 2012-10-02 2015-06-17 닛산 가가쿠 고교 가부시키 가이샤 네가티브형 감광성 수지조성물
KR20210106011A (ko) 2013-10-21 2021-08-27 닛산 가가쿠 가부시키가이샤 네가티브형 감광성 수지 조성물
KR20160075566A (ko) 2013-10-21 2016-06-29 닛산 가가쿠 고교 가부시키 가이샤 네가티브형 감광성 수지 조성물
JP7050411B2 (ja) 2016-08-31 2022-04-08 東京応化工業株式会社 ネガ型感光性樹脂組成物、感光性レジストフィルム、パターン形成方法、硬化膜、硬化膜の製造方法
KR20190045178A (ko) * 2016-08-31 2019-05-02 도오꾜오까고오교 가부시끼가이샤 네거티브형 감광성 수지 조성물, 감광성 레지스트 필름, 패턴 형성 방법, 경화막, 경화막의 제조 방법
JP2018036533A (ja) * 2016-08-31 2018-03-08 東京応化工業株式会社 ネガ型感光性樹脂組成物、感光性レジストフィルム、パターン形成方法、硬化膜、硬化膜の製造方法
US11415888B2 (en) 2016-08-31 2022-08-16 Tokyo Ohka Kogyo Co., Ltd. Negative type photosensitive resin composition, photosensitive resist film, pattern forming method, cured film, and method of producing cured film
KR102466040B1 (ko) * 2016-08-31 2022-11-10 도오꾜오까고오교 가부시끼가이샤 네거티브형 감광성 수지 조성물, 감광성 레지스트 필름, 패턴 형성 방법, 경화막, 경화막의 제조 방법
WO2021059843A1 (fr) 2019-09-24 2021-04-01 東レ株式会社 Composition de résine, film de composition de résine, film durci, structure creuse utilisant ce dernier et dispositif semi-conducteur
KR20220065788A (ko) 2019-09-24 2022-05-20 도레이 카부시키가이샤 수지 조성물, 수지 조성물 필름, 경화막, 이들을 사용한 중공 구조체 및 반도체 장치
WO2022202486A1 (fr) 2021-03-23 2022-09-29 東レ株式会社 Composition de résine photosensible négative, film de composition de résine photosensible négative, produit durci, procédé de préparation de produit durci, structure creuse et composant électronique
KR20230160231A (ko) 2021-03-23 2023-11-23 도레이 카부시키가이샤 네거티브형 감광성 수지 조성물, 네거티브형 감광성수지 조성물 필름, 경화물, 경화물의 제조 방법, 중공 구조체, 및 전자 부품
WO2023162718A1 (fr) 2022-02-24 2023-08-31 東レ株式会社 Composition de résine, film de revêtement de composition de résine, film de composition de résine, film durci et dispositif à semi-conducteur utilisant ces produits
KR20240155861A (ko) 2022-02-24 2024-10-29 도레이 카부시키가이샤 수지 조성물, 수지 조성물 피막, 수지 조성물 필름, 경화막 및 이들을 사용한 반도체 장치

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JP4913142B2 (ja) 2012-04-11
TW200813625A (en) 2008-03-16
TWI425311B (zh) 2014-02-01
JPWO2008007764A1 (ja) 2009-12-10

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