Classifications

• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/20—Filters
  • G02B5/22—Absorbing filters
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
• • 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
• • 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
• • 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
  • G03F7/075—Silicon-containing compounds
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
  • H05B33/00—Electroluminescent light sources
  • H05B33/12—Light sources with substantially two-dimensional [2D] radiating surfaces
  • H05B33/22—Light sources with substantially two-dimensional [2D] radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers

Definitions

• the present invention relates to a positive photosensitive resin composition having excellent pattern processability, being curable at a low temperature, and having a cured film having excellent chemical resistance, the cured film thereof, and an optical device including the cured film.
• Patent Documents 1 to 3 describe a photosolubilized positive photosensitive material containing a siloxane polymer and a quinonediazide compound. These materials have achieved high resolution capable of forming patterns with dimensions of 5 ⁇ m or less. Then, it is cured by heat treatment at 200 to 230 ° C., and the result shows solvent resistance (chemical resistance). Further, Patent Document 4 and Patent Document 5 describe a photocurable negative photosensitive material containing an alkali-soluble polymer, a polymerization initiator, and other additives. The material described in Patent Document 4 has achieved a resolution of 10 ⁇ m, is cured by heating at 120 ° C., and exhibits chemical resistance. Further, the material described in Patent Document 5 is cured even at a lower temperature of 100 ° C. and exhibits chemical resistance.
• Patent Documents 1 to 4 have a problem that curing is insufficient and chemical resistance is lowered when heated at a low temperature for this type of photosensitive material of 100 ° C. or lower. Further, the material described in Patent Document 5 has a problem that the resolution is 50 ⁇ m or more.
• An object of the present invention is to provide a photosensitive resin composition that achieves these requirements.
• the present invention discloses the following photosensitive resin composition in order to solve the above problems.
• a positive photosensitive resin composition comprising and / or a photoacid generator (C1').
• R 1 is a hydrogen atom or a methyl group
• R 2 and R 3 are single-bonded, substituted or unsubstituted hydrocarbon groups having 1 to 8 carbon atoms. The asterisk is directly connected to a silicon atom.
• A2 Polysiloxane having an organic group containing an unsaturated double bond in the repeating unit, a naphthoquinone diazide compound (B), and a photoradical generator (C2) and / or a photoacid generator (C2'.
• a positive photosensitive resin composition characterized by the above.
• photosensitive resin compositions are disclosed as preferred embodiments of these photosensitive resin compositions (3) the photoradical generator (C1) or the photoacid generator (C1'), or the photoradical generator (C2).
• R4 is a single-bonded, substituted or unsubstituted divalent hydrocarbon group having 1 to 6 carbon atoms and may have a substituent.
• the total amount of the structures represented by the general formulas (1) and (2) is 30 to 60 mL% with respect to the total amount of silicon atoms in the polysiloxane (A1) or the polysiloxane (A2).
• the photoradical generator (C1) or photoacid generator (C1') or the photoradical generator (C2) or photoacid generator (C2') has a maximum absorption wavelength in the range of 300 nm to 360 nm. Any positive photosensitive resin composition.
• the method of using the photosensitive resin composition of the present invention and the ones used are as follows. (12) A method for producing a cured film in which the following steps are performed in this order. (I) A step of applying the positive photosensitive resin composition according to any one of claims 1 to 11 onto a substrate to form a coating film. (Ii) Pattern exposure of the coating film so that the exposure amount of light of any one of 365 nm, 405 nm, and 436 nm is 10 mJ / m2 or more in total, and the exposure amount of light having a wavelength of less than 350 nm is 1 mJ / m2 or less in total. Then, the step of removing the exposed portion of the coating film by developing with a developing solution.
• the coating film remaining after the development is subjected to the photoradical generator (C1) and / or the acid generator (C1'), or the photoradical generator (C2) and / or the acid generator (C2').
• the step of exposing so that the exposure amount at a wavelength of 200 to 350 nm is 10 mJ / m 2 or more in total.
• a step of heating the coating film after the exposure (13) A cured film of any of the above positive photosensitive resin compositions.
• An optical device or an electronic material including at least one selected from the group consisting of an optical waveguide, a flattening film, a protective film, and an interlayer insulating film composed of the cured film.
• the resin composition of the present invention has excellent pattern processability and can be cured under low temperature conditions, and the cured film thereof has excellent chemical resistance.
• the photosensitive resin composition of the present invention has a polysiloxane (A) having a structure represented by the general formulas (1) and (2), a naphthoquinone diazide compound (B), and a maximum absorption wavelength at 200 to 360 nm (C1). ) And / or a photoacid generator (C1'), which is a positive photosensitive resin composition.
• the photosensitive composition of another aspect of the present invention comprises a polysiloxane (A2) having an organic group containing an unsaturated double bond in a repeating unit, a naphthoquinone diazide compound (B), and a photoradical generator (C2).
• the polysiloxane (A1) used in the present invention has a structure represented by the above general formulas (1) and (2).
• the polysiloxane has a structure represented by the above general formulas (1) and (2) having high copolymerizability, high heat resistance and chemical resistance can be imparted by thermal polymerization during thermosetting. Furthermore, if necessary, the required heat resistance and chemical resistance can be achieved by curing at a lower temperature.
• polysiloxane (A1) examples include polysiloxanes that can be obtained by hydrolyzing and condensing an alkoxysilane compound containing a styryl group and an alkoxysilane compound containing a (meth) acrylic group.
• polysiloxane (A2) examples include polysiloxanes that can be obtained by hydrolyzing and condensing an alkoxysilane compound containing a styryl group or an alkoxysilane compound containing a (meth) acrylic group.
• the polysiloxane (A2) also preferably has the structures of both the general formulas (1) and (2) like the polysiloxane (A1).
• Alkoxysilane compounds used as raw materials for these are commercially available, so they are easily available.
• alkoxysilane compounds having a styryl group include styryltrimethoxysilane, styryltriethoxysilane, styryltri (methoxyethoxy) silane, styryltri (propoxy) silane, styryltri (butoxy) silane, styrylmethyldimethoxysilane, and styrylethyldimethoxysilane.
• Styrylmethyldiethoxysilane styrylmethyldi (methoxyethoxy) silane and the like.
• alkoxysilane compounds containing a (meth) acrylic group include ⁇ -acryloylpropyltrimethoxysilane, ⁇ -acryloylpropyltriethoxysilane, ⁇ -methacryloylpropyltrimethoxysilane, ⁇ -methacryloylpropyltriethoxysilane, and ⁇ -.
• alkoxysilane compounds containing a (meth) acrylic group include ⁇ -acryloylpropyltrimethoxysilane, ⁇ -acryloylpropyltriethoxysilane, ⁇ -methacryloylpropyltrimethoxysilane, ⁇ -methacryloylpropyltriethoxysilane, and ⁇ -.
• the proportion of the structures represented by the general formulas (1) and (2) contained in the polysiloxane (A1) is not particularly limited, but silicon in which the structures represented by the general formulas (1) and (2) are directly linked.
• the atom is preferably 20 to 80 mol% with respect to the total amount of silicon atoms in the polysiloxane, and more preferably the total amount of the structures represented by the above general formulas (1) and (2) is the total amount of silicon atoms in the polysiloxane. It is 30 to 60 mol% with respect to.
• the total amount of the structure represented by (1) is preferably 1.0 to 3.0 in terms of the mol ratio with respect to the total amount of the structure represented by (2).
• the unsaturated double bond contained in the polysiloxane (A2) is preferably one having radical polymerization property.
• the silicon atom to which the organic group containing the unsaturated double bond contained in the polysiloxane (A2) is bonded is preferably 20 to 80 mol%, more preferably 30 to 60 mol% with respect to the total amount of silicon atoms in the polysiloxane. %.
• the polysiloxane (A2) has both the structures of the general formulas (1) and (2)
• the total amount of the structure represented by (1) is the total amount of the structure represented by (2) in the mol ratio. It is preferably 1.0 to 3.0.
• the remaining 20 to 60 mL, more preferably 40 to 70 mL, has a structure that can be introduced when an alkoxysilane compound described later is used as a raw material, and specific examples thereof include a methyl group, an ethyl group, and a propoxy group. , Acetoxy group, methoxy group, ethoxy group, phenyl group, vinyl group directly linked to silicon atom, or structure represented by the general formula (3) described later, R of the general formulas (4) to (6) described later. Examples thereof include a structure in which one or more of 5 to R 7 , R 9 to R 11 , and R 13 to R 15 are linked to an oxygen atom.
• R 4 is a single-bonded, substituted or unsubstituted saturated hydrocarbon group having 1 to 6 carbon atoms and may have a substituent.
• substituent include a methyl group, an ethyl group, a hydroxy group and the like.
• the star mark is directly connected to the silicon atom.
• alkoxysilane compounds are vinyltrimethoxysilane, vinyltriethoxysilane, vinyl-n-propoxysilane, vinyltri-1-propoxysilane, vinyltriacetoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane.
• the structures represented by the general formulas (1), (2) and (3) for example, the styryl group and the (meth) acrylic group and the vinyl group contribute to heat resistance and chemical resistance, but are highly hydrophobic. On the outer peripheral portion of the substrate, the wet spread is poor, and the yield may decrease. It is desirable to introduce a hydrophilic group into the polysiloxane in order to apply evenly to the outer peripheral portion of the substrate and improve the yield. In addition, by having a hydrophilic group in polysiloxane, the solubility in an alkaline solution as a developing solution is improved, the residue after development is suppressed, and the sensitivity and resolution in exposure are increased even after long-term storage at room temperature. It will be possible to keep. As the hydrophilic group, an organic group having a carboxyl group or a carboxylic acid anhydride is more preferable.
• alkoxysilane compound which is a raw material of this polysiloxane having an organic group having a carboxyl group or a carboxylic acid anhydride is commercially available, it is easy to obtain.
• alkoxysilane compound include an organosilane compound represented by any of the following general formulas (4) to (6). Two or more of these may be used.
• R 5 to R 7 , R 9 to R 11 and R 13 to R 15 are alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, and phenyl. It represents a group, a phenoxy group, or an alkylcarbonyloxy group having 2 to 6 carbon atoms. At least one of R 5 to R 7 , R 9 to R 11 and R 13 to R 15 is an alkoxy having 1 to 6 carbon atoms.
• R 8, R 12 and R 16 to a group is a single bond, or a chain aliphatic hydrocarbon group having 1 to 10 carbon atoms, cyclic aliphatic hydrocarbon group having 3 to 16 carbon atoms, carbon atoms 2 Represents an alkylcarbonyloxy group, a carbonyl group, an ether group, an ester group, an amide group, an aromatic group, or a divalent group having any of these of 6 to 6. These groups may be substituted h.
• R 12 and R 16 represents an integer of 0 ⁇ 3, -C 2 H 4 -., - C 3 H 6 -, - C 4 H 8 -, - O-, -C 3 H 6 OCH 2 CH ( OH) CH 2 O 2 C -, - CO -, - CO 2 -, - CONH-, organic group, and the like mentioned below).
• Specific examples of the alkoxysilane compound represented by the general formula (4) include [3- (trimethoxysilyl) propyl] succinic anhydride, [3- (triethoxycysilyl) propyl] succinic anhydride, and 3.
• organosilane compound represented by the general formula (5) include 3-trimethoxysilylpropylcyclohexyldicarboxylic acid anhydride and the like.
• alkoxysilane compound represented by the general formula (6) include 3-trimethoxycyclylpropylphthalic anhydride and the like.
• alkoxysilane compound in addition to the above alkoxysilane compound, another alkoxysilane compound may be used as a raw material.
• alkoxysilane compounds include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, and ethyl.
• bifunctional alkoxysilane compound examples include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, and ⁇ -glycidoxypropyl.
• the trifunctional alkoxysilane compound for example, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane are preferable from the viewpoint of chemical resistance of the obtained coating film.
• dimethyldialkoxysilane is preferably used for the purpose of imparting flexibility to the obtained coating film.
• examples of the tetrafunctional alkoxysilane compound include tetramethoxysilane and tetraethoxysilane.
• alkoxysilane compounds may be used alone or in combination of two or more.
• the polysiloxane (A1) or polysiloxane (A2) used in the photosensitive resin composition of the present invention hydrolyzes an alkoxysilane compound and then condenses the hydrolyzate in the presence of a solvent or in the absence of a solvent. Can be obtained by
• Examples of the catalyst used in the hydrolysis reaction include an acid catalyst and a base catalyst.
• Examples of the acid catalyst include hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, polyvalent carboxylic acid or its anhydride, ion exchange resin and the like.
• the preferable content of the catalyst is preferably 0.05 parts by weight or more, more preferably 0.1 parts by weight or more, and more preferably 0.1 parts by weight or more, based on 100 parts by weight of the total alkoxysilane compound used in the hydrolysis reaction. It is preferably 10 parts by weight or less, more preferably 5 parts by weight or less.
• the total amount of the alkoxysilane compound means an amount including all of the alkoxysilane compound, its hydrolyzate and its condensate, and the same shall apply hereinafter.
• the amount of the catalyst is 0.05 parts by weight or more, the hydrolysis proceeds smoothly, and when the amount is 10 parts by weight or less, the hydrolysis reaction can be easily controlled.
• the solvent used for the hydrolysis reaction is not particularly limited, but is appropriately selected in consideration of the stability, wettability, volatility, etc. of the resin composition. Not only one type of solvent but also two or more types can be used. Specific examples of the solvent include, for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-.
• Alcohols such as 3-methoxy-1-butanol and diacetone alcohol; glycols such as ethylene glycol and propylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Ethers such as monopropyl ether, propylene glycol monobutyl ether, propylene glycol mono-t-butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethyl ether; methyl ethyl ketone, acetyl acetone, methyl propyl ketone, methyl butyl ketone, Ketones such as methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, 2-heptanone; amides such as dimethylformamide and dimethylacetamide
• diacetone alcohol propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol Monobutyl ether, propylene glycol mono-t-butyl ether, ⁇ -butyrolactone and the like are preferably used.
• concentration is also preferable to adjust the concentration to an appropriate level as a resin composition by further adding a solvent after the completion of the hydrolysis reaction. It is also possible to distill and remove all or part of the produced alcohol or the like by heating and / or under reduced pressure after hydrolysis, and then add a suitable solvent.
• the amount of the solvent used in the hydrolysis reaction is preferably 50 parts by mass or more, more preferably 80 parts by mass or more, and preferably 500 parts by mass or less, based on 100 parts by mass of the total alkoxysilane compound. Preferably, it is 200 parts by mass or less. Gel formation can be suppressed by setting the amount of the solvent to 50 parts by mass or more. Further, when the content is 500 parts by mass or less, the hydrolysis reaction proceeds rapidly. Further, as the water used for the hydrolysis reaction, ion-exchanged water is preferable. The amount of water can be arbitrarily selected, but it is preferably used in the range of 1.0 to 4.0 mol with respect to 1 mol of the alkoxysilane compound.
• the polysiloxane solution after hydrolysis and partial condensation does not contain the above catalyst, and the catalyst can be removed if necessary.
• the removal method is not particularly limited, but water washing and / or treatment with an ion exchange resin is preferable from the viewpoint of ease of operation and removability.
• the water washing is a method in which a polysiloxane solution is diluted with an appropriate hydrophobic solvent and then washed several times with water to concentrate the obtained organic layer with an evaporator or the like.
• the treatment with an ion exchange resin is a method of contacting a polysiloxane solution with an appropriate ion exchange resin.
• the weight average molecular weight (Mw) of the polysiloxane (A1) or polysiloxane (A2) used in the photosensitive resin composition of the present invention is not particularly limited, but in terms of polystyrene measured by gel permeation chromatography (GPC). , It is preferably 1,000 or more, and more preferably 2,000 or more. Further, it is preferably 100,000 or less, more preferably 50,000 or less. By setting Mw in the above range, good coating characteristics can be obtained, and solubility in a developing solution at the time of pattern formation is also improved.
• the content of polysiloxane (A1) or polysiloxane (A2) is not particularly limited and can be arbitrarily selected depending on a desired film thickness and application, but the resin composition of the present invention. Generally, 10 parts by mass to 80 parts by mass with respect to 100 parts by mass of the solid content of the product.
• the photosensitive resin composition of the present invention contains the naphthoquinone diazide compound (B).
• the naphthoquinone diazide compound By using the naphthoquinone diazide compound, the exposed part exhibits positive photosensitivity in which it is removed by a developing solution.
• the naphthoquinone diazide compound a compound in which a sulfonic acid of naphthoquinone diazide is bonded to a compound having a phenolic hydroxyl group by an ester is preferable.
• the naphthoquinone diazide compound to be used is not particularly limited, but a compound in which a sulfonic acid of naphthoquinone diazide is bonded to a compound having a phenolic hydroxyl group by an ester is preferable.
• Examples of the compound having a phenolic hydroxyl group used here include Bis-Z, BisOC-Z, BisOPP-Z, BisP-CP, Bis26X-Z, BisOTBP-Z, BisOCHP-Z, BisOCR-CP, and BisP-MZ.
• BisP-EZ Bis26X-CP, BisP-PZ, BisP-IPZ, BisCR-IPZ, BisOCP-IPZ, BisOIPP-CP, Bis26X-IPZ, BisOTBP-CP, TekP-4HBPA (Terkis P-DO-BPA), TrisP -HAP, TrisP-PA, BisOFP-Z, BisRS-2P, BisPG-26X, BisRS-3P, BisOC-OCHP, BisPC-OCHP, Bis25X-OCHP, Bis26X-OCHP, BisOCHP-OC, Bis236T-OCHP, Methylenetris- FR-CR, BisRS-26X, BisRS-OCHP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC- F, 4PC, BIR-BIPC-F, TEP-BIP-A (trade name, manufactured by Asahi Organic Materials Industry
• compounds having a preferable phenolic hydroxyl group include, for example, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP- IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X, BIP-PC, BIR-PC, BIR-PTBP, BIR-BIPC-F And so on.
• compounds having a particularly preferable phenolic hydroxyl group include, for example, Bis-Z, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisRS-2P, BisRS-3P, BIR-PC, BIR-PTBP, BIR. -BIPC-F, 4,4'-sulfonyldiphenol, BPFL.
• These compounds having phenolic hydroxyl groups include 1,2-naphthoquinonediazide-4-sulfonic acid, 2,1-naphthoquinonediazide-4-sulfonic acid, 1,2-naphthoquinonediazide-5-sulfonic acid, and 2,1-naphtho.
• Examples thereof include those in which 4- (or 5-) naphthoquinonediazide sulfonic acid is introduced by an ester bond, such as quinonediazide-5-sulfonic acid.
• Other compounds can also be used.
• the molecular weight of the naphthoquinone diazide compound is preferably 300 to 1500, more preferably 350 to 1200. By setting the molecular weight to 300 or more, the effect of suppressing dissolution of the unexposed portion can be obtained. Further, by setting the molecular weight to 1500 or less, a good relief pattern without scum or the like can be obtained.
• naphthoquinone diazide compounds may be used alone or in combination of two or more.
• the content of these compounds is 1 to 50 parts by mass, more preferably 2 to 10 parts by mass with respect to 100 parts by mass of the solid content of the resin composition of the present invention.
• amount By setting the amount to 1 part by mass or more, pattern formation can be performed with practical sensitivity. Further, when the content is 50 parts by mass or less, a resin composition having excellent transmittance and pattern resolution can be obtained.
• an unreacted photosensitizer may remain in the unexposed area, and the film may be colored after heat curing.
• the resin composition of the present invention contains a photoradical generator (C1 or C2) and / or a photoacid generator (C1'or C2').
• a photoradical generator is a radical that is an active species capable of initiating addition polymerization of a styryl group, a (meth) acrylic group or a vinyl group by exposure to radiation such as visible light, ultraviolet rays, far ultraviolet rays, electron beams, and X-rays. It is a compound capable of generating.
• the photoacid generator is a compound capable of releasing an acid upon exposure to the above radiation.
• the generated active species or acid is considered to contribute to a cross-linking reaction such as addition reaction or polycondensation of polysiloxane and a compound having an acid anhydride group described later.
• these compounds are decomposed by exposure after the development step, not by exposure before the development step, to generate active seeds or acids, and absorption is small at the wavelength at the time of exposure before the development step. Is desirable.
• the naphthoquinone diazide compound (B) has absorption in the g-line (436 nm), h-line (405 nm), and i-line (365 nm) regions. Therefore, it is possible to perform pattern exposure with these light sources, develop the pattern to form a pattern, and further expose the pattern with a light source including light having a shorter wavelength to cure the pattern.
• the photoradical generator (C1) and photoacid generator (C1') that can be used in the present invention have maximum absorption values between wavelengths of 200 nm and 360 nm. Further, it is more preferable to have a maximum absorption value between 300 nm and 360 nm. If there is no maximum absorption wavelength between 200 nm and ⁇ 360 nm and there is a maximum at wavelengths above 360 nm, curing will proceed excessively during pattern exposure prior to the development process, and pattern processability will deteriorate. There is a risk of
• the photoradical generator (C2) and photoacid generator (C2') that can be used in the present invention have a maximum extinction coefficient at 200 to 360 nm. It is preferable that the maximum value of the extinction coefficient at 360 nm to 450 nm is twice or more, and the maximum value of the extinction coefficient at 200 to 360 nm is four times or more the maximum value of the extinction coefficient at 360 nm to 450 nm. More preferred. This requirement is the same for the photoradical generator (C1) and the photoacid generator (C1') that can be used in the first invention.
• the maximum value is the maximum value of the extinction coefficient in each range and the end of each range. It is the larger of the extinction coefficients at the wavelengths. If there is no maximum value, it will be the larger of the extinction coefficients at the wavelength at the end of each range.
• the maximum value of the extinction coefficient at 360 nm to 450 nm is preferably less than 500 mL / g ⁇ cm. Further, even when the maximum absorption value is between 300 nm and 360 nm, or when the maximum value of the extinction coefficient at 200 to 360 nm and the maximum value of the extinction coefficient at 360 nm to 450 nm satisfy the above ratios.
• the maximum value of the extinction coefficient at 300 to 360 nm is less than 3000 mL / g ⁇ cm, the chemical resistance may deteriorate. Therefore, the maximum value of the extinction coefficient at 300 to 360 nm is 3000 mL / g ⁇ cm or more. Is preferable.
• Examples of compounds satisfying the above include NCI-930, N-1919, NCI-831 (trade name, manufactured by ADEKA Corporation), Irgacure 127, Irgacure 184, Irgacure500, Irgacure 651, Irgacare MBF, and examples of photoradical generators.
• Examples of photoacid generators such as Irgacure 754, Irgacure 907, Darkur 1173 (trade name, manufactured by BASF Japan Ltd.), etc. include SP-082, SP-606, SP-171 (trade name, manufactured by ADEKA Corporation), etc. Examples include, but are not limited to, PAG169, CGI725, and the like.
• a benzophenone-based photoradical generator examples include phenylglycilic acid methyl ester and oxyphenyl acetic acid 2- [2-hydroxy-ethoxy] -ethyl ester. , Oxyphenyl acetic acid 2- [2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl ester, and the like.
• the content of the photoradical generator and the photoacid generator is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more, and 0 by mass, based on 100 parts by mass of the solid content of the resin composition of the present invention. 5.5 parts by mass or more is more preferable. Further, 20 parts by mass or less is preferable, 10 parts by mass or less is more preferable, and 5 parts by mass or less is further preferable. Within the above range, curing is promoted, chemical resistance can be expected to be improved, and excessive curing can be prevented.
• the photosensitive resin composition of the present invention may further contain a compound having an acid anhydride group. Since this compound is hydrolyzed by heating at a relatively low temperature and releases an acid, it promotes the condensation reaction of polysiloxane and contributes to the improvement of chemical resistance of the obtained cured film. In addition, heating at a relatively low temperature can react with functional groups and additives in polysiloxane to form a crosslinked structure, which contributes to improving the chemical resistance of the cured film.
• Examples of compounds having an acid anhydride group are succinic anhydride, octyl succinic dianhydride, phthalic dianhydride, tetrahydro phthalic dianhydride, hexahydro phthalic dianhydride, methyl tetrahydro phthalic dianacid, methyl hexahydro phthalic dianhydride, and Nagic dianhydride.
• succinic anhydride from the viewpoint of solubility (developability) and chemical resistance, succinic anhydride, phthalic anhydride, cis-1,2-cyclohexene dicarboxylic acid anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride Things and the like are particularly preferable.
• the content of the compound having an acid anhydride group is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more, and 0.5 part by mass with respect to 100 parts by mass of the solid content of the resin composition of the present invention. More than a portion is more preferable. Further, 20 parts by mass or less is preferable, 10 parts by mass or less is more preferable, and 5 parts by mass or less is further preferable. Within the above range, curing is promoted, chemical resistance can be expected to be improved, and storage stability is prevented from being lowered.
• the photosensitive resin composition of the present invention may contain a polyfunctional monomer (E) having two or more unsaturated double bonds in addition to the polysiloxane having an unsaturated double bond.
• This compound reacts with each other and with functional groups in polysiloxane by exposure or the above-mentioned photoradical generator to promote curing.
• a compound is not particularly limited, but a polyfunctional monomer having a (meth) acrylic group is preferable in consideration of easiness of radical polymerization.
• Examples of such compounds include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylpropandiacrylate, and tri.
• the content of these compounds is preferably 3 parts by mass or more, preferably 30 parts by mass or less, based on 100 parts by mass of the solid content of the resin composition of the present invention.
• the photosensitive resin composition of the present invention may contain a solvent.
• a solvent having a boiling point of 250 ° C. or lower under atmospheric pressure can be preferably used, and two or more of these may be used. Further, if the solvent remains in the cured film obtained by heat-curing the photosensitive resin composition of the present invention, the chemical resistance and the adhesion to the substrate are impaired over time, so that the boiling point under atmospheric pressure is 150 ° C. It is preferable that the following solvent is 50 parts by mass or more of the whole solvent in the photosensitive resin composition.
• Examples of the solvent having a boiling point of 150 ° C. or lower under atmospheric pressure include ethanol, isopropyl alcohol, 1-propyl alcohol, 1-butanol, 2-butanol, isopentyl alcohol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, and ethylene glycol mono.
• Ethyl ether methoxymethyl acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monopropyl ether, ethylene glycol monomethyl ether acetate, 1-methoxypropyl-2-acetate, acetol, acetylacetone, methyl Isobutyl ketone, methyl ethyl ketone, methyl propyl ketone, methyl lactate, toluene, cyclopentanone, cyclohexane, normal heptane, benzene, methyl acetate, ethyl acetate, propyl acetate, isobutyl acetate, butyl acetate, isopentyl acetate, pentyl acetate, 3-hydroxy- Examples thereof include 3-methyl-2-butanone, 4-hydroxy-3-methyl-2-butanone, and 5-hydroxy-2-p
• Examples of the solvent having a boiling point of 150 to 250 ° C. under atmospheric pressure include ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-tert-butyl ether, propylene glycol mono n-butyl ether, and propylene glycol mono t-.
• the content of the solvent is not particularly limited, and an arbitrary amount can be used depending on the coating method and the like.
• the film is formed by spin coating, it is generally 50 parts by mass or more and 95 parts by mass or less of the entire photosensitive resin composition of the present invention.
• the photosensitive resin composition of the present invention may contain various surfactants in order to improve the flowability and the uniformity of the film thickness at the time of coating.
• the type of the surfactant is not particularly limited, and for example, a fluorine-based surfactant, a silicone-based surfactant, a polyalkylene oxide-based surfactant, a poly (meth) acrylate-based surfactant, or the like can be used. Of these, a fluorine-based surfactant is particularly preferably used from the viewpoint of flowability and film thickness uniformity.
• the content of the surfactant is usually 0.001 to 10 parts by mass with respect to 100 parts by mass of the polysiloxane contained in the resin composition. These may be used alone or in combination of two or more at the same time.
• the photosensitive resin composition of the present invention may contain a polymerization inhibitor for the purpose of suppressing thermal polymerization at the time of prebaking, for example.
• the content of the polymerization inhibitor in the photosensitive resin composition of the present invention is preferably 0.000005 to 0.2 parts by mass, and 0.00005 to 0.1 parts by mass with respect to the entire photosensitive resin composition. Is more preferable. Further, 0.0001 to 0.5 parts by mass is preferable, and 0.001 to 0.2 parts by mass is more preferable with respect to all the components other than the organic solvent.
• the resin composition of the present invention may contain a viscosity modifier, a stabilizer, a colorant, a sensitizer, an ultraviolet absorber and the like, if necessary.
• the photosensitive resin composition of the present invention is applied onto a base substrate by a known method such as microgravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating, slit coating, etc., and is applied to a hot plate, an oven, etc.
• the prebaking is preferably carried out in the range of 50 to 130 ° C. for 30 seconds to 30 minutes, and the film thickness after prebaking is preferably 0.1 to 15 ⁇ m.
• exposure is performed using an exposure machine such as a stepper, a mirror projection mask aligner (MPA), or a parallel light mask aligner (PLA).
• the exposure amount is about 10 to 4000 J / m 2 , and this light is irradiated with or without a desired mask.
• the exposure light source is not limited, and ultraviolet rays such as i-line, g-line, and h-line, KrF (wavelength 248 nm) laser, ArF (wavelength 193 nm) laser, and the like can be used, but from the viewpoint of pattern processability, g-line It is desirable to use a (436 nm), h-line (405 nm), i-line (365 nm) or a mixed light source thereof.
• the exposed part can be melted by development to obtain a positive pattern.
• a developing method it is preferable to immerse the developer in a developing solution for 5 seconds to 10 minutes by a method such as showering, dipping, or paddle.
• a known alkaline developing solution can be used. Specific examples include alkali metal hydroxides, carbonates, phosphates, silicates, borates and other inorganic alkalis, 2-diethylaminoethanol, monoethanolamine, diethanolamine and other amines, and tetramethylammonium hydroxyides.
• An aqueous solution containing one or more quaternary ammonium salts such as choline.
• dry baking can be performed in the range of 50 to 130 ° C.
• this film is exposed by a light source containing light having a wavelength of 360 nm or less, and the film is heated in a heating device such as a hot plate or an oven at 60 to 200 ° C. for about 15 minutes to 3 hours.
• a heating device such as a hot plate or an oven at 60 to 200 ° C. for about 15 minutes to 3 hours.
• PGMEA Propylene glycol monomethyl ether acetate
• DAA Diacetone alcohol
• TMAH Tetramethylammonium hydroxide
• IPA Isopropanol.
• the solid content concentration of the polysiloxane solution was determined by the following method. 1.0 g of the polysiloxane solution was weighed in an aluminum cup and heated at 250 ° C. for 30 minutes using a hot plate to evaporate the liquid content. The solid content remaining in the aluminum cup after heating was weighed to determine the solid content concentration of the polysiloxane solution.
• UV-260 ultraviolet-visible spectrophotometer
• the measurement was carried out using only acetonitrile, and the absorbance of the photoradical generator and the photoacid generator was determined by subtracting the absorbance of acetonitrile from the absorbance of each solution. Further, the extinction coefficient (mL / g ⁇ cm) was calculated by dividing each absorbance by the concentration (g / mL).
• Synthesis Example 2 Synthesis of P-2 In the same procedure as in Synthesis Example 1, 71.30 g (0.52 mol) of MeTMS, 14.68 g (0.065 mol) of StTMS, and 15.33 g (0.065 mol) of AcTMS DAA. was charged at 84.24 g, and a mixed solution of 35.34 g of water and 0.50 g of phosphoric acid was added to synthesize P-2. 29 The molar amounts of the styryl group and the acrylic group with respect to the silicon atom measured by Si-NMR were 10 mol% and 10 mol%, respectively.
• Synthesis Example 3 Synthesis of P-3 In the same procedure as in Synthesis Example 1, 49.02 g (0.36 mol) of MeTMS, 44.03 g (0.20 mol) of StTMS, and 23.00 g (0.10 mol) of AcTMS DAA was charged in 106.35 g, and a mixed solution of 35.34 g of water and 0.58 g of phosphoric acid was added to synthesize P-3. 29 The molar amounts of the styryl group and the acrylic group with respect to the silicon atom measured by Si-NMR were 30 mol% and 15 mol%, respectively.
• Synthesis Example 4 Synthesis of P-4 In the same procedure as in Synthesis Example 1, 49.02 g (0.36 mol) of MeTMS, 44.03 g (0.20 mol) of StTMS, and 15.33 g (0.065 mol) of AcTMS DAA. was charged, and a mixed solution of 33.57 g of water and 0.54 g of phosphoric acid was added to synthesize P-4. 29 The molar amounts of the styryl group and the acrylic group with respect to the silicon atom measured by Si-NMR were 30 mol% and 10 mol%, respectively.
• Synthesis Example 5 Synthesis of P-5 In the same procedure as in Synthesis Example 1, 62.39 g (0.45 mol) of MeTMS, 29.36 g (0.13 mol) of StTMS, and 15.33 g (0.065 mol) of AcTMS DAA. was charged, and a mixed solution of 35.34 g of water and 0.54 g of phosphoric acid was added to synthesize P-5. 29 The molar amounts of the styryl group and the acrylic group with respect to the silicon atom measured by Si-NMR were 20 mol% and 10 mol%, respectively.
• Synthesis Example 6 Synthesis of P-6 In the same procedure as in Synthesis Example 1, 53.48 g (0.39 mol) of MeTMS, 29.36 g (0.13 mol) of StTMS, and 30.67 g (0.13 mol) of AcTMS DAA. was charged in 102.52 g, and a mixed solution of 35.34 g of water and 0.57 g of phosphoric acid was added to synthesize P-6. 29 The molar amounts of the styryl group and the acrylic group with respect to the silicon atom measured by Si-NMR were 20 mol% and 20 mol%, respectively.
• Synthesis Example 7 Synthesis of P-7 In the same procedure as in Synthesis Example 1, 35.65 g (0.26 mol) of MeTMS, 58.71 g (0.26 mol) of StTMS, and 30.67 g (0.13 mol) of AcTMS DAA. 122.27 g was charged, and a mixed solution of 35.34 g of water and 0.63 g of phosphoric acid was added to synthesize P-7. 29 The molar amounts of the styryl group and the acrylic group with respect to the silicon atom measured by Si-NMR were 40 mol% and 20 mol%, respectively.
• Synthesis Example 8 Synthesis of P-8 In the same procedure as in Synthesis Example 1, MeTMS was 44.57 g (0.33 mol), StTMS was 44.03 g (0.20 mol), and AcTMS was 23.00 g (0.10 mol). 4.85 g (0.03 mol) of VnTMS and 106.94 g of DAA were charged, and a mixed solution of 35.34 g of water and 0.58 g of phosphoric acid was added to synthesize P-8. 29 The molar amounts of the styryl group and the acrylic group with respect to the silicon atom measured by Si-NMR were 30 mol% and 15 mol%, respectively.
• Synthesis Example 9 Synthesis of P-9 In the same procedure as in Synthesis Example 1, 40.11 g (0.29 mol) of MeTMS, 44.03 g (0.20 mol) of StTMS, 23.00 g (0.10 mol) of AcTMS, Add 4.85 g (0.03 mol) of VnTMS, 8.58 g (0.03 mol) of SucTMS, 114.02 g of DAA, add a mixed solution of 35.93 g of water and 0.56 g of phosphoric acid, and add P-9. Synthesized. 29 The molar amounts of the styryl group and the acrylic group with respect to the silicon atom measured by Si-NMR were 30 mol% and 15 mol%, respectively.
• Synthesis Example 10 Synthesis of P-10 In the same procedure as in Synthesis Example 1, MeTMS was 44.57 g (0.33 mol), StTMS was 44.03 g (0.20 mol), and AcTMS was 23.00 g (0.10 mol). 8.58 g (0.03 mol) of SucTMS and 113.43 g of DAA were charged, and a mixed solution of 35.93 g of water and 0.56 g of phosphoric acid was added to synthesize P-10. 29 The molar amounts of the styryl group and the acrylic group with respect to the silicon atom measured by Si-NMR were 30 mol% and 15 mol%, respectively.
• Synthesis Example 12 Synthesis of R-2 In the same procedure as in Synthesis Example 11, 49.02 g (0.36 mol) of MeTMS, 69.00 g (0.29 mol) of AcTMS, 109.30 g of DAA, and 35.34 g of water were charged. And 0.59 g of phosphoric acid were added to synthesize R-2. 29 The molar amount of acrylic group measured by Si-NMR was 45 mol%.
• Synthesis Example 13 Synthesis of R-3 In the same procedure as in Synthesis Example 11, 62.39 g (0.46 mol) of MeTMS, 38.93 g (0.20 mol) of PhTMS, 84.25 g of DAA, and 35.34 g of water were charged. And 0.51 g of phosphoric acid were added to synthesize R-3.
• Synthesis Example 14 Synthesis of R-4 In the same procedure as in Synthesis Example 11, 62.39 g (0.46 mol) of MeTMS, 44.03 g (0.20 mol) of StTMS, 91.91 g of DAA, and 35.34 g of water were charged. And 0.53 g of phosphoric acid were added to synthesize R-4. 29 The molar amount of the styryl group measured by Si-NMR was 30 mol%.
• Synthesis Example 15 Synthesis of R-5 In the same procedure as in Synthesis Example 11, 49.02 g (0.36 mol) of MeTMS, 66.05 g (0.29 mol) of StTMS, 104.88 g of DAA, and 35.34 g of water were charged. And 0.58 g of phosphoric acid were added to synthesize R-5. 29 The molar amount of the styryl group measured by Si-NMR was 45 mol%.
• Synthesis Example 16 Synthesis of R-6 In the same procedure as in Synthesis Example 11, MeTMS was 44.57 g (0.33 mol), StTMS was 66.05 g (0.29 mol), and VnTMS was 4.85 g (0.03 mol). 105.47 g of DAA was charged, and a mixed solution of 35.34 g of water and 0.58 g of phosphoric acid was added to synthesize R-6. 29 The molar amount of the styryl group measured by Si-NMR was 45 mol%. The compositions of Synthesis Examples 1 to 16 are summarized in Table 1.
• Example 1 6.90 g of DAA solution (40%) of P-1 as polysiloxane (A), 0.23 g of STP-528 (trade name, AZ Electronic Materials Co., Ltd.) as naphthoquinone diazide compound (B), photoradical 0.15 g of NCI-831 (trade name, BASF Japan Ltd.) as the generating agent (C), 1.28 g and 1.39 g of PGMEA and DAA as the solvent, were mixed under a yellow light, and after shaking and stirring. A resin composition was obtained by filtering with a filter having a diameter of 0.2 ⁇ m. The composition is shown in Table 2.
• B-1 STP-528 manufactured by AZ Electronic Materials Co., Ltd.
• C-1 NCI-831 manufactured by ADEKA Corporation
• C-2 Darocur1173 BASF Japan Co., Ltd. C-3; Irgacare819 BASF Japan Co., Ltd.
• C-4 Irgacure907 BASF Japan Co., Ltd.
• C-5 Irgacure754 BASF Japan Co., Ltd.
• C-7 SP-082 ADEKA Corporation
• C-8 SP-056 ADEKA Corporation
• C-9 Irgasure OXE02 BASF Japan Ltd.
• D-1 Maleic anhydride Fuji Film Wako Junyaku Co., Ltd.
• D-2 Succinic anhydride Fuji Film Wako Junyaku Co., Ltd.
• E-1 DPHA (Dipentaerythritol hexaacrylate) Nippon Kayaku Co., Ltd.
• PGMEA Propropylene glycol monomethyl ether acetate
• DAA Diacetone alcohol.
• the maximum absorption wavelength of NCI-831 is 276,370 nm
• the maximum absorption wavelength of Darocure-1173 is 247,273 nm
• the maximum absorption wavelength of Irgacare-819 is 203,291,368,390 nm
• the maximum absorption wavelength of Irgacare-907 is 228,302 nm
• Irgacare-754 has a maximum absorption wavelength of 253,336 nm
• SP-606 has a maximum absorption wavelength of 231,344 nm
• SP-082 has a maximum absorption wavelength of 228,337 nm
• SP-056 has a maximum absorption wavelength of 231. It is 266,274 nm.
• Table 3 shows the maximum extinction coefficient of each photoradical generator and photoacid generator at 200 to 360 nm, the maximum extinction coefficient at 300 to 360 nm, and the maximum extinction coefficient at 360 to 450 nm. ..
• a cured film was prepared by the following method using the prepared resin composition.
• the cured film was evaluated by the following method. The evaluation results are shown in Table 4.
• a photosensitive resin composition is placed on a 4-inch silicon wafer substrate using a spin coater (model name: Clean Track Mark 7 manufactured by Tokyo Electron Limited) at a rotation speed of the desired film thickness. It was applied. After coating, the substrate was prebaked at 80 ° C. for 3 minutes using a hot plate SCW-636 (manufactured by Dainippon Screen Mfg. Co., Ltd.).
• the minimum pattern dimension x after development at the exposure amount for forming an L / S pattern of 40 ⁇ m in a width of 1: 1 was defined as the resolution, and the determination was made as follows.
• the presence or absence of residue in microscopic observation was determined as follows. -For the smaller pattern of minimum pattern size x or 30 um A: No residue in microscopic observation. B: There is a residue in microscopic observation.
• the photosensitive resin composition of the present invention is excellent in low temperature curability and pattern processability. Further, it can be seen that the cured film has excellent chemical resistance.
• the cured film formed by the photosensitive resin composition of the present invention is used for various electronic components, especially optical devices such as solid-state image sensors, antireflection films, antireflection plates, optical filters, and displays.
• optical devices such as solid-state image sensors, antireflection films, antireflection plates, optical filters, and displays.
• Specific examples of use include optical waveguides, microlenses, flattening materials, protective films for liquid crystal displays and color filters, interlayer insulating films for organic EL elements and liquid crystal display elements, etc., which are formed on solid-state image sensors and the like. Be done.

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