WO2014199967A1 - 感光性樹脂組成物、硬化物及びその製造方法、樹脂パターン製造方法、硬化膜、液晶表示装置、有機el表示装置、並びに、タッチパネル表示装置 - Google Patents
感光性樹脂組成物、硬化物及びその製造方法、樹脂パターン製造方法、硬化膜、液晶表示装置、有機el表示装置、並びに、タッチパネル表示装置 Download PDFInfo
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- WO2014199967A1 WO2014199967A1 PCT/JP2014/065297 JP2014065297W WO2014199967A1 WO 2014199967 A1 WO2014199967 A1 WO 2014199967A1 JP 2014065297 W JP2014065297 W JP 2014065297W WO 2014199967 A1 WO2014199967 A1 WO 2014199967A1
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- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical compound C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 125000005328 phosphinyl group Chemical group [PH2](=O)* 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 229920000962 poly(amidoamine) Polymers 0.000 description 1
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920003050 poly-cycloolefin Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 229940116423 propylene glycol diacetate Drugs 0.000 description 1
- 125000001042 pteridinyl group Chemical group N1=C(N=CC2=NC=CN=C12)* 0.000 description 1
- 125000000561 purinyl group Chemical group N1=C(N=C2N=CNC2=C1)* 0.000 description 1
- DNXIASIHZYFFRO-UHFFFAOYSA-N pyrazoline Chemical compound C1CN=NC1 DNXIASIHZYFFRO-UHFFFAOYSA-N 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 229940081623 rose bengal Drugs 0.000 description 1
- 229930187593 rose bengal Natural products 0.000 description 1
- STRXNPAVPKGJQR-UHFFFAOYSA-N rose bengal A Natural products O1C(=O)C(C(=CC=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 STRXNPAVPKGJQR-UHFFFAOYSA-N 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000005394 sealing glass Substances 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 125000005463 sulfonylimide group Chemical group 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- XKXIQBVKMABYQJ-UHFFFAOYSA-M tert-butyl carbonate Chemical group CC(C)(C)OC([O-])=O XKXIQBVKMABYQJ-UHFFFAOYSA-M 0.000 description 1
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 1
- MCZDHTKJGDCTAE-UHFFFAOYSA-M tetrabutylazanium;acetate Chemical compound CC([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC MCZDHTKJGDCTAE-UHFFFAOYSA-M 0.000 description 1
- JCJNUSDBRRKQPC-UHFFFAOYSA-M tetrahexylazanium;hydroxide Chemical compound [OH-].CCCCCC[N+](CCCCCC)(CCCCCC)CCCCCC JCJNUSDBRRKQPC-UHFFFAOYSA-M 0.000 description 1
- MRYQZMHVZZSQRT-UHFFFAOYSA-M tetramethylazanium;acetate Chemical compound CC([O-])=O.C[N+](C)(C)C MRYQZMHVZZSQRT-UHFFFAOYSA-M 0.000 description 1
- IEVVGBFMAHJELO-UHFFFAOYSA-M tetramethylazanium;benzoate Chemical compound C[N+](C)(C)C.[O-]C(=O)C1=CC=CC=C1 IEVVGBFMAHJELO-UHFFFAOYSA-M 0.000 description 1
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- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
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- 239000002562 thickening agent Substances 0.000 description 1
- 150000003553 thiiranes Chemical class 0.000 description 1
- 125000004149 thio group Chemical group *S* 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 229950003937 tolonium Drugs 0.000 description 1
- HNONEKILPDHFOL-UHFFFAOYSA-M tolonium chloride Chemical compound [Cl-].C1=C(C)C(N)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 HNONEKILPDHFOL-UHFFFAOYSA-M 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 125000002088 tosyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])S(*)(=O)=O 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 1
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- 125000005409 triarylsulfonium group Chemical group 0.000 description 1
- 150000003627 tricarboxylic acid derivatives Chemical class 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 125000005580 triphenylene group Chemical group 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 150000003732 xanthenes Chemical class 0.000 description 1
- 150000007964 xanthones Chemical class 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
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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
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
- G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
- G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
- G06F3/0443—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means using a single layer of sensing electrodes
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
- G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
- G06F3/0446—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means using a grid-like structure of electrodes in at least two directions, e.g. using row and column electrodes
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
- G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
- G06F2203/04103—Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
- G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
- G06F2203/04111—Cross over in capacitive digitiser, i.e. details of structures for connecting electrodes of the sensing pattern where the connections cross each other, e.g. bridge structures comprising an insulating layer, or vias through substrate
Definitions
- the present invention relates to a photosensitive resin composition (hereinafter sometimes simply referred to as “the resin composition of the present invention” or “the composition of the present invention”). Further, a cured product obtained by curing the photosensitive resin composition and a production method thereof, a resin pattern production method using the photosensitive resin composition, a cured film obtained by curing the photosensitive resin composition, and The present invention relates to various image display devices using the cured film.
- a photosensitive resin composition suitable for forming a flattening film, a protective film, and an interlayer insulating film of electronic components such as a liquid crystal display device, an organic EL display device, an integrated circuit element, and a solid-state image sensor, and the use thereof
- the present invention relates to a method for producing a cured film.
- the problem to be solved by the present invention is a photosensitive resin composition having a high refractive index, a low relative dielectric constant, and excellent transparency, a cured product using the photosensitive resin composition, and The manufacturing method, the resin pattern manufacturing method, and a liquid crystal display device, an organic EL display device, and a touch panel display device having the cured product.
- ⁇ 1> metal oxide particles
- Component B a compound represented by the following formula (I)
- Component C a solvent
- Component D a group in which an acid group is protected by an acid-decomposable group.
- a photosensitive resin composition comprising: a polymer containing a structural unit having; and (Component E) a photoacid generator,
- Ar 1 and Ar 2 each independently represent an arylene group, and R 1 and R 2 each independently represent a hydroxy group, a carboxy group, an alkoxy group, or a hydroxy group, a carboxy group, or an epoxy group.
- R 3 and R 4 each independently represent a monovalent substituent
- p and q are each independently Represents an integer of 0 to 4, and different R 3 s and different R 4 s may combine to form an alicyclic ring or an aromatic ring.
- Ar 1 and Ar 2 each independently represent an arylene group
- R 5 and R 6 each independently represent a hydrogen atom or a group consisting of a hydroxy group, a carboxy group, an epoxy group, and an oxetanyl group.
- a method for producing a cured product comprising at least steps (a) to (c) in this order, (A) Application step of applying the photosensitive resin composition according to any one of the above ⁇ 1> to ⁇ 8> on a substrate (b) Solvent removal step of removing the solvent from the applied resin composition ( c) a heat treatment step of heat-treating the resin composition from which the solvent has been removed ⁇ 10> a resin pattern manufacturing method comprising at least steps (1) to (4) in this order; (1) Application step of applying the photosensitive resin composition according to any one of the above ⁇ 1> to ⁇ 8> onto a substrate (2) Solvent removal step of removing the solvent from the applied resin composition ( 3) An exposure step in which the resin composition from which the solvent has been removed is exposed in a pattern with actinic rays.
- the obtained cured product has a high refractive index, a low relative dielectric constant, a photosensitive resin composition excellent in transparency, a cured product using the photosensitive resin composition, and a method for producing the same,
- a resin pattern manufacturing method, and a liquid crystal display device, an organic EL display device and a touch panel display device having the cured product can be provided.
- 1 is a conceptual diagram of a configuration of an example of a liquid crystal display device.
- the schematic sectional drawing of the active matrix substrate in a liquid crystal display device is shown, and it has the cured film 17 which is an interlayer insulation film.
- 1 shows a conceptual diagram of a configuration of an example of an organic EL display device.
- a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided.
- It is sectional drawing which shows the structure of an electrostatic capacitance type input device.
- component A metal oxide particles
- component A a structural unit having a group in which an acid group is protected by an acid-decomposable group
- structural unit (a1) a structural unit having a group in which an acid group is protected by an acid-decomposable group
- the description which does not describe substitution and unsubstituted includes the thing which has a substituent with the thing which does not have a substituent.
- the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
- “parts by mass” and “% by mass” are synonymous with “parts by weight” and “% by weight”, respectively. In the present invention, a combination of preferred embodiments is more preferred.
- the photosensitive resin composition of the present invention (hereinafter also simply referred to as “resin composition”) comprises (Component A) metal oxide particles, (Component B) a compound represented by the following formula (I), (Component C) And (component D) a polymer containing a structural unit having a group in which an acid group is protected by an acid-decomposable group, and (component E) a photoacid generator.
- Ar 1 and Ar 2 each independently represent an arylene group, and R 1 and R 2 each independently represent a hydroxy group, a carboxy group, an alkoxy group, or a hydroxy group, a carboxy group, an epoxy.
- the photosensitive resin composition of the present invention can be suitably used as a positive resist composition.
- the photosensitive resin composition of the present invention is preferably a resin composition having a property of being cured by heat.
- the photosensitive resin composition of the present invention is preferably a positive photosensitive resin composition, and is a chemically amplified positive photosensitive resin composition (chemically amplified positive photosensitive resin composition). Is more preferable.
- the photosensitive resin composition of the present invention preferably contains no 1,2-quinonediazide compound as a photoacid generator sensitive to actinic rays. A 1,2-quinonediazide compound generates a carboxy group by a sequential photochemical reaction, but its quantum yield is always 1 or less.
- (Component E) photoacid generator used in the present invention is such that the acid generated in response to actinic light acts as a catalyst for the deprotection of the protected acid group in Component A. Therefore, the acid generated by the action of one photon contributes to many deprotection reactions, and the quantum yield exceeds 1, for example, a large value such as the power of 10, which is a result of so-called chemical amplification. As a result, high sensitivity can be obtained.
- the photosensitive resin composition of the present invention is a resin composition for optical members such as microlenses, optical waveguides, antireflection films, LED sealing materials, and LED chip coating materials, or wiring used for touch panels.
- a resin composition for reducing the visibility of an electrode is preferable.
- the composition for reducing the visibility of the wiring electrode used for the touch panel is a composition for a member that reduces the visibility of the wiring electrode used for the touch panel, that is, makes the wiring electrode difficult to see. Examples thereof include an interlayer insulating film between ITO (indium tin oxide) electrodes, and the photosensitive resin composition of the present invention can be suitably used for the application.
- metal oxide particles In order to improve the refractive index, when using metal oxide particles, it is preferable to include a large amount of metal oxide particles as a solid content in the composition.
- the relative dielectric constant of the metal oxide particles themselves is extremely high, so that the relative dielectric constant of the film after formation becomes extremely high, For example, it has been found that when used as an insulating member between wiring layers, it may cause wiring delay and the like. It has also been found that the inclusion of metal oxide particles may increase the haze value of the film after formation (transparency deteriorates).
- the resin composition of the present invention contains metal oxide particles for the purpose of adjusting the refractive index and light transmittance. Since the metal oxide particles have high transparency and light transmittance, a positive photosensitive resin composition having a high refractive index and excellent transparency can be obtained.
- Component A preferably has a refractive index higher than that of the resin composition made of a material excluding the particles. Specifically, the refractive index in light having a wavelength of 400 to 750 nm is 1.50.
- the above particles are more preferable, particles having a refractive index of 1.70 or more are further preferable, and particles having a refractive index of 1.90 or more are particularly preferable.
- the refractive index of light having a wavelength of 400 to 750 nm being 1.50 or more means that the average refractive index of light having a wavelength in the above range is 1.50 or more. It is not necessary that the refractive index of all light having a wavelength is 1.50 or more.
- the average refractive index is a value obtained by dividing the sum of the measured values of the refractive index for each light having a wavelength in the above range by the number of measurement points.
- the metal of the metal oxide particles in the present invention includes semimetals such as B, Si, Ge, As, Sb, and Te.
- the light-transmitting and high refractive index metal oxide particles include Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, Ti, Zr, Hf, and Nb.
- Oxide particles containing atoms such as Mo, W, Zn, B, Al, Si, Ge, Sn, Pb, Sb, Bi, and Te are preferable.
- Titanium oxide, titanium composite oxide, zinc oxide, zirconium oxide, indium / Tin oxide and antimony / tin oxide are more preferable, titanium oxide, titanium composite oxide and zirconium oxide are more preferable, titanium oxide and zirconium oxide are particularly preferable, and titanium oxide is most preferable.
- Titanium oxide is particularly preferably a rutile type having a high refractive index. The surface of these metal oxide particles can be treated with an organic material in order to impart dispersion stability.
- the average primary particle size of Component A is preferably 1 to 200 nm, more preferably 3 to 80 nm, and particularly preferably 5 to 50 nm.
- the average primary particle diameter of the particles refers to an arithmetic average obtained by measuring the particle diameter of 200 arbitrary particles with an electron microscope. When the particle shape is not spherical, the longest side is the diameter.
- the component A may be used individually by 1 type, and can also use 2 or more types together.
- the content of the metal oxide particles in the resin composition of the present invention may be appropriately determined in consideration of the refractive index required for the optical member obtained from the resin composition, light transmittance, etc.
- the total solid content of the resin composition is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, still more preferably 15 to 60% by mass, and further preferably 20 to 50% by mass. It is especially preferable to set it as the mass%.
- the particles can be used as a dispersion prepared by mixing and dispersing in a suitable dispersant and solvent using a mixing device such as a ball mill or a rod mill.
- a suitable dispersant and solvent such as 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, in addition to the (Component C) solvent described below.
- -Alcohols such as pentanol, 2-pentanol, 3-pentanol, 3-methyl-1-butanol, 2-methyl-2-butanol, neopentanol, cyclopentanol, 1-hexanol, cyclohexanol, etc. Can be mentioned.
- These solvents can be used singly or in combination of two or more.
- the photosensitive resin composition of the present invention contains (Component B) a compound represented by the following formula (I).
- Ar 1 and Ar 2 each independently represent an arylene group, and R 1 and R 2 each independently represent a hydroxy group, a carboxy group, an alkoxy group, or a hydroxy group, a carboxy group, an epoxy.
- Ar 1 and Ar 2 are each independently preferably a divalent aromatic hydrocarbon group, more preferably a phenylene group or a naphthylene group, from the viewpoints of synthesis and relative dielectric constant, more preferably 1,4-phenylene. Group or a 2,6-naphthylene group is more preferable, and a 1,4-phenylene group is particularly preferable.
- Ar 1 and Ar 2 are each independently preferably a naphthylene group, more preferably a 2,6-naphthylene group from the viewpoint of refractive index. From the viewpoints of synthesis and relative dielectric constant, Ar 1 and Ar 2 are preferably the same group. Ar 1 and Ar 2 may each independently have a substituent on the aromatic ring.
- Preferred examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, and an arylthio group, and a halogen atom, an alkyl group, and an aryl group are more preferred. More preferred examples include alkyl groups and aryl groups. Moreover, the said substituent may couple
- R 1 and R 2 are each independently a hydroxy group, a carboxy group, an alkoxy group, or a monovalent organic group having at least one group selected from the group consisting of a hydroxy group, a carboxy group, an epoxy group, and an oxetanyl group. And at least one of R 1 and R 2 is a monovalent organic group having at least one group selected from the group consisting of a hydroxy group, a carboxy group, or a hydroxy group, a carboxy group, an epoxy group, and an oxetanyl group. It is a group.
- R 1 and R 2 are each independently at least one group selected from the group consisting of a hydroxy group, a carboxy group, or a hydroxy group, a carboxy group, an epoxy group, and an oxetanyl group. It is preferably a monovalent organic group having a hydroxyl group, more preferably a monovalent organic group having at least one group selected from the group consisting of a hydroxy group or a hydroxy group, an epoxy group and an oxetanyl group. The monovalent organic group having at least one group selected from the group consisting of an epoxy group and an oxetanyl group is more preferable, and a monovalent organic group having an epoxy group is particularly preferable.
- R 1 and R 2 are preferably a hydroxy group or a monovalent organic group having a hydroxy group from the viewpoint of sensitivity, and a monovalent organic group having an epoxy group or an oxetanyl group from the viewpoint of transparency. Is preferred. Furthermore, R 1 and R 2 are particularly preferably the same group from the viewpoint of synthesis.
- the monovalent organic group having at least one group selected from the group consisting of a hydroxy group, a carboxy group, an epoxy group, and an oxetanyl group in R 1 and R 2 is a hydroxy group, a carboxy group, an epoxy group, and an oxetanyl group at the terminal. It is preferably a monovalent organic group having at least one group selected from the group consisting of:
- the partial structure other than the hydroxy group, carboxy group, epoxy group, and oxetanyl group in the monovalent organic group includes an alkylene group, an ether bond, a thioether bond, a carbonyl group, an amide bond, and a combination of these. Preferably mentioned.
- the monovalent organic group is preferably a group having an ether bond, an alkyleneoxy group or a polyalkyleneoxy group, and more preferably an ether bond or an alkyleneoxy group.
- the carbon number of the monovalent organic group in R 1 and R 2 is preferably 0 to 60, more preferably 0 to 40, and still more preferably 0 to 20.
- R 1 and R 2 are each independently a hydroxy group, glycidyloxy group, 3-alkyl-3-oxetanylmethyloxy group, glycidyloxyalkyleneoxy group, or glycidyloxypoly It is preferably an alkyleneoxy group, more preferably a hydroxy group, a glycidyloxy group, or a glycidyloxyalkyleneoxy group, still more preferably a glycidyloxy group or a glycidyloxyalkyleneoxy group, and glycidyloxy An alkyleneoxy group is particularly preferred.
- R 3 and R 4 each independently represents a monovalent substituent.
- Preferred examples of the monovalent substituent in R 3 and R 4 include a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, and an arylthio group.
- a halogen atom, an alkyl group, and an alkoxy group Can be illustrated more preferably, and an alkyl group can be illustrated more preferably.
- the carbon number of the monovalent organic group in R 3 and R 4 is preferably 0 to 40, more preferably 0 to 30, and still more preferably 0 to 20.
- p and q each independently represents an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 2, and particularly preferably 0. It is also possible to form an alicyclic or aromatic ring by bonding different R 3 and between different R 4 together. When forming the said ring, it is preferable to form an aromatic ring and it is more preferable to form the following rings with a fluorene ring.
- the compound represented by the formula (I) preferably has 4 to 8 benzene rings, more preferably 5 to 8, and still more preferably 6 to 8.
- the refractive index is more excellent.
- the naphthalene ring is assumed to have two benzene rings.
- the molecular weight of the compound represented by formula (I) is preferably less than 1,000, more preferably from 400 to less than 1,000, from the viewpoint of solubility in a developer and optical properties. It is preferably 400 to 800, more preferably 400 to 600.
- the compound represented by the formula (I) is preferably a compound represented by the formula (II).
- Ar 1 and Ar 2 each independently represent an arylene group
- R 5 and R 6 each independently comprise a hydrogen atom, or a hydroxy group, a carboxy group, an epoxy group, and an oxetanyl group.
- Ar 1, Ar 2, R 3 in formula (II), R 4, p and q are respectively the same as Ar 1, Ar 2, R 3 , R 4, p and q in formula (I), preferred embodiments Is the same.
- R 5 and R 6 are each independently preferably a hydrogen atom or a monovalent organic group having at least one group selected from the group consisting of a hydroxy group, an epoxy group and an oxetanyl group, A monovalent organic group having at least one group selected from the group consisting of oxetanyl groups is more preferable, and a monovalent organic group having an epoxy group is more preferable.
- R 5 and R 6 are particularly preferably the same group from the viewpoint of synthesis.
- Examples of the partial structure other than the hydroxy group, carboxy group, epoxy group and oxetanyl group in the monovalent organic group of R 5 and R 6 include an alkylene group, an ether bond, a thioether bond, a carbonyl group, an amide bond, and A combination of these is preferred.
- the carbon number of the monovalent organic group in R 5 and R 6 is preferably 0 to 60, more preferably 0 to 40, and still more preferably 0 to 20.
- R 5 and R 6 are each independently a hydrogen atom, glycidyl group, 3-alkyl-3-oxetanylmethyl group, glycidyloxyalkyl group, or glycidylpolyalkyleneoxyalkyl.
- Group preferably a hydroxy group, a glycidyl group, or a glycidyloxyalkyl group, more preferably a glycidyl group or a glycidyloxyalkyl group, and a glycidyloxyalkyl group. Particularly preferred.
- the compound represented by formula (I) is more preferably a compound represented by formula (III) or formula (IV), and is a compound represented by formula (V) or formula (VI). More preferably.
- R 5 and R 6 are each independently a hydrogen atom or at least one group selected from the group consisting of a hydroxy group, a carboxy group, an epoxy group, and an oxetanyl group.
- R 3 , R 4 , R 7 and R 8 each independently represents a monovalent substituent, and p, q, m and n are each independently an integer of 0 to 4 M ′ and n ′ each independently represents an integer of 0 to 6, and different R 3 s and different R 4 s may be bonded to form an alicyclic ring or an aromatic ring.
- R 3, R 4, p and q in formula (III) ⁇ formula (VI) are each and R 3, R 4, p and q synonymous in the formula (I), preferable embodiments thereof are also the same.
- R 5 and R 6 in formula (III) ⁇ formula (VI) are each with R 5 and R 6 synonymous in Formula (II), preferable embodiments thereof are also the same.
- R 7 and R 8 in formula (III) to formula (VI) each independently represent a monovalent substituent, and are a halogen atom, alkyl group, alkenyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, or An arylthio group is preferable, a halogen atom, an alkyl group, or an aryl group is more preferable, and an alkyl group and an aryl group are still more preferable.
- M and n in formula (III) to formula (VI) each independently represents an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, and 0. More preferably.
- M ′ and n ′ in formula (III) to formula (VI) each independently represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, More preferably.
- the compound represented by the formula (I) include 9,9-bis (glycidyloxyalkoxy-alkylphenyl) fluorene ⁇ for example, 9,9-bis [4- (2-glycidyloxyethoxy) -3- 9,9-bis (glycidyloxy C2-4alkoxy-mono or di-C1-4 such as methylphenyl] fluorene, 9,9-bis [4- (2-glycidyloxyethoxy) -3,5-dimethylphenyl] fluorene Alkylphenyl) fluorene ⁇ , 9,9-bis (glycidyloxydialkoxy-alkylphenyl) fluorene ⁇ eg, 9,9-bis ⁇ 4- [2- (2-glycidyloxyethoxy) ethoxy] -3-methylphenyl ⁇ Fluorene, 9,9-bis ⁇ 4- [2- (2-glycidyloxyethoxy) ethoxy] -3,5-d
- a reflux cooling device was provided with 13 g of 9,9-bis (hydroxyphenyl) fluorene (BPF: manufactured by Osaka Gas Chemical Co., Ltd.), 35 g of 2-bromoethanol and 3 g of sodium hydroxide together with 12 g of water and 3 g of 1,4-dioxane.
- BPF 9,9-bis (hydroxyphenyl) fluorene
- 2-bromoethanol 35 g
- sodium hydroxide 35 g
- the flask was placed in a 300 ml three-necked flask and stirred vigorously. Subsequently, the mixture was heated and stirred at a heater temperature of 120 ° C. for 5 hours, and then returned to room temperature (25 ° C.).
- the aqueous sodium hydroxide solution in the flask was removed and the sample was washed 5 times with water. 16.2 g of a compound represented by the following structural formula (x) was obtained.
- the compounds represented by the formula (I) may be used alone or in combination of two or more.
- the content of the compound represented by formula (I) in the photosensitive resin composition of the present invention is preferably 1 to 200 parts by mass with respect to 100 parts by mass of the total content of Component D, and 5 to 150 parts by mass. More preferred is 10 to 150 parts by mass, still more preferred is 50 to 120 parts by mass.
- cured material obtained is higher, a relative dielectric constant is lower, and it is excellent by transparency.
- the fluorene epoxy compound is acrylated and cured by photopolymerization, but in the present invention, the compound represented by the formula (I) is used. Therefore, the density of the fluorene ring in the photosensitive resin composition becomes higher, and the photosensitive resin composition of the present invention is considered to have better optical properties such as refractive index and transparency.
- the photosensitive resin composition of the present invention contains (Component C) a solvent.
- the photosensitive resin composition of the present invention is preferably prepared as a solution obtained by dissolving the essential components of the present invention and further optional components described later in (Component C) solvent.
- solvent used in the photosensitive resin composition of the present invention known solvents can be used, such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl.
- Ethers propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether Examples include acetates, esters, ketones, amides, lactones and the like.
- Specific examples of the solvent used in the photosensitive resin composition of the present invention include the solvents described in paragraphs 0174 to 0178 of JP2011-221494A, and the paragraphs 0167 to 0168 of JP2012-194290A. The solvents described are also included, the contents of which are incorporated herein.
- Component C is preferably a solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C., a solvent having a boiling point of 160 ° C. or higher, or a mixture thereof.
- Solvents having a boiling point of 130 ° C. or higher and lower than 160 ° C. include propylene glycol monomethyl ether acetate (boiling point 146 ° C.), propylene glycol monoethyl ether acetate (boiling point 158 ° C.), propylene glycol methyl-n-butyl ether (boiling point 155 ° C.), propylene glycol An example is methyl-n-propyl ether (boiling point 131 ° C.).
- Solvents having a boiling point of 160 ° C or higher include ethyl 3-ethoxypropionate (boiling point 170 ° C), diethylene glycol methyl ethyl ether (boiling point 176 ° C), propylene glycol monomethyl ether propionate (boiling point 160 ° C), dipropylene glycol methyl ether acetate.
- the content of the (component C) solvent in the photosensitive resin composition of the present invention is preferably 50 to 95 parts by mass, and preferably 60 to 90 parts by mass per 100 parts by mass of component D in the photosensitive resin composition. More preferably.
- (Component D) Polymer having a constitutional unit having a group in which an acid group is protected with an acid-decomposable group The photosensitive resin composition of the present invention is a group in which (Component D) an acid group is protected with an acid-decomposable group
- the polymer which has a structural unit which has is contained is also referred to as “(a1) a structural unit having a group in which an acid group is protected by an acid-decomposable group”.
- the photosensitive resin composition of the present invention may further contain a polymer other than the polymer having a structural unit having a group in which an acid group is protected with an acid-decomposable group.
- the photosensitive resin composition of the present invention preferably contains a polymer component including a polymer that satisfies at least one of the following (1) and (2). (1) (a1) a polymer having a structural unit having an acid group protected with an acid-decomposable group and (a2) a structural unit having a crosslinkable group (2) (a1) an acid group having an acid-decomposable group And (a2) a polymer having a structural unit having a crosslinkable group
- the photosensitive resin composition of the present invention further contains a polymer other than these. May be.
- component D in the present invention means one including other polymers added as necessary in addition to the above (1) and / or (2). It is preferable that the photosensitive resin composition of this invention contains the component which satisfy
- a polymer having a structural unit having a group in which an acid group is protected by an acid-decomposable group and / or (a2) cross-linking A polymer having a structural unit having a functional group may be contained. Moreover, even when it contains a component satisfying the above (2), it has (a1) a structural unit having a group in which an acid group is protected by an acid-decomposable group and (a2) a structural unit having a crosslinkable group. When it contains at least what corresponds to a polymer, it corresponds when it contains the component which satisfy
- Component D is preferably an addition polymerization type resin, and more preferably a polymer containing a structural unit derived from (meth) acrylic acid and / or an ester thereof.
- a polymer containing a structural unit derived from (meth) acrylic acid and / or an ester thereof you may have structural units other than the structural unit derived from (meth) acrylic acid and / or its ester, for example, the structural unit derived from styrene, the structural unit derived from a vinyl compound, etc.
- the “structural unit derived from (meth) acrylic acid and / or its ester” is also referred to as “acrylic structural unit”.
- (meth) acrylic acid” means “methacrylic acid and / or acrylic acid”.
- Component D includes (a1) a polymer having at least a structural unit having a group in which an acid group is protected with an acid-decomposable group.
- component D contains a polymer having the structural unit (a1), a highly sensitive photosensitive resin composition can be obtained.
- group in which the acid group is protected with an acid-decomposable group those known as an acid group and an acid-decomposable group can be used, and are not particularly limited.
- Specific examples of the acid group preferably include a carboxyl group and a phenolic hydroxyl group.
- Examples of the acid-decomposable group include groups that are relatively easily decomposed by an acid (for example, an ester structure of a group represented by the formula (a1-10) described later, a tetrahydropyranyl ester group, a tetrahydrofuranyl ester group, etc. Acetal functional groups) and groups that are relatively difficult to decompose with acid (for example, tertiary alkyl ester groups such as tert-butyl ester groups and tertiary alkyl carbonate groups such as tert-butyl carbonate groups). it can.
- an acid for example, an ester structure of a group represented by the formula (a1-10) described later, a tetrahydropyranyl ester group, a tetrahydrofuranyl ester group, etc.
- Acetal functional groups groups that are relatively difficult to decompose with acid (for example, tertiary alkyl ester groups such as tert-butyl ester
- a structural unit having a group in which an acid group is protected with an acid-decomposable group is a structural unit having a protected carboxyl group in which a carboxyl group is protected with an acid-decomposable group (“protection protected with an acid-decomposable group” Or a structural unit having a protected phenolic hydroxyl group in which the phenolic hydroxyl group is protected by an acid-decomposable group (having a protected phenolic hydroxyl group protected by an acid-decomposable group). It is also preferably referred to as a “structural unit”.
- the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is a protected carboxyl in which the carboxyl group of the structural unit having a carboxyl group is protected by an acid-decomposable group described in detail below.
- a structural unit having a group is not particularly limited, and a known structural unit can be used.
- a structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, or an unsaturated tricarboxylic acid
- a structural unit (a1-1-2) having both an ethylenically unsaturated group and a structure derived from an acid anhydride.
- the structural units having both the unsaturated group and the structure derived from the acid anhydride will be described in order.
- ⁇ (a1-1-1) Structural Unit Derived from Unsaturated Carboxylic Acid etc. Having at least One Carboxyl Group in the Molecule >>>
- the unsaturated carboxylic acid used in the present invention as the structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule include those listed below. . That is, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, ⁇ -chloroacrylic acid, cinnamic acid, 2- (meth) acryloyloxyethyl succinic acid, and 2- (meth) acryloyl.
- Examples include loxyethyl hexahydrophthalic acid and 2- (meth) acryloyloxyethyl phthalic acid.
- Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid.
- the acid anhydride may be sufficient as unsaturated polyhydric carboxylic acid used in order to obtain the structural unit which has a carboxyl group. Specific examples include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like.
- the unsaturated polyvalent carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester of a polyvalent carboxylic acid, such as succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2 -Methacryloyloxyethyl), mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate and the like.
- the unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of a dicarboxy polymer at both ends, and examples thereof include ⁇ -carboxypolycaprolactone monoacrylate and ⁇ -carboxypolycaprolactone monomethacrylate.
- unsaturated carboxylic acid acrylic acid-2-carboxyethyl ester, methacrylic acid-2-carboxyethyl ester, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, 4-carboxystyrene and the like can also be used.
- the structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule acrylic acid, methacrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl phthalic acid, anhydride of unsaturated polyvalent carboxylic acid, etc. It is preferable to use acrylic acid, methacrylic acid, and 2- (meth) acryloyloxyethyl hexahydrophthalic acid.
- the structural unit (a1-1-1) derived from an unsaturated carboxylic acid or the like having at least one carboxyl group in the molecule may be composed of one kind alone or two or more kinds. May be.
- a structural unit having both an ethylenically unsaturated group and a structure derived from an acid anhydride is obtained by reacting a hydroxyl group present in the structural unit having an ethylenically unsaturated group with an acid anhydride.
- a unit derived from the obtained monomer is preferred.
- the acid anhydride known ones can be used, and specifically, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride, etc.
- phthalic anhydride, tetrahydrophthalic anhydride, or succinic anhydride is preferable from the viewpoint of developability.
- the reaction rate of the acid anhydride with respect to the hydroxyl group is preferably 10 to 100 mol%, more preferably 30 to 100 mol% from the viewpoint of developability.
- the above-mentioned acid-decomposable groups can be used.
- these acid-decomposable groups it is a protected carboxyl group in which the carboxyl group is protected in the form of an acetal. It is preferable from the viewpoint of the storage stability of the composition.
- the carboxyl group is more preferably a protected carboxyl group protected in the form of an acetal represented by the following formula (a1-10) from the viewpoint of sensitivity.
- the carboxyl group is a protected carboxyl group protected in the form of an acetal represented by the following formula (a1-10)
- the entire protected carboxyl group is — (C ⁇ O) —O—CR 101 R
- the structure is 102 (OR 103 ).
- R 101 and R 102 each independently represent a hydrogen atom, an alkyl group or an aryl group, provided that, .R 103 except in the case of the R 101 and R 102 are both hydrogen atoms Represents an alkyl group or an aryl group, and R 101 or R 102 and R 103 may be linked to form a cyclic ether.
- R 101 and R 102 each independently represents a hydrogen atom, an alkyl group or an aryl group
- R 103 represents an alkyl group or an aryl group
- the alkyl group is linear. It may be branched or cyclic.
- both R 101 and R 102 do not represent a hydrogen atom, and at least one of R 101 and R 102 represents an alkyl group.
- R 101 , R 102 and R 103 represent an alkyl group
- the alkyl group may be linear, branched or cyclic.
- the linear or branched alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms.
- methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, n examples include -hexyl group, texyl group (2,3-dimethyl-2-butyl group), n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group and the like.
- the cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, and still more preferably 4 to 6 carbon atoms.
- Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, and an isobornyl group.
- the alkyl group may have a substituent, and examples of the substituent include a halogen atom, an aryl group, and an alkoxy group.
- R 101 , R 102 and R 103 When it has a halogen atom as a substituent, R 101 , R 102 and R 103 become a haloalkyl group, and when it has an aryl group as a substituent, R 101 , R 102 and R 103 become an aralkyl group.
- the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a fluorine atom or a chlorine atom is preferable.
- the aryl group is preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 12 carbon atoms.
- Specific examples include a phenyl group, an ⁇ -methylphenyl group, a naphthyl group, and the like, and examples of the entire alkyl group substituted with an aryl group, that is, an aralkyl group include a benzyl group, an ⁇ -methylbenzyl group, a phenethyl group, A naphthylmethyl group etc. can be illustrated.
- the alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms, and still more preferably a methoxy group or an ethoxy group.
- the alkyl group is a cycloalkyl group
- the cycloalkyl group may have a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent, and the alkyl group is a linear chain. Or a branched alkyl group, it may have a cycloalkyl group having 3 to 12 carbon atoms as a substituent. These substituents may be further substituted with the above substituents.
- R 101 , R 102 and R 103 represent an aryl group
- the aryl group preferably has 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms. preferable.
- the aryl group may have a substituent, and preferred examples of the substituent include an alkyl group having 1 to 6 carbon atoms. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a cumenyl group, and a 1-naphthyl group.
- R 101 , R 102 and R 103 can be bonded together to form a ring together with the carbon atom to which they are bonded.
- Examples of the ring structure when R 101 and R 102 , R 101 and R 103 or R 102 and R 103 are bonded include, for example, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group, an adamantyl group, and a tetrahydropyrani group. And the like.
- any one of R 101 and R 102 is preferably a hydrogen atom or a methyl group.
- radical polymerizable monomer used for forming the structural unit having a protected carboxyl group represented by the above formula (a1-10) a commercially available one may be used, or one synthesized by a known method Can also be used. For example, it can be synthesized by a method such as the synthesis method described in paragraphs 0037 to 0040 of JP2011-212494A.
- a first preferred embodiment of the structural unit (a1-1) having a protected carboxyl group protected by the acid-decomposable group is a structural unit represented by the following formula.
- R 1 and R 2 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R 1 and R 2 is an alkyl group or an aryl group, and R 3 is an alkyl group. Or R 1 or R 2 and R 3 may be linked to form a cyclic ether, R 4 represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group. .
- R 1 and R 2 are alkyl groups, alkyl groups having 1 to 10 carbon atoms are preferred. When R 1 and R 2 are aryl groups, a phenyl group is preferred. R 1 and R 2 are preferably each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R 3 represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. X represents a single bond or an arylene group, and a single bond is preferable.
- a second preferred embodiment of the structural unit (a1-1) having a protected carboxyl group protected by the acid-decomposable group is a structural unit represented by the following formula.
- R 121 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
- L 1 represents a carbonyl group or a phenylenecarbonyl group
- R 122 to R 128 each independently represents a hydrogen atom or 1 to 4 represents an alkyl group.
- R 121 is preferably a hydrogen atom or a methyl group.
- L 1 is preferably a carbonyl group.
- R 122 to R 128 are preferably hydrogen atoms.
- R represents a hydrogen atom or a methyl group.
- the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group is a protected phenolic group in which the structural unit having a phenolic hydroxyl group is protected by an acid-decomposable group described in detail below.
- ⁇ (a1-2-1) Structural unit having phenolic hydroxyl group Examples of the structural unit having a phenolic hydroxyl group include a hydroxystyrene-based structural unit and a structural unit in a novolac-based resin. Among these, a structural unit derived from hydroxystyrene or ⁇ -methylhydroxystyrene is sensitive. From the viewpoint of In addition, as a structural unit having a phenolic hydroxyl group, a structural unit represented by the following formula (a1-20) is also preferable from the viewpoint of sensitivity.
- R 220 represents a hydrogen atom or a methyl group
- R 221 represents a single bond or a divalent linking group
- R 222 represents a halogen atom or a linear or branched group having 1 to 5 carbon atoms.
- R 220 represents a hydrogen atom or a methyl group, and is preferably a methyl group.
- R 221 represents a single bond or a divalent linking group. A single bond is preferable because the sensitivity can be improved and the transparency of the cured film can be further improved.
- the divalent linking group for R 221 include an alkylene group, preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 8 carbon atoms, and still more preferably an alkylene group having 1 to 3 carbon atoms.
- R 221 is an alkylene group
- R 221 is an alkylene group
- R 221 is preferably a single bond, a methylene group, an ethylene group, a 1,2-propylene group, a 1,3-propylene group, or a 2-hydroxy-1,3-propylene group.
- the divalent linking group may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, and an alkoxy group.
- A represents an integer of 1 to 5, but a is preferably 1 or 2 and more preferably 1 from the viewpoint of the effects of the present invention and the ease of production.
- the bonding position of the hydroxyl group in the benzene ring is preferably bonded to the 4-position when the carbon atom bonded to R 221 is defined as the reference (first position).
- R 222 each independently represents a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms.
- a chlorine atom, a bromine atom, a methyl group, or an ethyl group is preferable from the viewpoint of easy production.
- B represents 0 or an integer of 1 to 4;
- the acid-decomposable group that can be used in the structural unit (a1-2) having a protected phenolic hydroxyl group protected by the acid-decomposable group includes a structure having a protected carboxyl group protected by the acid-decomposable group Similar to the acid-decomposable group that can be used for the unit (a1-1), known ones can be used and are not particularly limited.
- a structural unit having a protected phenolic hydroxyl group protected with acetal is a basic physical property of the photosensitive resin composition, particularly sensitivity and pattern shape, storage stability of the photosensitive resin composition, contact This is preferable from the viewpoint of hole formability.
- the phenolic hydroxyl group is more preferably a protected phenolic hydroxyl group protected in the form of an acetal represented by the above formula (a1-10) from the viewpoint of sensitivity.
- the phenolic hydroxyl group is a protected phenolic hydroxyl group protected in the form of an acetal represented by the above formula (a1-10)
- the entire protected phenolic hydroxyl group is —Ar—O—CR 101 R 102.
- the structure is (OR 103 ).
- Ar represents an arylene group.
- Examples of the radical polymerizable monomer used to form a structural unit having a protected phenolic hydroxyl group in which the phenolic hydroxyl group is protected in the form of an acetal include, for example, paragraph 0042 of JP2011-215590A And the like.
- a 1-alkoxyalkyl protector of 4-hydroxyphenyl methacrylate and a tetrahydropyranyl protector of 4-hydroxyphenyl methacrylate are preferable from the viewpoint of transparency.
- acetal protecting group for the phenolic hydroxyl group examples include a 1-alkoxyalkyl group, such as a 1-ethoxyethyl group, a 1-methoxyethyl group, a 1-n-butoxyethyl group, and a 1-isobutoxyethyl group.
- 1- (2-chloroethoxy) ethyl group, 1- (2-ethylhexyloxy) ethyl group, 1-n-propoxyethyl group, 1-cyclohexyloxyethyl group, 1- (2-cyclohexylethoxy) ethyl group, 1 -A benzyloxyethyl group etc. can be mentioned, These can be used individually by 1 type or in combination of 2 or more types.
- the radical polymerizable monomer used for forming the structural unit (a1-2) having a protected phenolic hydroxyl group protected by the acid-decomposable group a commercially available one may be used, or a known method may be used. What was synthesize
- combined by can also be used. For example, it can be synthesized by reacting a compound having a phenolic hydroxyl group with vinyl ether in the presence of an acid catalyst. In the above synthesis, a monomer having a phenolic hydroxyl group may be previously copolymerized with another monomer, and then reacted with vinyl ether in the presence of an acid catalyst.
- R represents a hydrogen atom or a methyl group.
- the content of the structural unit (a1) is 20 to 100 in the polymer having the structural unit (a1).
- the mol% is preferable, and 30 to 90 mol% is more preferable.
- the polymer having the structural unit (a1) has the following structural unit (a2)
- the content of the structural unit (a1) is in the polymer having the structural unit (a1) and the structural unit (a2). From the viewpoint of sensitivity, it is preferably 3 to 70 mol%, more preferably 10 to 60 mol%.
- the structural unit (a1) is a structural unit having a protected carboxyl group in which the carboxyl group is protected in the form of an acetal, 20 to 50 mol% is preferable.
- the “structural unit” is synonymous with the “monomer unit”.
- the “monomer unit” may be modified after polymerization by a polymer reaction or the like. The same applies to the following.
- the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is more developed than the structural unit (a1-2) having a protected phenolic hydroxyl group protected with the acid-decomposable group. Is characterized by being fast. Therefore, when it is desired to develop quickly, the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is preferred. Conversely, when it is desired to delay the development, it is preferable to use the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group.
- Component D contains a polymer having a structural unit (a2) having a crosslinkable group.
- the crosslinkable group is not particularly limited as long as it is a group that causes a curing reaction by heat treatment.
- Preferred embodiments of the structural unit having a crosslinkable group are represented by an epoxy group, an oxetanyl group, and —NH—CH 2 —O—R (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms).
- the component D includes a structural unit including at least one of an epoxy group and an oxetanyl group.
- Component D preferably contains a polymer having a structural unit (structural unit (a2-1)) having an epoxy group and / or an oxetanyl group.
- a 3-membered cyclic ether group is also called an epoxy group, and a 4-membered cyclic ether group is also called an oxetanyl group.
- the structural unit (a2-1) having an epoxy group and / or oxetanyl group may have at least one epoxy group or oxetanyl group in one structural unit, one or more epoxy groups and one It may have an oxetanyl group, two or more epoxy groups, or two or more oxetanyl groups, and is not particularly limited, but preferably has a total of 1 to 3 epoxy groups and / or oxetanyl groups, It is more preferable to have one or two epoxy groups and / or oxetanyl groups in total, and it is even more preferable to have one epoxy group or oxetanyl group.
- radical polymerizable monomer used for forming the structural unit having an epoxy group include, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl ⁇ -ethyl acrylate, and glycidyl ⁇ -n-propyl acrylate.
- radical polymerizable monomer used for forming the structural unit having an oxetanyl group include, for example, a (meth) acryl having an oxetanyl group described in paragraphs 0011 to 0016 of JP-A No. 2001-330953. Acid esters, and the like, the contents of which are incorporated herein.
- radical polymerizable monomer used for forming the structural unit (a2-1) having the epoxy group and / or oxetanyl group include a monomer having a methacrylic ester structure and an acrylic ester structure. It is preferable that it is a monomer to contain.
- These structural units can be used individually by 1 type or in combination of 2 or more types.
- R represents a hydrogen atom or a methyl group.
- (a2-2) Structural unit having an ethylenically unsaturated group is a structural unit (a2-2) having an ethylenically unsaturated group (hereinafter also referred to as “structural unit (a2-2)”).
- the structural unit (a2-2) having an ethylenically unsaturated group is preferably a structural unit having an ethylenically unsaturated group in the side chain, having an ethylenically unsaturated group at the terminal, and having 3 to 16 carbon atoms.
- a structural unit having a side chain is more preferred.
- the copolymer used in the present invention is a structural unit (a2-3) having a group represented by —NH—CH 2 —O—R (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). Is also preferable.
- a curing reaction can be caused by a mild heat treatment, and a cured film having excellent characteristics can be obtained.
- R is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 9 carbon atoms, and still more preferably an alkyl group having 1 to 4 carbon atoms.
- the alkyl group may be a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group.
- the structural unit (a2) is more preferably a structural unit having a group represented by the following formula (a2-30).
- R 31 represents a hydrogen atom or a methyl group
- R 32 represents an alkyl group having 1 to 20 carbon atoms.
- R 32 is preferably an alkyl group having 1 to 9 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.
- the alkyl group may be a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group.
- Specific examples of R 32 include methyl group, ethyl group, n-butyl group, i-butyl group, cyclohexyl group, and n-hexyl group. Of these, i-butyl group, n-butyl group and methyl group are preferable.
- the content of the structural unit (a2) is 5 to 90 in the polymer having the structural unit (a2).
- the mol% is preferable, and 20 to 80 mol% is more preferable.
- the polymer having the structural unit (a2) has the structural unit (a1), the content of the single structural unit (a2) in the polymer having the structural unit (a1) and the structural unit (a2) From the viewpoint of chemical resistance, it is preferably 3 to 70 mol%, more preferably 10 to 60 mol%.
- the structural unit (a2) is preferably contained in an amount of 3 to 70 mol%, more preferably 10 to 60 mol% in all the structural units of the component D, regardless of any embodiment.
- the cured film obtained from the photosensitive resin composition has good transparency and chemical resistance.
- the component D may have another structural unit (a3) in addition to the structural units (a1) and / or (a2). These structural units may be contained in the polymer component (1) and / or (2).
- the polymer component has another structural unit (a3) substantially free from the structural unit (a1) and the structural unit (a2). It may be.
- the blending amount of the polymer component is preferably 60% by mass or less, more preferably 40% by mass or less, and still more preferably 20% by mass or less in all polymer components.
- a monomer used as another structural unit (a3) For example, styrenes, (meth) acrylic acid alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated Dicarboxylic acid diesters, bicyclounsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, and other unsaturated compounds be able to.
- the monomer which becomes another structural unit (a3) can be used individually by 1 type or in combination of 2 or more types.
- the other structural unit (a3) include styrene, methylstyrene, hydroxystyrene, ⁇ -methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, 4 -Hydroxybenzoic acid (3-methacryloyloxypropyl) ester, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, ( For 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acrylonitrile, ethylene glycol monoacetoacetate mono
- a structural unit derived from a monomer having a styrene or an aliphatic cyclic skeleton is preferable from the viewpoint of electrical characteristics.
- Specific examples include styrene, termethylstyrene, hydroxystyrene, ⁇ -methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, and the like.
- the other structural unit (a3) a structural unit derived from (meth) acrylic acid alkyl ester is preferable from the viewpoint of adhesion.
- Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and n-butyl (meth) acrylate, and methyl (meth) acrylate is more preferable.
- the content of the structural unit (a3) is preferably 60 mol% or less, more preferably 50 mol% or less, and still more preferably 40 mol% or less.
- 0 mol% may be sufficient, it is preferable to set it as 1 mol% or more, for example, and it is more preferable to set it as 5 mol% or more.
- various properties of the cured film obtained from the photosensitive resin composition are improved.
- the polymer contained in Component D preferably has a structural unit having an acid group as the other structural unit (a3).
- the acid group in the present invention means a proton dissociable group having a pKa of less than 10.5.
- the acid group is usually incorporated into the polymer as a structural unit containing an acid group using a monomer capable of forming an acid group. By including such a structural unit containing an acid group in the polymer, the polymer tends to be easily dissolved in an alkaline developer.
- Examples of the acid group used in the present invention include a carboxylic acid group, a sulfonamide group, a phosphonic acid group, a sulfonic acid group, a phenolic hydroxyl group, a sulfonamide group, a sulfonylimide group, and acid anhydride groups of these acid groups, And the group etc. which neutralized these acid groups and made it into salt structure are illustrated, and a carboxylic acid group and / or a phenolic hydroxyl group are preferable.
- An alkali metal salt, alkaline-earth metal salt, and organic ammonium salt can illustrate preferably.
- the structural unit containing an acid group used in the present invention is more preferably a structural unit derived from styrene, a structural unit derived from a vinyl compound, a structural unit derived from (meth) acrylic acid and / or an ester thereof.
- a structural unit derived from styrene a structural unit derived from a vinyl compound
- a structural unit derived from (meth) acrylic acid and / or an ester thereof .
- compounds described in paragraphs 0021 to 0023 and paragraphs 0029 to 0044 of JP2012-88459A can be used, the contents of which are incorporated herein.
- structural units derived from p-hydroxystyrene, (meth) acrylic acid, maleic acid, and maleic anhydride are preferred.
- a polymer having another structural unit (a3) substantially not including the structural unit (a1) and the structural unit (a2) is included. You may go out.
- a resin having a carboxyl group in the side chain is preferable.
- methacrylic acid copolymer acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc.
- side chain examples thereof include acidic cellulose derivatives having a carboxyl group, those obtained by adding an acid anhydride to a polymer having a hydroxyl group, and high molecular polymers having a (meth) acryloyl group in the side chain.
- benzyl (meth) acrylate / (meth) acrylic acid copolymer 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, described in JP-A-7-140654 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2 -Hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid
- Known polymer compounds described in JP-A-2003-233179, JP-A-2009-52020, and the like can be used, and the contents thereof are incorporated herein. These polymers may contain only 1 type and may contain 2 or more types.
- SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, SMA 3840F (above, manufactured by Sartomer), ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920, ARUFON UC-3080 (above, manufactured by Toagosei Co., Ltd.), JONCRYL 690, JONCRYL 678, JONCRYL 67, JONCRYL 586 (above, manufactured by BASF), etc. are used. You can also.
- the structural unit containing an acid group is preferably from 1 to 80 mol%, more preferably from 1 to 50 mol%, still more preferably from 5 to 40 mol%, particularly preferably from 5 to 30 mol%, based on the structural units of all polymer components. Most preferred is 5 to 20 mol%.
- any polymer includes a structural unit containing at least an acid group as the other structural unit (a3).
- -Fifth embodiment- In addition to the polymer component (1) or (2), an embodiment having a polymer having another structural unit (a3) substantially not having the structural unit (a1) and the structural unit (a2). .
- -Sixth embodiment- A mode comprising a combination of two or more of the first to fifth embodiments.
- the molecular weight of the polymer in Component D is a weight average molecular weight in terms of polystyrene, and is preferably in the range of 1,000 to 200,000, more preferably 2,000 to 50,000. Various characteristics are favorable in the range of said numerical value.
- the ratio (dispersity, Mw / Mn) between the number average molecular weight Mn and the weight average molecular weight Mw is preferably 1.0 to 5.0, more preferably 1.5 to 3.5.
- the weight average molecular weight and the number average molecular weight are preferably measured by gel permeation chromatography.
- the measurement by gel permeation chromatography in the present invention uses HLC-8020GPC (manufactured by Tosoh Corporation), and TSKgel Super HZ MH, TSK gel Super HZ4000, TSKgel SuperHZ200 (manufactured by Tosoh Corporation), 4.6 mm ID ⁇ 15 cm) and THF (tetrahydrofuran) as the eluent is preferably used.
- radicals used to form at least the structural unit (a1) and the structural unit (a3) can be synthesized by polymerizing a radical polymerizable monomer mixture containing a polymerizable monomer in an organic solvent using a radical polymerization initiator. It can also be synthesized by a so-called polymer reaction.
- the content of component D in the photosensitive resin composition of the present invention is preferably 5 to 95% by mass, and preferably 10 to 70% by mass, based on the total solid content of the photosensitive resin composition. More preferably, it is 15 to 50% by mass. When the content is within this range, the pattern formability during development is good, and a cured product having a higher refractive index can be obtained.
- the solid content amount of the photosensitive resin composition represents an amount excluding volatile components such as a solvent.
- the photosensitive resin composition of the present invention contains (Component E) a photoacid generator.
- the photoacid generator (also referred to as “component E”) used in the present invention is preferably a compound that generates an acid in response to an active ray having a wavelength of 300 nm or more, preferably 300 to 450 nm.
- the structure is not limited.
- a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can also be used as a sensitizer if it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination.
- the photoacid generator used in the present invention is preferably a photoacid generator that generates an acid having a pKa of 4 or less, more preferably a photoacid generator that generates an acid having a pKa of 3 or less, and a pKa of 2 or less. Most preferred is a photoacid generator that generates an acid.
- photoacid generator examples include trichloromethyl-s-triazines, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among these, it is preferable to use an oxime sulfonate compound from the viewpoint of insulation and sensitivity.
- photoacid generators can be used singly or in combination of two or more.
- trichloromethyl-s-triazines diaryliodonium salts, triarylsulfonium salts, quaternary ammonium salts, and diazomethane derivatives include the compounds described in paragraphs 0083 to 0088 of JP2011-212494A. It can be illustrated.
- oxime sulfonate compound that is, a compound having an oxime sulfonate structure
- a compound containing an oxime sulfonate structure represented by the following formula (E1) can be preferably exemplified, and the contents thereof are incorporated in the present specification.
- R 21 represents an alkyl group or an aryl group, the wavy line portion represents a bonding site to another group.
- the alkyl group for R 21 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms.
- the alkyl group represented by R 21 is an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group (7,7-dimethyl-2-oxonorbornyl group or the like). It may be substituted with a cyclic group, preferably a bicycloalkyl group or the like.
- aryl group for R 21 an aryl group having 6 to 11 carbon atoms is preferable, and a phenyl group or a naphthyl group is more preferable.
- the aryl group of R 21 may be substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom.
- the above compound containing an oxime sulfonate structure represented by the above formula (E1) is also preferably an oxime sulfonate compound represented by the following formula (E2).
- R 42 represents an alkyl group or an aryl group
- X represents an alkyl group, an alkoxy group, or a halogen atom
- m4 represents an integer of 0 to 3
- m4 is 2 or 3. In some cases, multiple Xs may be the same or different.
- the alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
- the alkoxy group as X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.
- the halogen atom as X is preferably a chlorine atom or a fluorine atom.
- m4 is preferably 0 or 1. In the above formula (E2), m4 is 1, X is a methyl group, the substitution position of X is the ortho position, R 42 is a linear alkyl group having 1 to 10 carbon atoms, 7,7-dimethyl A compound having a -2-oxonorbornylmethyl group or a p-toluyl group is particularly preferable.
- the compound containing an oxime sulfonate structure represented by the above formula (E1) is also preferably an oxime sulfonate compound represented by the following formula (E3).
- R 43 has the same meaning as R 42 in the formula (E2).
- X 1 represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, cyano Represents a group or a nitro group, and n4 represents an integer of 0 to 5.
- R 43 in the above formula (E3) is a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-octyl group, a trifluoromethyl group, a pentafluoroethyl group, a perfluoro-n-propyl group, A perfluoro-n-butyl group, a p-tolyl group, a 4-chlorophenyl group or a pentafluorophenyl group is preferred, and an n-octyl group is particularly preferred.
- X 1 is preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group.
- n4 is preferably an integer of 0 to 2, particularly preferably 0 or 1.
- the compound containing an oxime sulfonate structure represented by the above formula (E1) is also preferably a compound represented by the following formula (OS-1).
- R 101 represents a hydrogen atom, alkyl group, alkenyl group, alkoxy group, alkoxycarbonyl group, acyl group, carbamoyl group, sulfamoyl group, sulfo group, cyano group, aryl group, or hetero Represents an aryl group.
- R102 represents an alkyl group or an aryl group.
- X 101 represents —O—, —S—, —NH—, —NR 105 —, —CH 2 —, —CR 106 H—, or —CR 105 R 107 —, wherein R 105 to R 107 are alkyl groups. Or an aryl group.
- R 121 to R 124 each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group, or Represents an aryl group.
- Two of R 121 to R 124 may be bonded to each other to form a ring.
- R 121 to R 124 are each independently preferably a hydrogen atom, a halogen atom or an alkyl group, and an embodiment in which at least two of R 121 to R 124 are bonded to each other to form an aryl group is also preferable. Can be mentioned. Among these, an embodiment in which R 121 to R 124 are all hydrogen atoms is preferable from the viewpoint of sensitivity. Any of the aforementioned functional groups may further have a substituent.
- the compound represented by the formula (OS-1) is preferably a compound represented by the formula (OS-2) described in paragraphs 0087 to 0089 of JP2012-163937A, for example. This content is incorporated herein.
- the compound having an oxime sulfonate structure represented by the above formula (E1) is represented by the following formula (OS-3), the following formula (OS-4) or the following formula (OS-5). It is preferably an oxime sulfonate compound.
- R 22 , R 25 and R 28 each independently represents an alkyl group, an aryl group or a heteroaryl group
- R 23 , R 26 and R 29 are Each independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom
- R 24 , R 27 and R 30 each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxy group.
- X 1 to X 3 each independently represents an oxygen atom or a sulfur atom
- n 1 to n 3 each independently represents 1 or 2
- m 1 to m 3 each independently represents 0 Represents an integer of ⁇ 6)
- the compound containing an oxime sulfonate structure represented by the above formula (E1) is represented by, for example, general formulas (OS-6) to (OS-11) described in paragraph 0117 of JP2012-163937A. It is particularly preferred that the compound is represented by any of the above), the contents of which are incorporated herein.
- oxime sulfonate compounds represented by the above formulas (OS-3) to (OS-5) include the compounds described in paragraphs 0114 to 0120 of JP2011-221494A. The invention is not limited to these.
- the compound containing an oxime sulfonate structure represented by the above formula (E1) is also preferably an oxime sulfonate compound represented by the following formula (E1-4).
- R e1 represents an alkyl group or an aryl group
- R e2 represents an alkyl group, an aryl group, or a heteroaryl group
- R e3 to R e6 are each a hydrogen atom, alkyl group, an aryl group, a halogen atom.
- R e3 and R e4, R e4 and R e5, or R e5 and R e6 are bonded to may also form a cycloaliphatic or aromatic ring .
- X e is , -O- or -S-.
- R e1 represents an alkyl group or an aryl group.
- the alkyl group is preferably a branched alkyl group or a cyclic alkyl group.
- the alkyl group preferably has 3 to 10 carbon atoms. In particular, when the alkyl group has a branched structure, an alkyl group having 3 to 6 carbon atoms is preferable, and when the alkyl group has a cyclic structure, an alkyl group having 5 to 7 carbon atoms is preferable.
- alkyl group examples include propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, 1,1-dimethylpropyl group, hexyl group. 2-ethylhexyl group, cyclohexyl group, octyl group and the like, preferably isopropyl group, tert-butyl group, neopentyl group, and cyclohexyl group.
- the aryl group preferably has 6 to 12 carbon atoms, more preferably 6 to 8 carbon atoms, and still more preferably 6 to 7 carbon atoms.
- Examples of the aryl group include a phenyl group and a naphthyl group, and a phenyl group is preferable.
- the alkyl group and aryl group represented by R e1 may have a substituent.
- substituents examples include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a linear, branched or cyclic alkyl group (eg, a methyl group, an ethyl group, a propyl group), an alkenyl group, an alkynyl group, Aryl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, cyano group, carboxyl group, hydroxyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, heterocyclic oxy group, acyloxy group, amino group, A nitro group, a hydrazino group, a heterocyclic group, etc. are mentioned. Further, these groups may be further substituted. Preferably, they are a halogen atom and a methyl group.
- R e1 is preferably an alkyl group from the viewpoint of transparency, and R e1 has a branched structure having 3 to 6 carbon atoms from the viewpoint of achieving both storage stability and sensitivity.
- An alkyl group, an alkyl group having a cyclic structure having 5 to 7 carbon atoms, or a phenyl group is preferable, and an alkyl group having a branched structure having 3 to 6 carbon atoms or an alkyl group having a cyclic structure having 5 to 7 carbon atoms is more preferable.
- By adopting such a bulky group (particularly a bulky alkyl group) as R e1 it becomes possible to further improve the transparency.
- an isopropyl group, a tert-butyl group, a neopentyl group, and a cyclohexyl group are preferable, and a tert-butyl group and a cyclohexyl group are more preferable.
- R e2 represents an alkyl group, an aryl group, or a heteroaryl group.
- the alkyl group represented by R e2 is preferably a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms.
- Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, and a cyclohexyl group. It is a group.
- As the aryl group an aryl group having 6 to 10 carbon atoms is preferable.
- Examples of the aryl group include a phenyl group, a naphthyl group, a p-toluyl group (p-methylphenyl group), and a phenyl group and a p-toluyl group are preferable.
- Examples of the heteroaryl group include a pyrrole group, an indole group, a carbazole group, a furan group, and a thiophene group.
- the alkyl group, aryl group, and heteroaryl group represented by R e2 may have a substituent. As a substituent, it is synonymous with the substituent which the alkyl group and aryl group which Re1 represents may have.
- R e2 is preferably an alkyl group or an aryl group, more preferably an aryl group, and more preferably a phenyl group.
- As the substituent for the phenyl group a methyl group is preferred.
- R e3 to R e6 each independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom (a fluorine atom, a chlorine atom, a bromine atom or an iodine atom).
- the alkyl group represented by R e3 to R e6 has the same meaning as the alkyl group represented by R e2 , and the preferred range is also the same.
- the aryl group represented by R e3 to R e6 has the same meaning as the aryl group represented by R e1 , and the preferred range is also the same.
- R e3 to R e6 may combine to form a ring, and the ring forms an alicyclic ring or aromatic ring And a benzene ring is more preferable.
- R e3 to R e6 are a hydrogen atom, an alkyl group, a halogen atom (fluorine atom, chlorine atom, bromine atom), or R e3 and R e4 , R e4 and R e5 , or R e5 and R e6 are bonded.
- Benzene ring is preferably formed, and a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, a bromine atom, or R e3 and R e4 , R e4 and R e5 , or R e5 and R e6 are bonded. It is more preferable that a benzene ring is formed.
- R e3 to R e6 are as follows. (Aspect 1) At least two are hydrogen atoms. (Aspect 2) The number of alkyl groups, aryl groups, or halogen atoms is one or less.
- X e represents —O— or —S—.
- Ts represents a tosyl group (p-toluenesulfonyl group)
- Me represents a methyl group
- Bu represents an n-butyl group
- Ph represents a phenyl group.
- the photoacid generator is preferably used in an amount of 0.1 to 30 parts by mass with respect to 100 parts by mass of Component D in the photosensitive resin composition. It is more preferable to use 5 to 20 parts by mass.
- the component E may be used individually by 1 type, and can also use 2 or more types together.
- the photosensitive resin composition of the present invention preferably contains (Component F) a dispersant.
- a dispersing agent By containing a dispersing agent, the dispersibility in the resin composition of the component A can be improved more.
- a known dispersant can be used.
- a known pigment dispersant can be appropriately selected and used.
- a polymer dispersant can be preferably used.
- the polymer dispersant is a dispersant having a molecular weight (weight average molecular weight) of 1,000 or more.
- the resin composition of the present invention preferably contains (Component F) a dispersant represented by the following formula (S) and having at least one acid group as (Component F) a dispersant. Since the resin composition of the present invention contains the component S, there are few coarse particles when the metal oxide particles are dispersed, and there is no aggregation when the dispersion and the polymer component are mixed. A cured product having excellent transparency can be formed.
- R 3 represents an (m + n) -valent linking group
- R 4 and R 5 each independently represents a single bond or a divalent linking group
- a 2 represents an organic dye structure or a heterocyclic ring.
- Structure, acid group, group having basic nitrogen atom, urea group, urethane group, group having coordinating oxygen atom, hydrocarbon group having 4 or more carbon atoms, alkoxysilyl group, epoxy group, isocyanate group and hydroxyl group Represents a monovalent organic group containing at least one partial structure selected from the group, n A 2 and R 4 may be the same or different, m represents 0 to 8, n represents 2 to 9, m + n is 3 to 10, P 2 represents a polymer skeleton, and m P 2 and R 5 may be the same or different.
- Component S is a dispersant having at least one acid group.
- an acid group By having an acid group, it is presumed to act as an adsorbing group for the metal oxide particles, and the dispersibility of the metal oxide particles is excellent.
- the acid group include a carboxylic acid group (carboxy group), a sulfonic acid group, a phosphoric acid group, a phenolic hydroxyl group, and the like. From the viewpoint of adsorbing power and dispersibility on metal oxide particles, a carboxylic acid group, a sulfone group, and the like. It is preferably at least one selected from the group consisting of an acid group and a phosphate group, and a carboxylic acid group is particularly preferable.
- the acid groups in the dispersant may have one of these alone or in combination of two or more.
- the acid group in component S may have any structure of formula (S). Specifically, for example, acid groups, both of the above formulas may be included in the A 2 in (S), also it may be included in the polymer backbone represented by P 2, A 2 and P 2 it may be included in, from the viewpoint of effect, it is preferably included in a 2.
- a 2 represents an organic dye structure, a heterocyclic structure, an acid group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, or a group having 4 or more carbon atoms.
- n A 2 present in the formula (S) may be the same or different.
- the above A 2 is a structure having an adsorption ability for metal oxide particles such as an organic dye structure or a heterocyclic structure, an acid group, a group having a basic nitrogen atom, a urea group, a urethane group, or a coordinating oxygen.
- a monovalent group containing at least one functional group capable of adsorbing to metal oxide particles such as a group having an atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group. Represents an organic group.
- the partial structure having the ability to adsorb to the metal oxide particles (the above structure and functional group) will be collectively referred to as “adsorption site” as appropriate.
- the adsorption sites are in one A 2, it may be contained at least one, may contain two or more kinds.
- the “monovalent organic group containing at least one kind of adsorption site” means the aforementioned adsorption site, 1 to 200 carbon atoms, 0 to 20 nitrogen atoms, 0 To 100 oxygen atoms, 1 to 400 hydrogen atoms, and a linking group consisting of 0 to 40 sulfur atoms are monovalent organic groups.
- adsorption sites themselves may constitute a monovalent organic group
- adsorption sites itself may be a monovalent organic group represented by A 2.
- the adsorption site constituting A 2 will be described below.
- organic dye structure examples include, for example, phthalocyanine, insoluble azo, azo lake, anthraquinone, quinacridone, dioxazine, diketopyrrolopyrrole, anthrapyridine, ansanthrone, indanthrone, flavan.
- preferable dye structures of throne, perinone, perylene, and thioindigo are phthalocyanine, azo lake, anthraquinone, dioxazine, and diketopyrrolopyrrole, and phthalocyanine and anthraquinone.
- a diketopyrrolopyrrole dye structure is particularly preferred.
- the “heterocyclic structure” may be a group having at least one heterocyclic ring.
- the heterocyclic ring in the “heterocyclic structure” include, for example, thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, triazole, thiadiazole, pyran, Pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, benzimidazolone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine,
- the “organic dye structure” or “heterocyclic structure” may further have a substituent.
- substituents include alkyl groups having 1 to 20 carbon atoms such as a methyl group and an ethyl group.
- Acyl groups having 1 to 6 carbon atoms such as aryl groups, hydroxyl groups, amino groups, carboxy groups, sulfonamido groups, N-sulfonylamido groups, acetoxy groups, etc., such as aryl groups, phenyl groups, naphthyl groups, etc.
- Alkoxy groups having 1 to 20 carbon atoms such as methoxy group and ethoxy group, halogen atoms such as chlorine atom and bromine atom, alkoxy having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group
- carbonic acid ester groups such as a carbonyl group, a cyano group, and a t-butyl carbonate group.
- these substituents may be bonded to the organic dye structure or the heterocyclic structure through the following structural unit or a linking group constituted by combining the structural units.
- Examples of the “acid group” include carboxylic acid group, sulfonic acid group, monosulfate group, phosphoric acid group, monophosphate group, and boric acid group.
- Preferred examples include carboxylic acid group, sulfonic acid group, A monosulfate group, a phosphate group, and a monophosphate group are more preferable, a carboxylic acid group, a sulfonic acid group, and a phosphate group are more preferable, and a carboxylic acid group is particularly preferable.
- Examples of the “group having a basic nitrogen atom” include an amino group (—NH 2 ), a substituted imino group (—NHR 8 , —NR 9 R 10 , wherein R 8 , R 9 and R 10 Each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms), a guanidyl group represented by the following formula (a1), the following formula ( Preferred examples include the amidinyl group represented by a2).
- R 11 and R 12 each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms.
- R 13 and R 14 each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms.
- an amino group (—NH 2 ), a substituted imino group (—NHR 8 , —NR 9 R 10 , wherein R 8 , R 9 and R 10 are each independently an alkyl having 1 to 10 carbon atoms.
- Examples of the “urea group” include —NR 15 CONR 16 R 17 (wherein R 15 , R 16 and R 17 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a carbon number of 6 The above aryl group or an aralkyl group having 7 or more carbon atoms may be mentioned as a preferred example, and —NR 15 CONHR 17 (wherein R 15 and R 17 are each independently a hydrogen atom, 1 carbon atom) More preferably an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms, and —NHCONHR 17 (wherein R 17 represents a hydrogen atom, 1 to 10 carbon atoms). Or an alkyl group having 6 or more carbon atoms or an aralkyl group having 7 or more carbon atoms) is particularly preferable.
- Examples of the “urethane group” include —NHCOOR 18 , —NR 19 COOR 20 , —OCONHR 21 , —OCONR 22 R 23 (here, R 18 , R 19 , R 20 , R 21 , R 22 and R 23).
- each R 18 and R 21 are independently an alkyl group having from 1 to 10 carbon atoms, having 6 or more aryl group having a carbon or a carbon number of 7 or more It represents an aralkyl group.) And the like are particularly preferred.
- Examples of the “group having a coordinating oxygen atom” include an acetylacetonato group and a group having a crown ether structure.
- hydrocarbon group having 4 or more carbon atoms include an alkyl group having 4 or more carbon atoms, an aryl group having 6 or more carbon atoms, an aralkyl group having 7 or more carbon atoms, and the like. More preferably, an alkyl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an alkyl group having 4 to 15 carbon atoms (for example, an octyl group, a dodecyl group, etc.), and 6 to 15 carbon atoms. Particularly preferred are aryl groups such as phenyl group and naphthyl group, and aralkyl groups having 7 to 15 carbon atoms (such as benzyl group).
- alkoxysilyl group examples include a trimethoxysilyl group and a triethoxysilyl group.
- the linking group bonded to the adsorption site may be a single bond or 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200.
- a linking group comprising up to 0 hydrogen atoms and 0 to 20 sulfur atoms is preferred, and this linking group may be unsubstituted or may further have a substituent.
- Specific examples of this linking group include the following structural units or groups formed by combining the structural units.
- examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, and an aryl group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group.
- halogen atom such as a chlorine atom or a bromine atom, an alkoxycarbonyl group having 2 to 7 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group or a cyclohexyloxycarbonyl group, a carbonate group such as a cyano group or a t-butyl carbonate group Is mentioned.
- a 2 a portion selected from the group consisting of an organic dye structure, a heterocyclic structure, an acid group, a group having a basic nitrogen atom, a urea group, and a hydrocarbon group having 4 or more carbon atoms
- a monovalent organic group containing at least one structure is preferable, and a monovalent organic group containing at least one acid group is particularly preferable.
- a 2 is more preferably a monovalent organic group represented by the following formula (4).
- B 1 represents the adsorption site (that is, an organic dye structure, a heterocyclic structure, an acid group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, A partial structure selected from the group consisting of a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group), and R 24 represents a single bond or a (a + 1) -valent linking group.
- a represents an integer of 1 to 10
- B 1 existing in the formula (4) may be the same or different.
- Examples of the adsorption site represented by B 1 include those similar to the adsorption site constituting A 2 of the above formula (S), and preferred examples are also the same.
- a partial structure selected from the group consisting of an organic dye structure, a heterocyclic structure, an acid group, a group having a basic nitrogen atom, a urea group, and a hydrocarbon group having 4 or more carbon atoms is preferable, and an acid group is particularly preferable preferable.
- R 24 represents a single bond or a (a + 1) -valent linking group
- a represents an integer of 1 to 10, preferably an integer of 1 to 7, more preferably an integer of 1 to 5, An integer of 1 to 3 is particularly preferable.
- (A + 1) valent linking groups include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, In addition, a group composed of 0 to 20 sulfur atoms is included, which may be unsubstituted or may further have a substituent.
- (a + 1) -valent linking group examples include the following structural units or groups formed by combining the structural units (which may form a ring structure).
- R 24 may be a single bond or 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to 100 hydrogen atoms, And a (a + 1) -valent linking group consisting of 0 to 10 sulfur atoms, preferably a single bond or 1 to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 More preferred are (a + 1) -valent linking groups consisting of from 1 to 15 oxygen atoms, from 1 to 50 hydrogen atoms, and from 0 to 7 sulfur atoms, a single bond or from 1 to 10 Consisting of up to 5 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms ( The a + 1) -valent linking group is particularly preferable.
- examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, and a naphthyl group.
- Carbons having 1 to 6 carbon atoms such as aryl groups, hydroxyl groups, amino groups, carboxy groups, sulfonamido groups, N-sulfonylamido groups, acetoxy groups, etc. having 6 to 16 carbon atoms, methoxy groups, ethoxy groups, etc.
- R 4 and R 5 each independently represents a single bond or a divalent linking group.
- n R 4 s may be the same or different.
- m R 5 s may be the same or different.
- Examples of the divalent linking group in R 4 and R 5 include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, and 1 to 200. And a group consisting of 0 to 20 sulfur atoms, may be unsubstituted or may further have a substituent.
- divalent linking group examples include the following structural units or groups formed by combining the structural units.
- R 4 and R 5 are each independently a single bond, or 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to 100 Divalent linking groups consisting of up to 10 hydrogen atoms and 0 to 10 sulfur atoms are preferred, single bonds or 1 to 30 carbon atoms, 0 to 6 nitrogen atoms More preferred are divalent linking groups consisting of atoms, 0 to 15 oxygen atoms, 1 to 50 hydrogen atoms, and 0 to 7 sulfur atoms, a single bond or 1 From 0 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms. Particularly preferred are divalent linking groups.
- examples of the substituent include carbon numbers such as an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, and a naphthyl group. 1 to 6 carbon atoms such as aryl group, hydroxyl group, amino group, carboxy group, sulfonamido group, N-sulfonylamido group, acetoxy group and the like having 6 to 16 carbon atoms, methoxy group, ethoxy group, etc.
- alkoxy groups such as chlorine and bromine atoms
- alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group, cyclohexyloxycarbonyl group, cyano group, and t-butyl carbonate group And the like, and the like.
- R 3 represents a (m + n) -valent linking group.
- m + n satisfies 3 to 10.
- the (m + n) -valent linking group represented by R 3 includes 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to Groups comprising up to 100 hydrogen atoms and 0 to 20 sulfur atoms are included, which may be unsubstituted or may further have a substituent.
- (M + n) -valent linking group includes 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 40 oxygen atoms, 1 to 120 hydrogen atoms, And preferred are groups consisting of 0 to 10 sulfur atoms, preferably 1 to 50 carbon atoms, 0 to 10 nitrogen atoms, 0 to 30 oxygen atoms, 1 to More preferred are groups consisting of up to 100 hydrogen atoms and 0 to 7 sulfur atoms, 1 to 40 carbon atoms, 0 to 8 nitrogen atoms, 0 to 20 atoms. Particularly preferred are groups consisting of up to oxygen atoms, 1 to 80 hydrogen atoms, and 0 to 5 sulfur atoms.
- examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, and a naphthyl group.
- Carbons having 1 to 6 carbon atoms such as aryl groups, hydroxyl groups, amino groups, carboxy groups, sulfonamido groups, N-sulfonylamido groups, acetoxy groups, etc. having 6 to 16 carbon atoms, methoxy groups, ethoxy groups, etc.
- the most preferable (m + n) -valent linking group is the following group from the viewpoint of availability of raw materials, ease of synthesis, and solubility in various solvents.
- n 2 to 9. n is preferably 2 to 8, more preferably 2 to 7, and particularly preferably 3 to 6.
- P 2 in the formula (S) represents a polymer skeleton and can be selected from known polymers according to the purpose and the like.
- M P 2 present in the formula (S) may be the same or different.
- polymers in order to constitute a polymer skeleton, a polymer or copolymer of vinyl monomers, ester polymers, ether polymers, urethane polymers, amide polymers, epoxy polymers, silicone polymers, and these Modified products or copolymers of [for example, polyether / polyurethane copolymers, copolymers of polyether / vinyl monomers, etc. (any of random copolymers, block copolymers, and graft copolymers). May be included).
- the polymer is preferably soluble in an organic solvent.
- Component S is preferably soluble in an organic solvent.
- the polymer skeleton in P 2 preferably has at least one acid group.
- the polymer skeleton in P 2 preferably has no acid group.
- the polymer having an acid group constituting the polymer skeleton include, for example, a polyamidoamine and salt thereof, a polycarboxylic acid and salt thereof, a high molecular weight unsaturated acid ester, a modified polyurethane, a modified polyester, and a modified polymer having an acid group.
- a (meth) acrylic acid copolymer is preferable.
- the means for introducing an acid group into the polymer skeleton is not particularly limited.
- a means for introducing an acid group with a vinyl monomer, a means for introducing an acid group using a crosslinkable side chain, and the like are adopted.
- the mode in which the acid group is introduced by the constitution of the polymer skeleton including a structural unit derived from a vinyl monomer having an acid group makes it easy to control the amount of acid group introduced.
- the “acid group” may be the same as those mentioned as the “acid group” in the description of A 2 above, and is preferably a carboxy group.
- vinyl monomer For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides Styrenes, vinyl ethers, vinyl ketones, olefins, maleimides, (meth) acrylonitrile, vinyl monomers having an acid group, and the like are preferable.
- acrylic acid esters crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters
- (meth) acrylamides Styrenes vinyl ethers, vinyl ketones, olefins, maleimides, (meth) acrylonitrile, vinyl monomers having an acid group, and the like are preferable.
- preferable examples of these vinyl monomers will be described.
- Examples of (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, amyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2-Methylhexyl acrylate, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, (meth
- Examples of the crotonic acid esters include butyl crotonic acid and hexyl crotonic acid.
- Examples of vinyl esters include vinyl acetate, vinyl chloroacetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.
- Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.
- Examples of fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.
- Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.
- (Meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn-butyl Acrylic (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N -Diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-nitrophenyl acrylamide, N-ethyl-N-phenyl acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide, N- Methylo Le acrylamide, N- hydroxy
- styrenes examples include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethyl
- styrene examples include styrene, hydroxystyrene protected with a group deprotectable by an acidic substance (for example, t-butoxycarbonyl group (t-Boc), etc.), methyl vinylbenzoate, and ⁇ -methylstyrene.
- Examples of vinyl ethers include methyl vinyl ether, ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, methoxyethyl vinyl ether, and phenyl vinyl ether.
- Examples of vinyl ketones include methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
- Examples of olefins include ethylene, propylene, isobutylene, butadiene, isoprene and the like.
- Examples of maleimides include maleimide, butyl maleimide, cyclohexyl maleimide, and phenyl maleimide.
- (meth) acrylonitrile heterocyclic compounds substituted with vinyl groups (eg, vinylpyridine, N-vinylpyrrolidone, vinylcarbazole, etc.), N-vinylformamide, N-vinylacetamide, N-vinylimidazole, vinylcaprolactone, etc. it can.
- vinyl groups eg, vinylpyridine, N-vinylpyrrolidone, vinylcarbazole, etc.
- N-vinylformamide N-vinylacetamide
- N-vinylimidazole N-vinylimidazole
- vinylcaprolactone etc. it can.
- vinyl monomers having a functional group such as a urethane group, a urea group, a sulfonamide group, a phenol group, and an imide group can also be used.
- a monomer having a urethane group or urea group can be appropriately synthesized by utilizing an addition reaction between an isocyanate group and a hydroxyl group or an amino group, for example.
- an addition reaction between an isocyanate group-containing monomer and a compound containing one hydroxyl group, or a compound containing one primary or secondary amino group, or a hydroxyl group-containing monomer, primary or It can be appropriately synthesized by an addition reaction between a secondary amino group-containing monomer and monoisocyanate.
- vinyl monomer having an acid group used for introducing an acid group into the polymer skeleton P 2
- vinyl monomer having an acid group examples include a vinyl monomer having a carboxy group and a vinyl monomer having a sulfonic acid group.
- vinyl monomer having a carboxy group examples include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer.
- an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ⁇ -carboxypolycaprolactone mono (Meth) acrylate and the like can also be used.
- a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ⁇ -carboxypolycaprolactone mono (Meth) acrylate and the like
- anhydride containing monomers such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxy group.
- (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, and the like.
- Examples of the vinyl monomer having a sulfonic acid group include 2-acrylamido-2-methylpropanesulfonic acid, and examples of the vinyl monomer having a phosphoric acid group include phosphoric acid mono (2-acryloyloxyethyl ester) and phosphoric acid mono (1-methyl-2-acryloyloxyethyl ester) and the like.
- the vinyl monomer having an acid group a vinyl monomer containing a phenolic hydroxy group or a vinyl monomer containing a sulfonamide group can be used.
- the polymer skeleton P 2 includes a monomer unit derived from a vinyl monomer containing an acid group
- the content of the monomer unit derived from a vinyl monomer having an acid group in the polymer skeleton is expressed in terms of mass in the entire polymer skeleton.
- the content is preferably 3% by mass to 40% by mass, and more preferably in the range of 5% by mass to 20% by mass.
- R 3 Specific example (1), (2), (10), (11), (16) or (17) above
- R 4 a single bond, or the following structural unit or a combination of the structural units: “1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10”
- a divalent linking group comprising an oxygen atom, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms (which may have a substituent,
- an alkyl group having 1 to 20 carbon atoms such as a methyl group or an ethyl group
- an aryl group having 6 to 16 carbon atoms such as a phenyl group or a naphthyl group, a hydroxyl group, an amino group, a carboxy group, a sulfonamide group, N— C1-C
- R 5 single bond, ethylene group, propylene group, the following group (a) or the following group (b)
- R 12 represents a hydrogen atom or a methyl group
- L represents 1 or 2.
- P 2 a copolymer of a vinyl monomer having a carboxy group and another vinyl monomer; a polymer or copolymer of a vinyl monomer having no acid group; an ester-based polymer, an ether-based polymer, and a urethane-based polymer; and A polymer m selected from the group consisting of these modified products and may contain at least one acid group: 0.5-3 n: 3-6
- the content of acid groups in the component S is appropriately determined depending on the acid value of the component S.
- the acid value of component S is preferably 20 to 300 mgKOH / g, more preferably 50 to 250 mgKOH / g, and particularly preferably 50 to 210 mgKOH / g.
- the acid value is 20 mgKOH / g or more, sufficient alkali developability of the photosensitive resin composition is obtained, and when the acid value is 300 mgKOH / g or less, the dispersibility and dispersion stability of the metal oxide particles are improved. Excellent.
- the molecular weight of component S is preferably 2,000 to 200,000, more preferably 2,000 to 15,000, and particularly preferably 2,500 to 10,000 in terms of weight average molecular weight.
- the weight average molecular weight is within the above range, the effects of the plurality of adsorption sites introduced at the ends of the polymer are sufficiently exhibited, and the adsorptivity to the solid surface is exhibited.
- the resin composition of this invention contains the component S, the component S to contain may be only 1 type, and 2 or more types may be sufficient as it. In the case of two or more types, the total is preferably in the above range.
- exemplary compounds of component S will be listed, but the present invention is not limited thereto, and can take any structure as long as it is included in formula (S).
- P1 and P2 can take arbitrary values in terms of mass.
- the polymer chain in the following compound may be bonded to any monomer unit with a sulfur atom, and when the polymer chain includes two types of monomer units, even if the polymer chain is obtained by random polymerization, It may be a block copolymer chain.
- the content ratio (P1: P2) of the monomer unit having a carboxylic acid ester and the monomer unit having a carboxy group in the polymer skeleton is in the range of 100: 0 to 80:20 in terms of mass. It is preferable that Moreover, the structure of the other end of the polymer chain in the exemplified compound is not particularly limited, and may be a known structure.
- Component S can be synthesized, for example, with reference to the methods described in Japanese Patent No. 5036269 and Japanese Patent No. 5171005.
- a dispersing agent may be used individually by 1 type, or may be used together 2 or more types.
- the content of the dispersant in the photosensitive resin composition of the present invention is preferably in the range of 5 to 70% by mass and more preferably in the range of 10 to 50% by mass with respect to the total solid content of the photosensitive resin composition.
- the photosensitive resin composition of the present invention preferably contains (Component G) a crosslinking agent, if necessary.
- a crosslinking agent By adding a crosslinking agent, the cured film obtained by the photosensitive resin composition of the present invention can be made a stronger film.
- the crosslinking agent is not limited as long as it causes a crosslinking reaction by heat (except for component D). That is, a thermal crosslinking agent is preferably used as the crosslinking agent.
- the addition amount of the crosslinking agent in the photosensitive resin composition of the present invention is preferably 0.01 to 50 parts by mass, and preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive resin composition.
- the amount is more preferably part by mass, and further preferably 0.5 to 20 parts by mass. By adding in this range, a cured film excellent in mechanical strength and solvent resistance can be obtained.
- a plurality of crosslinking agents may be used in combination. In that case, the content is calculated by adding all the crosslinking agents.
- JER152, JER157S70, JER157S65, JER806, JER828, JER1007 manufactured by Mitsubishi Chemical Holdings Co., Ltd.
- ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S aboveve, manufactured by ADEKA Corporation
- NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN- 502 aboveve, manufactured by ADEKA Corporation
- bisphenol A type epoxy resins bisphenol F type epoxy resins, phenol novolac type epoxy resins and aliphatic epoxy resins are more preferable, and bisphenol A type epoxy resins are particularly preferable.
- Aron oxetane OXT-121, OXT-221, OX-SQ, PNOX manufactured by Toagosei Co., Ltd.
- the compound containing an oxetanyl group individually or in mixture with the compound containing an epoxy group.
- alkoxymethyl group-containing crosslinking agents described in paragraphs 0107 to 0108 of JP2012-8223A, compounds having at least one ethylenically unsaturated double bond, and the like are also preferably used. be able to.
- alkoxymethyl group-containing crosslinking agent alkoxymethylated glycoluril is preferable.
- a blocked isocyanate compound can also be preferably employed as a crosslinking agent.
- the blocked isocyanate compound is not particularly limited as long as it is a compound having a blocked isocyanate group, but is preferably a compound having two or more blocked isocyanate groups in one molecule from the viewpoint of curability.
- the blocked isocyanate group in this invention is a group which can produce
- the group which reacted the blocking agent and the isocyanate group and protected the isocyanate group can illustrate preferably.
- the blocked isocyanate group is preferably a group capable of generating an isocyanate group by heat at 90 ° C. to 250 ° C.
- the skeleton of the blocked isocyanate compound is not particularly limited and may be any as long as it has two isocyanate groups in one molecule, and is aliphatic, alicyclic or aromatic.
- Polyisocyanates may be used, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetramethylene Diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2, '-Diethyl ether diisocyanate, diphenylmethane-4,4'-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, methylene bis (cyclohexyl isocyanate), cyclohexane-1,3
- TDI tolylene diisocyanate
- MDI diphenylmethane diisocyanate
- HDI hexamethylene diisocyanate
- IPDI isophorone diisocyanate
- Examples of the matrix structure of the blocked isocyanate compound in the photosensitive resin composition of the present invention include biuret type, isocyanurate type, adduct type, and bifunctional prepolymer type.
- Examples of the blocking agent that forms the block structure of the blocked isocyanate compound include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds. be able to.
- a blocking agent selected from oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, and pyrazole compounds is particularly preferable.
- Examples of the oxime compound include aldoxime and ketoxime, and specific examples include acetoxime, formaldoxime, cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone oxime, and benzophenone oxime.
- Examples of the lactam compound include ⁇ -caprolactam and ⁇ -butyrolactam.
- Examples of the phenol compound include phenol, naphthol, cresol, xylenol, and halogen-substituted phenol.
- Examples of the alcohol compound include methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, and alkyl lactate.
- amine compound a primary amine and a secondary amine are mentioned, Any of an aromatic amine, an aliphatic amine, and an alicyclic amine may be sufficient, An aniline, diphenylamine, ethyleneimine, polyethyleneimine etc. can be illustrated.
- Examples of the active methylene compound include diethyl malonate, dimethyl malonate, ethyl acetoacetate, methyl acetoacetate and the like.
- pyrazole compound include pyrazole, methylpyrazole, dimethylpyrazole and the like.
- the mercaptan compound include alkyl mercaptans and aryl mercaptans.
- the blocked isocyanate compound that can be used in the photosensitive resin composition of the present invention is commercially available.
- Coronate AP Stable M Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (or more, Nippon Polyurethane Industry Co., Ltd.), Takenate B-830, B-815N, B-820NSU, B-842N, B-84N, B-870N, B-874N, B-882N (above, manufactured by Mitsui Chemicals, Inc.) ), Duranate 17B-60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000 (above , Manufactured by Asahi Kasei Chemicals Corporation, Death Module B 1100, BL1265 MPA / X, BL
- the photosensitive resin composition of the present invention may contain (Component H) an alkoxysilane compound (also simply referred to as “silane compound”).
- an alkoxysilane compound also simply referred to as “silane compound”.
- the (component H) alkoxysilane compound that can be used in the photosensitive resin composition of the present invention is an inorganic material serving as a substrate, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, gold, copper, molybdenum, titanium, A compound that improves the adhesion between a metal such as aluminum and the insulating film is preferable. Specifically, a known silane coupling agent or the like is also effective.
- silane coupling agents include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -glycidoxypropyltrialkoxysilane, ⁇ -glycidoxypropylalkyldialkoxysilane, and ⁇ -methacryloxy.
- ⁇ -glycidoxypropyltrialkoxysilane and ⁇ -methacryloxypropyltrialkoxysilane are more preferable, ⁇ -glycidoxypropyltrialkoxysilane is more preferable, and 3-glycidoxypropyltrimethoxysilane is particularly preferable. preferable. These can be used alone or in combination of two or more.
- R 1 is a hydrocarbon group having 1 to 20 carbon atoms having no reactive group
- R 2 is an alkyl group having 1 to 3 carbon atoms or a phenyl group
- n is an integer of 1 to 3 is there.
- Specific examples include the following compounds. Ph represents a phenyl group.
- the (component H) alkoxysilane compound in the photosensitive resin composition of the present invention is not particularly limited, and known compounds can be used.
- the content of the alkoxysilane compound in the photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by mass, and 0.5 to 20 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition. Part is more preferred.
- the photosensitive resin composition of the present invention preferably contains a sensitizer in order to promote its decomposition in combination with (Component E) a photoacid generator.
- the sensitizer absorbs actinic rays or radiation and enters an electronically excited state.
- the sensitizer in an electronically excited state comes into contact with the photoacid generator, and effects such as electron transfer, energy transfer, and heat generation occur.
- a photo-acid generator raise
- Examples of preferred sensitizers include compounds belonging to the following compounds and having an absorption wavelength in any of the wavelength ranges from 350 nm to 450 nm.
- Polynuclear aromatics eg, pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10-dipropyloxyanthracene
- xanthenes Eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal
- xanthones eg, xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone
- cyanines eg, thiacarbocyanine, oxacarbocyanine
- merocyanines Eg, merocyanine, carbomerocyanine
- rhodocyanines oxonols
- thiazines eg, thionine, methylene blue,
- polynuclear aromatics polynuclear aromatics, acridones, styryls, base styryls, and coumarins are preferable, and polynuclear aromatics are more preferable.
- polynuclear aromatics anthracene derivatives are most preferred.
- the addition amount of the sensitizer in the photosensitive resin composition of the present invention is preferably 0 to 1,000 parts by mass with respect to 100 parts by mass of the photoacid generator in the photosensitive resin composition.
- the amount is more preferably 500 parts by mass, and further preferably 50 to 200 parts by mass.
- a sensitizer may be used individually by 1 type and can also use 2 or more types together.
- the photosensitive resin composition of the present invention may contain (Component J) a basic compound.
- the basic compound can be arbitrarily selected from those used in chemically amplified resists. Examples include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like. Specific examples thereof include compounds described in paragraphs 0204 to 0207 of JP2011-221494A.
- aliphatic amine examples include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and the like.
- examples include ethanolamine, dicyclohexylamine, and dicyclohexylmethylamine.
- aromatic amine examples include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.
- heterocyclic amine examples include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine, Pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, N-cyclohexyl-N ′-[2- (4-morpholinyl) ethyl] thiourea, 1,5-diazabicyclo [4.3.0 ] -5-Nonene, 1,8-di And azabicyclo
- Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, tetra-n-hexylammonium hydroxide, and the like.
- Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, tetra-n-butylammonium benzoate and the like.
- heterocyclic amines are preferable, and 2,4,5-triphenylimidazole and / or N-cyclohexyl-N ′-[2- (4-morpholinyl) ethyl] thiourea is particularly preferable.
- the basic compounds that can be used in the present invention may be used singly or in combination of two or more.
- the content of the basic compound in the photosensitive resin composition of the present invention is preferably 0.001 to 3 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition, 0.005 More preferred is 1 part by mass.
- the photosensitive resin composition of the present invention may contain (Component K) a surfactant.
- a surfactant any of anionic, cationic, nonionic or amphoteric can be used, but a preferred surfactant is a nonionic surfactant.
- examples of the surfactant used in the composition of the present invention include those described in paragraphs 0201 to 0205 in JP2012-88459A and those described in paragraphs 0185 to 0188 in JP2011-215580A. And these descriptions are incorporated herein.
- nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. .
- the following trade names are KP-341, X-22-822 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No.
- the surfactant includes a structural unit A and a structural unit B represented by the following formula (K-1), and the weight in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent.
- K-1 the weight in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent.
- Preferred examples include copolymers having an average molecular weight (Mw) of 1,000 or more and 10,000 or less.
- R 401 and R 403 each independently represent a hydrogen atom or a methyl group
- R 402 represents a linear alkylene group having 1 to 4 carbon atoms
- R 404 represents a hydrogen atom or Represents an alkyl group having 1 to 4 carbon atoms
- L represents an alkylene group having 3 to 6 carbon atoms
- p and q are mass percentages representing a polymerization ratio
- p is 10 mass% to 80 mass%.
- a numerical value is represented, q represents a numerical value of 20 mass% or more and 90 mass% or less, r represents an integer of 1 or more and 18 or less, and s represents an integer of 1 or more and 10 or less.
- L is preferably a branched alkylene group represented by the following formula (K-2).
- R 405 in formula (J-2) represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability to the coated surface. Two or three alkyl groups are more preferred.
- the weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.
- the addition amount of the surfactant in the photosensitive resin composition of the present invention is preferably 10 parts by mass or less, and 0.001 to 10 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition. More preferably, the amount is 0.01 to 3 parts by mass.
- the photosensitive resin composition of the present invention preferably contains (Component L) a heterocyclic compound having two or more nitrogen atoms.
- Component L When the component L is adsorbed on the surface of the inorganic particles, electrostatic repulsion and steric repulsion between the inorganic particles are caused, and in particular, the haze is reduced in order to prevent aggregation of the inorganic particles when the composition is applied and dried. Presumed.
- a part of the compound corresponding to component L also corresponds to component J described above.
- Component L is not particularly limited except that it has two or more nitrogen atoms, but is preferably a heterocyclic compound having two or more nitrogen atoms as a ring member of the heterocyclic ring, and nitrogen at the 1,3-position.
- a compound having a heterocyclic structure having at least an atom is more preferable, and a compound having a 5-membered or 6-membered heterocyclic structure having at least a nitrogen atom at the 1,3-positions is more preferable. If it is the said aspect, the hardened
- heterocyclic structure having at least a nitrogen atom at positions 1 and 3 may be a structure in which nitrogen atoms are bonded to both sides of a carbon atom in the heterocyclic ring. It does not have to be in the third or third place.
- the ring member of the heterocyclic ring in component L is preferably composed of at least a carbon atom and a nitrogen atom, and may further contain an oxygen atom or a sulfur atom as a ring member, but consists of a carbon atom and a nitrogen atom. Is particularly preferred.
- the number of nitrogen atoms contained in the component L is 2 or more, preferably 2 to 6, and more preferably 2 to 4.
- Component L preferably has 2 to 4 nitrogen atoms, more preferably 2 or 3 as ring members of the heterocyclic ring, and more preferably 2 members. Further preferred.
- the heterocyclic ring in component L may be a saturated heterocyclic ring, an unsaturated heterocyclic ring, or an aromatic heterocyclic ring.
- the heterocyclic ring in component L may be further condensed with another ring.
- as said other ring not only a heterocyclic ring but an aliphatic ring or an aromatic ring may be sufficient.
- heterocyclic structure of component L include imidazole structure, benzimidazole structure, 1,2,4-triazole structure, 4,5-dihydro-1,2,4-triazole structure, tetrazole structure, 2-imidazoline.
- Preferred examples thereof include a ring structure selected from the group consisting of a structure, 4-imidazoline structure (2,3-dihydroimidazole structure), imidazolidine structure, pyrimidine structure, quinoxaline structure, purine structure, pteridine structure, and peridimine structure, Imidazole structure, benzimidazole structure, 1,2,4-triazole structure, 4,5-dihydro-1,2,4-triazole structure, tetrazole structure, 2-imidazoline structure, 4-imidazoline structure, imidazolidine structure, and A ring structure selected from the group consisting of pyrimidine structures Mentioned
- benzimidazole structure or imidazolidine structure are exemplified particularly preferred. If it is the said aspect, the hardened
- Component L preferably has a mercapto group (—SH) or a thioxo group ( ⁇ S). If it is the said aspect, the hardened
- Component L is preferably a compound represented by the following formula (La).
- R a1 and R a2 each independently represents a hydrogen atom, a halogen atom or a monovalent organic group, and R a1 and R a2 are bonded to form a divalent organic group.
- R a3 and R a4 each independently represents a hydrogen atom or a monovalent organic group
- L a1 represents a divalent linking group forming a 5-membered or 6-membered ring
- R a3 or R a a4 and L a1 may be bonded to form a ring
- the dotted bond indicates that when the nitrogen-containing double bond described by the dotted line is present, R a2 and R a4 are not present.
- the nitrogen-containing double bond represented by the dotted line is not present, it represents that R a2 and R a4 are present.
- Examples of the monovalent organic group in R a1 to R a4 include an alkyl group (including a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group, Aryl group, heterocyclic group (also called heterocyclic group), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group , Alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including alkylamino group, arylamino group, heterocyclic amino group), ammonio group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonyl Amino group,
- a mercapto group is particularly preferable as the monovalent organic group for R a1 and R a2 .
- the carbon number of the monovalent organic group in R a1 and R a2 is preferably 0 to 20, more preferably 0 to 8, and particularly preferably 0.
- Examples of the divalent organic group formed by combining R a1 and R a2 include an oxo group, a thioxo group, and an alkylidene group. Of these, a thioxo group is particularly preferable.
- R a1 and R a2 are each independently preferably a hydrogen atom or a mercapto group, and when R a1 and R a2 are combined to form a divalent organic group, they are thioxo groups. Is particularly preferred.
- the monovalent organic group for R a3 and R a4 is preferably an alkyl group or an aryl group, more preferably a morpholinomethyl group or a phenyl group.
- the alkyl group or aryl group may be substituted with a substituent.
- the carbon number of the monovalent organic group in R a3 and R a4 is preferably 0 to 20, more preferably 1 to 10, and still more preferably 4 to 8.
- R a3 and R a4 are each independently preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom, a methyl group, a morpholinomethyl group or a phenyl group, and a hydrogen atom, a methyl group or A phenyl group is more preferable, and a hydrogen atom or a methyl group is particularly preferable.
- L a1 represents a divalent linking group forming a 5-membered ring or a 6-membered ring, and forms a heterocyclic ring together with the carbon atom and the two nitrogen atoms in the formula (La).
- the divalent linking group is not particularly limited as long as it is a group that forms a 5-membered heterocyclic ring or a 6-membered heterocyclic ring with the carbon atom and the two nitrogen atoms in the formula (La). Is preferably a group formed from a carbon atom and / or a nitrogen atom, and more preferably a group forming a specific example of the heterocyclic structure described above.
- a group that forms a benzimidazole structure that is, a 1,2-phenylene group, a group that forms an imidazolidine structure, that is, a 1,2-ethylene group, a 1,1-dimethyl-1,2-ethylene group, or And more preferably an ethene-1,2-diyl group, and a 1,2-ethylene group, a 1,1-dimethyl-1,2-ethylene group, or an ethene-1,2-diyl group.
- a group that forms a benzimidazole structure that is, a 1,2-phenylene group
- a group that forms an imidazolidine structure that is, a 1,2-ethylene group, a 1,1-dimethyl-1,2-ethylene group, or And more preferably an ethene-1,2-diyl group, and a 1,2-ethylene group, a 1,1-dimethyl-1,2-ethylene group, or an ethene-1,2-diyl group.
- component L is more preferably a compound represented by the following formula (La-1) or formula (La-2).
- R a6 to R a8 each independently represents a hydrogen atom or a monovalent organic group
- L a2 and L a3 each independently Represents a divalent linking group that forms a 5-membered or 6-membered ring
- R a6 and L a2 may be bonded to form a ring
- R a7 or R a8 and L a3 are bonded And may form a ring.
- R a6 to R a8 in formula ( La -1) or ( La -2) have the same meanings as R a3 and R a4 in formula ( La ), and the preferred embodiments are also the same.
- L a2 and L a3 in Formula (L-a1) or formula (L-a2) has the same meaning as L a1 in formula (L-a), preferable embodiments thereof are also the same.
- Preferred specific examples (AF-1 to AF-14) of component L are shown below. However, the present invention is not limited to these.
- AF-3 to AF-14 are preferable, AF-3, AF-5, AF-6, AF-9, AF-12, AF-13 or AF-14 are more preferable, and AF-5, AF -9, AF-12, AF-13 or AF-14 is more preferred, and AF-9, AF-12, AF-13 or AF-14 is particularly preferred.
- component L may be used individually by 1 type, and can also use 2 or more types together.
- the content of component L in the photosensitive resin composition of the present invention is preferably 0.1 to 20% by mass, preferably 0.5 to 15%, based on the total solid content of the photosensitive resin composition of the present invention. More preferably, it is more preferably 0.5 to 10% by mass. When it is in the above range, a cured product having excellent dispersibility of the inorganic particles and smaller haze can be obtained.
- the photosensitive resin composition of the present invention includes an antioxidant, an ultraviolet absorber, a metal deactivator, an acid proliferator, a development accelerator, a plasticizer, and generation of thermal radicals as necessary.
- Known additives such as an agent, a thermal acid generator, a thickener, and an organic or inorganic suspending agent can be added.
- the descriptions in paragraphs 0201 to 0224 of JP2012-8859A can be referred to, and the contents thereof are incorporated in the present specification.
- the photosensitive resin composition of the present invention preferably contains an antioxidant.
- an antioxidant a well-known antioxidant can be contained. By adding an antioxidant, there is an advantage that coloring of the cured film can be prevented, or a decrease in film thickness due to decomposition can be reduced, and heat resistant transparency is excellent.
- antioxidants include phosphorus antioxidants, amides, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenolic antioxidants, ascorbic acids, zinc sulfate, sugars, Examples thereof include nitrates, sulfites, thiosulfates, and hydroxylamine derivatives.
- phenolic antioxidants hindered amine antioxidants, phosphorus antioxidants, amide antioxidants, hydrazide antioxidants, sulfur oxidations are particularly preferred from the viewpoint of coloring of the cured film and reduction of the film thickness.
- Inhibitors are preferred, and phenolic antioxidants are most preferred. These may be used individually by 1 type and may mix 2 or more types. Specific examples include the compounds described in paragraphs 0026 to 0031 of JP-A-2005-29515 and paragraphs 0106 to 0116 of JP-A-2011-227106, the contents of which are incorporated herein. .
- antioxidants examples include ADK STAB AO-15, ADK STAB AO-18, ADK STAB AO-20, ADK STAB AO-23, ADK STAB AO-30, ADK STAB AO-37, ADK STAB AO-40 and ADK STAB AO-50.
- ADK STAB AO-51 ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO-330, ADK STAB AO-412S, ADK STAB AO-503, ADK STAB A-611, ADK STAB A-612, ADK STAB A-613 , ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-8W, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB PEP-36Z, ADK STAB HP-10, ADK STAB 2112, ADK STAB 260, ADK STAB 1522, ADK STAB 1178, ADK STAB 1500, ADK STAB C, ADK STAB 135A, ADK STAB 3010, ADK STAB TPP, ADK STAB CDA-1, ADK STAB CDA-6, ADK STAB ZS-27, ADK STAB ZS-90, ADKS TAB 91 (above
- the content of the antioxidant is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, based on the total solid content of the photosensitive resin composition. It is particularly preferably 5 to 4% by mass. By setting it within this range, sufficient transparency of the formed film can be obtained, and the sensitivity at the time of pattern formation can be improved.
- various ultraviolet absorbers described in “New Development of Polymer Additives” (Nikkan Kogyo Shimbun Co., Ltd.), metal deactivators, and the like are used in the present invention. You may add to a resin composition.
- the photosensitive resin composition of the present invention may use an acid proliferating agent for the purpose of improving sensitivity.
- the acid proliferating agent that can be used in the present invention is a compound that can further generate an acid by an acid-catalyzed reaction to increase the acid concentration in the reaction system, and is a compound that exists stably in the absence of an acid. is there.
- Specific examples of such an acid proliferating agent include the acid proliferating agents described in paragraphs 0226 to 0228 of JP2011-221494A, the contents of which are incorporated herein.
- the content of the acid proliferating agent in the photosensitive resin composition is 10 to 1,000 parts by mass with respect to 100 parts by mass of the photoacid generator. From the viewpoint of dissolution contrast between the exposed part and the unexposed part. And more preferably 20 to 500 parts by mass.
- the photosensitive resin composition of the present invention can contain a development accelerator.
- a development accelerator any compound having a development acceleration effect can be used, and the development accelerator may be a compound having at least one structure selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, and an alkyleneoxy group.
- a compound having a carboxyl group or a phenolic hydroxyl group is more preferable, and a compound having a phenolic hydroxyl group is most preferable.
- the description in paragraphs 0171 to 0172 of JP2012-042837A can be referred to, and the contents thereof are incorporated in the present specification.
- a development accelerator may be used individually by 1 type, and can also use 2 or more types together.
- the addition amount of the development accelerator in the photosensitive resin composition of the present invention is preferably 0 to 30 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive resin composition, from the viewpoint of sensitivity and residual film ratio. More preferably, it is 1 to 20 parts by mass, and most preferably 0.5 to 10 parts by mass.
- the molecular weight of the development accelerator is preferably from 100 to 2,000, more preferably from 150 to 1,500, still more preferably from 150 to 1,000.
- the resin composition of the present invention may contain a plasticizer.
- the plasticizer include dibutyl phthalate, dioctyl phthalate, didodecyl phthalate, polyethylene glycol, glycerin, dimethyl glycerin phthalate, dibutyl tartrate, dioctyl adipate, and triacetyl glycerin.
- the plasticizer content in the resin composition of the present invention is preferably 0.1 to 30 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the component A content. .
- thermal radical generators described in paragraphs 0120 to 0121 of JP2012-8223A, and the nitrogen-containing compounds and thermal acid generators described in International Publication No. 2011-136004 may be used. The contents of which are incorporated herein by reference.
- a resin composition can be prepared by preparing a liquid in which the components are previously dissolved or dispersed in a solvent and then mixing them in a predetermined ratio.
- the composition prepared as described above can be used after being filtered using, for example, a filter having a pore size of 0.2 ⁇ m.
- a metal oxide particle dispersion containing (Component A) metal oxide particles, (Component C) solvent, and (Component F) dispersant is prepared in advance. It is particularly preferable to prepare a photosensitive resin composition by adding Component B, Component D and Component E, and an optional component.
- the resin pattern manufacturing method of the present invention preferably includes the following steps (1) to (4), and more preferably includes the following steps (1) to (5).
- a coating process for coating the photosensitive resin composition of the present invention on a substrate (2) a solvent removal step of removing the solvent from the applied resin composition; (3) An exposure step of exposing the resin composition from which the solvent has been removed to a pattern with actinic rays; (4) Development step of developing the exposed resin composition with an aqueous developer; (5) A heat treatment step of heat-treating the developed resin composition.
- the photosensitive resin composition of the present invention is preferably applied onto a substrate to form a wet film containing a solvent.
- substrate cleaning such as alkali cleaning or plasma cleaning
- the method for treating the substrate surface with hexamethyldisilazane is not particularly limited, and examples thereof include a method in which the substrate is exposed to hexamethyldisilazane vapor.
- the substrate examples include inorganic substrates, resins, resin composite materials, ITO, Cu substrates, polyethylene terephthalate, and plastic substrates such as cellulose triacetate (TAC).
- the inorganic substrate examples include glass, quartz, silicone, silicon nitride, and a composite substrate in which molybdenum, titanium, aluminum, copper, or the like is vapor-deposited on such a substrate.
- the resins include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamideimide, polyetherimide, poly Fluorine resins such as benzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, crosslinked fumaric acid diester resin, cyclic polyolefin, Is it a synthetic resin such as aromatic ether resin, maleimide-olefin resin, cellulose, episulfide resin, etc.
- all or part of the surface of the substrate is at least one selected from the group consisting of glass, SiO, ITO, IZO, a metal film, and a metal oxide film. It is particularly preferable that all or part of the surface of the substrate is ITO.
- ITO Indium Tin Oxide
- the photosensitive resin composition of the present invention has a very remarkable effect that generation of development residues can be suppressed even when all or part of the surface of the substrate is ITO.
- the coating method on the substrate is not particularly limited, and for example, a method such as an inkjet method, a slit coating method, a spray method, a roll coating method, a spin coating method, a casting coating method, a slit and spin method can be used. Furthermore, it is also possible to apply a so-called pre-wet method as described in JP-A-2009-145395.
- the coating film thickness is not particularly limited, and can be applied with a film thickness according to the application, but it is preferably used in the range of 0.5 to 10 ⁇ m.
- Ink jet method application compared with conventional application methods such as spin coating method and slit coating method, the amount of coating liquid used is greatly reduced, and the influence of mist adhering to the spin coating method is reduced. This is preferable from a comprehensive point of view, for example, generation of foreign matter is suppressed.
- the application conditions by the ink jet method may be appropriately selected depending on the composition of the photosensitive resin composition, the type of coating film to be manufactured, and the like.
- the discharge amount of the liquid photosensitive resin composition and the number of discharges to the same portion may be adjusted.
- what is necessary is just to select suitably the shape and position which apply
- the inkjet recording apparatus that can be used in the inkjet coating method is not particularly limited, and any known inkjet recording apparatus that can achieve the desired resolution can be selected and used. That is, if it is a well-known inkjet recording apparatus containing a commercial item, the application
- Examples of the ink jet recording apparatus that can be used in the present invention include an apparatus including a composition supply system and a temperature sensor.
- the ink supply system includes, for example, an original tank containing the photosensitive resin composition of the present invention, a supply pipe, a composition supply tank immediately before the inkjet head, a filter, and a piezo-type inkjet head.
- the piezo-type inkjet head preferably has a multi-size dot of 1 to 100 pl, more preferably 8 to 30 pl, preferably 320 ⁇ 320 to 4,000 ⁇ 4,000 dpi (dot per inch), more preferably 400 ⁇ 400.
- dpi represents the number of dots per 2.54 cm.
- the coating film thickness is not particularly limited, and can be applied with a film thickness according to the application, but it is preferably used in the range of 0.5 to 10 ⁇ m.
- the solvent removal step (2) it is preferable to form a dry coating film on the substrate by removing the solvent from the applied film by vacuum (vacuum) and / or heating.
- the heating conditions for the solvent removal step are preferably 70 to 130 ° C. and about 30 to 300 seconds. When the temperature and time are within the above ranges, the pattern adhesion is good and the residue can be reduced.
- the coating step (1) and the solvent removal step (2) may be performed in this order, simultaneously, or alternately. For example, after all of the inkjet application in the application step (1) is completed, the solvent removal step (2) may be performed, or the substrate is heated, and the photosensitive by the inkjet application method in the application step (1). The solvent may be removed while discharging the conductive resin composition. In particular, it is preferable to perform the solvent removal step (2) after all the inkjet coating in the coating step (1) is completed.
- the photoacid generator is decomposed to generate an acid.
- the acid-decomposable group contained in the coating film component is hydrolyzed to produce an acid group, for example, a carboxyl group or a phenolic hydroxyl group.
- an exposure light source using actinic light a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, etc.
- g-line (436 nm), i-line (365 nm), Actinic rays having a wavelength of 300 nm to 450 nm, such as 405 nm), can be preferably used.
- irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed.
- various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, and a laser exposure can be used.
- PEB Post Exposure Bake
- the temperature for performing PEB is preferably 30 ° C. or higher and 130 ° C. or lower, more preferably 40 ° C. or higher and 110 ° C. or lower, and particularly preferably 50 ° C. or higher and 100 ° C. or lower.
- the acid-decomposable group in the present invention has a low activation energy for acid decomposition and is easily decomposed by an acid derived from an acid generator by exposure to produce an acid group, for example, a carboxyl group or a phenolic hydroxyl group.
- a positive image can be formed by development without performing PEB.
- the developing step (4) it is preferable to develop a copolymer having a liberated acid group, for example, a carboxyl group or a phenolic hydroxyl group, using an alkaline developer.
- a positive image is formed by removing an exposed area containing a resin composition having an acid group that easily dissolves in an alkaline developer, such as a carboxyl group or a phenolic hydroxyl group.
- the developer used in the development step preferably contains a basic compound.
- Examples of the basic compound include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkalis such as sodium bicarbonate and potassium bicarbonate Metal bicarbonates; ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline hydroxide; aqueous solutions such as sodium silicate and sodium metasilicate can be used.
- An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.
- Preferred examples of the developer include a 0.4% by mass aqueous solution, a 0.5% by mass aqueous solution, a 0.7% by mass aqueous solution, or a 2.38% by mass aqueous solution of tetraethylammonium hydroxide.
- the pH of the developer is preferably 10.0 to 14.0.
- the development time is preferably 30 to 500 seconds, and the development method may be either a liquid piling method or a dipping method. After development, washing with running water can be performed for 30 to 300 seconds to form a desired pattern.
- a rinsing step can also be performed after development. In the rinsing step, the developed substrate and the development residue are removed by washing the developed substrate with pure water or the like.
- a known method can be used as the rinsing method. For example, a shower rinse, a dip rinse, etc. can be mentioned.
- the obtained positive image is heated to thermally decompose the acid-decomposable group to generate an acid group, for example, a carboxyl group or a phenolic hydroxyl group, and a crosslinkable group
- a cured film can be formed by crosslinking with a crosslinking agent or the like.
- This heating is performed using a heating device such as a hot plate or oven at a predetermined temperature, for example, 180 ° C. to 250 ° C. for a predetermined time, for example, 5 to 90 minutes on the hot plate, 30 to 120 minutes for the oven.
- a protective film and an interlayer insulating film having excellent heat resistance, hardness, and the like can be formed.
- the transparency can be improved by performing the heat treatment in a nitrogen atmosphere.
- heat treatment is preferably performed at 80 to 140 ° C. for 5 to 120 minutes.
- the heat treatment step can be performed after baking at a relatively low temperature (addition of a middle bake step).
- middle baking it is preferable to post-bake at a high temperature of 200 ° C. or higher after heating at 90 to 150 ° C. for 1 to 60 minutes.
- middle baking and post baking can be heated in three or more stages.
- the taper angle of the pattern can be adjusted by devising such middle baking and post baking.
- These heating methods can use well-known heating methods, such as a hotplate, oven, and an infrared heater.
- post-exposure the entire surface of the patterned substrate was re-exposed with actinic rays (post-exposure), and then post-baked to generate an acid from the photoacid generator present in the unexposed portion, thereby performing a crosslinking step. It can function as a catalyst to promote, and can accelerate the curing reaction of the film.
- the preferred exposure amount in the case of including a post-exposure step preferably 100 ⁇ 3,000mJ / cm 2, particularly preferably 100 ⁇ 500mJ / cm 2.
- the cured film obtained from the photosensitive resin composition of the present invention can also be used as a dry etching resist.
- dry etching processing such as ashing, plasma etching, ozone etching, or the like can be performed as the etching processing.
- the cured film of the present invention is a film obtained by curing the photosensitive resin composition of the present invention.
- the cured film of the present invention can be suitably used as an interlayer insulating film.
- the cured film of this invention is a film
- the photosensitive resin composition of the present invention an interlayer insulating film having excellent insulation and high transparency even when baked at high temperatures can be obtained. Since the interlayer insulating film using the photosensitive resin composition of the present invention has high transparency and excellent cured film properties, it is useful for applications of organic EL display devices, liquid crystal display devices, and touch panel display devices.
- the cured product of the present invention is a cured product obtained by curing the photosensitive resin composition of the present invention.
- the shape does not have to be a film, and may be any shape.
- the cured product of the present invention may be a cured product that has at least a part of the solvent removed from the photosensitive resin composition of the present invention to increase the hardness, but from the photosensitive resin composition of the present invention.
- a cured product obtained by removing the solvent and thermosetting is preferable.
- the production method of the cured product of the present invention is not particularly limited, but preferably includes at least the following steps (a) to (c) in this order.
- Step (c) is the same step as the heat treatment step except that the heat treatment target is a resin composition from which the solvent obtained in step (b) has been removed. Preferred embodiments such as time and heating means are also preferred.
- the cured product of the present invention is an optical member such as a microlens, an optical waveguide, an antireflection film, an organic EL or LED light extraction layer, an LED sealing material and an LED chip coating material, or a wiring used for a touch panel. It can be suitably used as a cured product for reducing the visibility of electrodes.
- the cured product of the present invention has a constant thickness of a planarizing film, an interlayer insulating film, a color filter protective film, and a liquid crystal layer in a liquid crystal display device as described later, for example, in a liquid crystal display device or an organic EL device. It can be suitably used for spacers for holding, structural members of MEMS (Micro Electro Mechanical Systems) devices, and the like.
- the liquid crystal display device of the present invention comprises the cured product of the present invention.
- the liquid crystal display device of the present invention is not particularly limited except that it has a planarizing film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and known liquid crystal display devices having various structures. Can be mentioned.
- specific examples of TFT (Thin-Film Transistor) included in the liquid crystal display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
- liquid crystal driving methods that can be taken by the liquid crystal display device of the present invention include TN (Twisted Nematic) method, VA (Vertical Alignment) method, IPS (In-Plane-Switching) method, FFS (Fringe Field Switching) method, OCB (OCB) method. Optically Compensated Bend) method.
- the cured film of the present invention can also be used in a COA (Color Filter on Array) type liquid crystal display device.
- the organic insulating film (115) described in JP-A-2005-284291 It can be used as the organic insulating film (212) described in Japanese Unexamined Patent Publication No. 2005-346054.
- the alignment method of the liquid crystal alignment film that the liquid crystal display device of the present invention can take include a rubbing alignment method and a photo alignment method.
- the polymer orientation may be supported by a PSA (Polymer Sustained Alignment) technique described in Japanese Patent Application Laid-Open Nos. 2003-149647 and 2011-257734.
- cured material of this invention are not limited to the said use, It can be used for various uses.
- a protective film for the color filter in addition to the planarization film and interlayer insulating film, a protective film for the color filter, a spacer for keeping the thickness of the liquid crystal layer in the liquid crystal display device constant, a microlens provided on the color filter in the solid-state imaging device, etc. Can be suitably used.
- FIG. 1 is a conceptual cross-sectional view showing an example of an active matrix liquid crystal display device 10.
- the color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and the liquid crystal panel includes all pixels disposed between two glass substrates 14 and 15 having a polarizing film attached thereto.
- the elements of the TFT 16 corresponding to are arranged.
- Each element formed on the glass substrate is wired with an ITO transparent electrode 19 that forms a pixel electrode through a contact hole 18 formed in the cured film 17.
- an RGB color filter 22 in which a liquid crystal 20 layer and a black matrix are arranged is provided.
- the light source of the backlight is not particularly limited, and a known light source can be used.
- the liquid crystal display device can be a 3D (stereoscopic) type or a touch panel type. Further, it can be made flexible, and used as the second interphase insulating film (48) described in JP2011-145686A or the interphase insulating film (520) described in JP2009-258758A. Can do.
- the organic EL display device of the present invention comprises the cured product of the present invention.
- the organic EL display device of the present invention is not particularly limited except that it has a light extraction layer, a planarizing film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and has various structures. Examples include various known organic EL display devices and liquid crystal display devices.
- TFT Thin-Film Transistor
- IGZO indium gallium zinc oxide
- IZO indium zinc oxide
- FIG. 2 is a conceptual diagram of an example of an organic EL display device.
- a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided.
- a bottom gate type TFT 1 is formed on a glass substrate 6, and an insulating film 3 made of Si 3 N 4 is formed so as to cover the TFT 1.
- a contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height: 1.0 ⁇ m) connected to the TFT 1 through the contact hole is formed on the insulating film 3.
- the wiring 2 is used to connect the TFT 1 with an organic EL element formed between the TFTs 1 or in a later process. Further, in order to flatten the unevenness due to the formation of the wiring 2, a planarizing layer 4 is formed on the insulating film 3 in a state where the unevenness due to the wiring 2 is embedded. On the planarizing film 4, a bottom emission type organic EL element is formed. That is, the first electrode 5 made of ITO is formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. The first electrode 5 corresponds to the anode of the organic EL element. An insulating film 8 having a shape covering the periphery of the first electrode 5 is formed.
- a short circuit between the first electrode 5 and the second electrode formed in the subsequent process is prevented. can do.
- a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited through a desired pattern mask, and then a second layer made of Al is formed on the entire surface above the substrate.
- An EL display device is obtained.
- MEMS devices include, for example, SAW (surface acoustic wave) filters, BAW (bulk acoustic wave) filters, gyro sensors, micro shutters for displays, image sensors, electronic paper, inkjet heads, biochips, sealants. And the like. More specific examples are exemplified in JP-T-2007-522531, JP-A-2008-250200, JP-A-2009-263544, and the like.
- the photosensitive resin composition of the present invention is excellent in flatness and transparency, for example, the bank layer (16) and the planarization film (57) described in FIG. Partition wall (12) and planarization film (102) shown in FIG. 4 (a) of JP-A-9793, and bank layer (221) and third interlayer insulating film (FIG. 10 of JP 2010-27591A). 216b), the second interlayer insulating film (125) and the third interlayer insulating film (126) described in FIG. 4A of JP-A-2009-128577, and the configuration described in FIG. 3 of JP-A-2010-182638. It can also be used to form a planarization film (12), a pixel isolation insulating film (14), and the like.
- the touch panel display device of the present invention includes a capacitive input device having the cured product of the present invention. Moreover, the capacitance-type input device of the present invention is characterized by having the film of the present invention.
- the capacitance-type input device of the present invention has at least the following elements (1) to (5) on the non-contact side of the front plate and the front plate, and the following (4) is the photosensitive resin of the present invention.
- a heat-treated product obtained by heat-treating the composition, preferably heat-cured is preferable.
- Mask layer (2) A plurality of first transparent electrode patterns formed by extending a plurality of pad portions in a first direction via connection portions (3) The first transparent electrode pattern and the electric A plurality of second transparent electrode patterns comprising a plurality of pad portions which are insulated and extend in a direction intersecting the first direction. (4) The first transparent electrode pattern and the second An insulating layer that electrically insulates the transparent electrode pattern of (5) electrically connected to at least one of the first transparent electrode pattern and the second transparent electrode pattern, and the first transparent electrode pattern and the above Conductive element different from the second transparent electrode pattern
- a transparent protective layer is further provided so as to cover all or part of the elements (1) to (5).
- the transparent protective layer is preferably And more preferably the cured film.
- FIG. 3 is a cross-sectional view showing the configuration of the capacitive input device.
- the capacitive input device 30 includes a front plate 31, a mask layer 32, a first transparent electrode pattern 33, a second transparent electrode pattern 34, an insulating layer 35, and a conductive element 36. And a transparent protective layer 37.
- the front plate 31 is composed of a light-transmitting substrate such as a glass substrate, and tempered glass represented by gorilla glass manufactured by Corning Inc. can be used. Moreover, in FIG. 3, the side in which each element of the front plate 31 is provided is called a non-contact surface. In the capacitive input device 30 of the present invention, input is performed by bringing a finger or the like into contact with the contact surface (the surface opposite to the non-contact surface) of the front plate 31.
- the front plate may be referred to as a “base material”.
- a mask layer 32 is provided on the non-contact surface of the front plate 31.
- the mask layer 32 is a frame-like pattern around the display area formed on the non-contact side of the touch panel front plate, and is formed so as not to show the lead wiring and the like.
- a mask layer 32 is provided so as to cover a part of the front plate 31 (a region other than the input surface in FIG. 4).
- the front plate 31 can be provided with an opening 38 in a part thereof as shown in FIG. A mechanical switch by pressing can be installed in the opening 38.
- a plurality of first transparent electrode patterns 33 formed with a plurality of pad portions extending in the first direction via the connection portions, A plurality of second transparent electrode patterns 34 each including a plurality of pad portions that are electrically insulated from one transparent electrode pattern 33 and extend in a direction crossing the first direction; An insulating layer 35 that electrically insulates the electrode pattern 33 and the second transparent electrode pattern 34 is formed.
- the first transparent electrode pattern 33, the second transparent electrode pattern 34, and the conductive element 36 to be described later are translucent conductive materials such as ITO (Indium Tin Oxide) and IZO (Indium Zinc Oxide). It can be made of a conductive metal oxide film.
- metal films examples include ITO films; metal films such as Al, Zn, Cu, Fe, Ni, Cr, and Mo; metal oxide films such as SiO 2 .
- the film thickness of each element can be set to 10 to 200 nm.
- the first transparent electrode pattern 33, the second transparent electrode pattern 34, and the conductive element 36 described later use a photosensitive transfer material having a photosensitive resin composition using the conductive fibers. Can also be manufactured.
- paragraphs 0014 to 0016 of Japanese Patent No. 4506785 can be referred to.
- At least one of the first transparent electrode pattern 33 and the second transparent electrode pattern 34 extends over both the non-contact surface of the front plate 31 and the region opposite to the front plate 31 of the mask layer 32. Can be installed.
- FIG. 3 a diagram is shown in which the second transparent electrode pattern is installed across both areas of the non-contact surface of the front plate 31 and the surface opposite to the front plate 31 of the mask layer 32. Yes.
- FIG. 5 is an explanatory diagram showing an example of the first transparent electrode pattern and the second transparent electrode pattern in the present invention.
- the first transparent electrode pattern 33 is formed such that a pad portion 33a extends in a first direction via a connection portion 33b.
- the second transparent electrode pattern 34 is electrically insulated by the first transparent electrode pattern 33 and the insulating layer 35 and extends in a direction intersecting the first direction (second direction in FIG. 5). It is constituted by a plurality of pad portions that are formed.
- the pad portion 33a and the connection portion 33b may be manufactured as one body, or only the connection portion 33b is manufactured, and the pad portion 33a and the second portion 33b are formed.
- the transparent electrode pattern 34 may be integrally formed (patterned).
- the pad portion 33a and the second transparent electrode pattern 34 are integrally formed (patterned), as shown in FIG. 5, a part of the connection part 33b and a part of the pad part 33a are connected, and an insulating layer is formed. Each layer is formed so that the first transparent electrode pattern 33 and the second transparent electrode pattern 34 are electrically insulated by 35.
- a conductive element 36 is provided on the surface of the mask layer 32 opposite to the front plate 31.
- the conductive element 36 is electrically connected to at least one of the first transparent electrode pattern 33 and the second transparent electrode pattern 34, and is different from the first transparent electrode pattern 33 and the second transparent electrode pattern 34. Is another element.
- FIG. 3 a view in which the conductive element 36 is connected to the second transparent electrode pattern 34 is shown.
- the transparent protective layer 37 is installed so that all of each component may be covered.
- the transparent protective layer 37 may be configured to cover only a part of each component.
- the insulating layer 35 and the transparent protective layer 37 may be made of the same material or different materials.
- the capacitance-type input device obtained by the manufacturing method of the present invention and the touch panel display device including the capacitance-type input device as a constituent element are “the latest touch panel technology” (issued July 6, 2009 (stock) ) Techno Times), supervised by Yuji Mitani, "Touch Panel Technology and Development", CMC Publishing (2004, 12), FPD International 2009 Forum T-11 Lecture Textbook, Cypress Semiconductor Corporation Application Note AN2292, etc.
- the configuration can be applied.
- the touch panel of the present invention is a touch panel in which all or a part of the insulating layer is made of a heat-treated product of the resin composition of the present invention. Moreover, it is preferable that the touch panel of this invention has a transparent substrate, an ITO electrode, and an insulating layer at least.
- the touch panel display device of the present invention is preferably a touch panel display device having the touch panel of the present invention.
- the manufacturing method of the touchscreen of this invention is a manufacturing method of the touchscreen which has a transparent substrate, an ITO electrode, and an insulating layer, Comprising: Inkjet application
- a transparent substrate in the touch panel of this invention a glass substrate, a quartz substrate, a transparent resin substrate, etc. are mentioned preferably.
- Ink-jet application in the step of applying the photosensitive resin composition for ink-jet application of the present invention by the ink-jet application method so as to be in contact with the ITO electrode can be performed in the same manner as the above-described application step, and the preferred embodiment is also the same. .
- coated photosensitive resin composition of this invention should just be in contact with the ITO electrode.
- the step of placing a mask having an opening pattern of a predetermined shape on the resin composition, irradiating with exposure to active energy rays, and the step of developing the resin composition after exposure are performed in the same manner as the exposure step described above.
- the preferred embodiment is also the same.
- the step of heating the resin composition after development to produce an insulating layer can be performed in the same manner as the heat treatment step described above, and the preferred embodiment is also the same.
- the pattern shown in FIG. 5 mentioned above is mentioned preferably.
- Dispersion I ⁇ Preparation of Dispersion I> -Composition of Dispersion I- Titanium oxide: 25.0% (TTO-51 (C) manufactured by Ishihara Sangyo Co., Ltd.) Dispersant 1 (solid content 30% PGMEA solution of the following compound): 7.5% as solid content PGMEA (propylene glycol monomethyl ether acetate, Showa Denko KK): 67.5%
- the dispersion composition having the above composition was circulated for 150 minutes at an ultra apex mill manufactured by Kotogiken Kogyo Co., Ltd. with a 0.05 mm zirconia bead filling rate of 75%, a peripheral speed of 12 m / sec, and a circulation flow rate of 180 g / min. Dispersion I was obtained.
- Dispersant 1 Solid content 30% PGMEA solution of the following compound, Mw 5,500, acid value 220 mgKOH / g
- L 5.5
- m 0.5
- n1: n2 86.5 mass%: 13.5 mass%.
- Dispersions II to IV were respectively prepared in the same manner as the dispersion I except that the titanium oxide and / or the dispersant was changed as described in Table 1.
- Dispersant 2 BYK-111: 95% solid content, DISPERBYK-111, manufactured by Big Chemie Japan Co., Ltd.
- Dispersant 3 Solid content 30% PGMEA solution, Mw 15,000, acid value 140 mgKOH / g
- Example 1 Preparation of positive photosensitive resin composition> After mixing and mixing with the following composition to obtain a uniform solution, the mixture was filtered using a polyethylene filter having a pore size of 0.2 ⁇ m to prepare a positive photosensitive resin composition of Example 1.
- oxime compound (1.8 g) was dissolved in acetone (20 mL), triethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g) were added under ice cooling, and the temperature was raised to room temperature (25 ° C.). The reaction was allowed to warm for 1 hour.
- E-1 compound (the above structure) (2.3 g).
- MATHF tetrahydrofuran-2-yl methacrylate (synthetic product)
- MAEVE 1-ethoxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
- MAA Methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.)
- GMA Glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
- OXE-30 Methacrylic acid (3-ethyloxetane-3-yl) methyl (Osaka Organic Chemical Industry Co., Ltd.)
- MMA Methyl methacrylate (Wako Pure Chemical Industries, Ltd.) St: Styrene (Wako Pure Chemical Industries, Ltd.)
- the PGMEA solution of polymer P1 was obtained by reacting at 70 ° C. for 2 hours. Further, PGMEA was added to adjust the solid content concentration to 40% by mass. The weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the obtained polymer P1 was 15,000.
- the obtained photosensitive resin composition was applied onto a silicon wafer substrate using a spinner, and dried at 80 ° C. for 120 seconds to form a 0.7 ⁇ m thick film.
- This substrate was exposed at 200 mJ / cm 2 (measured with i-line) using an ultrahigh pressure mercury lamp, and then heated in an oven at 230 ° C. for 60 minutes.
- the refractive index of the cured film at 550 nm was measured using an ellipsometer VUV-VASE (manufactured by JA Woollam Japan Co., Ltd.). A higher refractive index is preferable, and 1.70 or more is more preferable.
- a photosensitive resin composition is slit coated on a bare wafer (N-type low resistance) (manufactured by SUMCO) and then pre-baked on a hot plate at 80 ° C. for 2 minutes to form a photosensitive resin composition having a thickness of 0.7 ⁇ m. A layer was formed.
- the obtained photosensitive resin composition was exposed with a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. so that the integrated irradiation amount was 200 mJ / cm 2 (illuminance: 20 mW / cm 2 ), The substrate was heated in an oven at 230 ° C. for 1 hour to obtain a cured film.
- the relative dielectric constant was measured at a measurement frequency of 1 MHz using CVmap92A (made by Four Dimensions Inc.). This value is preferably as low as possible, and it can be said that the relative dielectric constant of the cured film is good.
- the obtained photosensitive resin composition was applied on a 100 mm ⁇ 100 mm glass substrate (trade name: XG, manufactured by Corning) with a spin coater, and dried (prebaked) for 120 seconds on an 80 ° C. hot plate. Next, the entire surface was exposed with an energy intensity of 20 mW / cm 2 and 200 mJ / cm 2 using a ghi-line high pressure mercury lamp exposure machine. Furthermore, the coating film was heat-treated (post-baked) for 60 minutes in an oven at 230 ° C. The initial coating thickness was adjusted so that the thickness was 1 ⁇ m after post-baking.
- the haze of the post-baked sample is NDH-5000 made by Nippon Denshoku Industries Co., Ltd., and the haze (haze) is determined in accordance with the plastic product test method (JIS K7136, JIS K7361, ASTM D1003). Value).
- a haze value refers to the value represented by the ratio (%) of the diffuse transmitted light with respect to all the light transmitted light. The smaller the haze value, the higher the transparency.
- Examples 2 to 114 and Comparative Examples 1 to 34 Except for changing each component of the photosensitive resin composition to the components shown in Tables 3 to 7, Examples 2 to 114 and Comparative Example were prepared in the same manner as the preparation of the positive photosensitive resin composition in Example 1.
- the photosensitive resin compositions of Examples 1 to 34 were prepared and evaluated in the same manner as in Example 1. The evaluation results are shown in Tables 3 to 7.
- E-4 PAG-103 (trade name, structure shown below, manufactured by BASF)
- G-1 jER157S65 (Novolac type epoxy resin, manufactured by Mitsubishi Chemical Holdings Corporation)
- G-2 jER828 (bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Holdings Corporation)
- G-3 jER1007 (bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Holdings Corporation)
- Example 115 In the active matrix liquid crystal display device described in FIG. 1 of Japanese Patent No. 3321003, a cured film 17 was formed as an interlayer insulating film as follows, and a liquid crystal display device of Example 115 was obtained. That is, the photosensitive resin composition of Example 34 was applied on a substrate, pre-baked on a hot plate (90 ° C./120 seconds), and then i-line (365 nm) was applied from the mask using a high-pressure mercury lamp to 45 mJ / cm.
- liquid crystal display device When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.
- Example 116 An organic EL display device using a thin film transistor (TFT) was produced by the following method (see FIG. 2).
- a bottom gate type TFT 1 was formed on a glass substrate 6, and an insulating film 3 made of Si 3 N 4 was formed so as to cover the TFT 1.
- a contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height 1.0 ⁇ m) connected to the TFT 1 through the contact hole is formed on the insulating film 3. .
- the wiring 2 is for connecting the TFT 1 with an organic EL element formed between the TFTs 1 or in a later process.
- the flattening film 4 was formed on the insulating film 3 in a state where the unevenness due to the wiring 2 was embedded.
- the planarization film 4 is formed on the insulating film 3 by spin-coating the photosensitive resin composition of Example 44 on a substrate, pre-baking (90 ° C./120 seconds) on a hot plate, and then applying high pressure from above the mask. After irradiating 45 mJ / cm 2 (illuminance 20 mW / cm 2 ) with i-line (365 nm) using a mercury lamp, a pattern was formed by developing with an alkaline aqueous solution, and heat treatment was performed at 230 ° C./30 minutes.
- the applicability when applying the photosensitive resin composition was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development and baking. Furthermore, the average step of the wiring 2 was 500 nm, and the thickness of the prepared planarizing film 4 was 2,000 nm.
- a bottom emission type organic EL element was formed on the obtained flattening film 4.
- a first electrode 5 made of ITO was formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7.
- a resist was applied, prebaked, exposed through a mask having a desired pattern, and developed.
- pattern processing was performed by wet etching using an ITO etchant.
- the resist pattern was stripped at 50 ° C. using a resist stripper (remover 100, manufactured by AZ Electronic Materials).
- the first electrode 5 thus obtained corresponds to the anode of the organic EL element.
- an insulating film 8 having a shape covering the periphery of the first electrode 5 was formed.
- the photosensitive resin composition of Example 34 was used, and the insulating film 8 was formed by the same method as described above. By providing this insulating film 8, it is possible to prevent a short circuit between the first electrode 5 and the second electrode formed in the subsequent process.
- a hole transport layer, an organic light emitting layer, and an electron transport layer were sequentially deposited through a desired pattern mask in a vacuum deposition apparatus.
- a second electrode made of Al was formed on the entire surface above the substrate.
- substrate was taken out from the vapor deposition machine, and it sealed by bonding together using the glass plate for sealing, and an ultraviolet curable epoxy resin.
- Example 117 A touch panel display device was produced using the photosensitive resin composition having a high refractive index of the present invention by the method described below.
- ⁇ Formation of first transparent electrode pattern> [Formation of transparent electrode layer]
- a formed front plate was obtained.
- the surface resistance of the ITO thin film was 80 ⁇ / ⁇ .
- etching resist was applied onto ITO and dried to form an etching resist layer.
- the distance between the exposure mask (quartz exposure mask having a transparent electrode pattern) surface and the etching resist layer is set to 100 ⁇ m, pattern exposure is performed at an exposure amount of 50 mJ / cm 2 (i-line), and then a dedicated developer And a post-bake treatment at 130 ° C. for 30 minutes to obtain a front plate on which a transparent electrode layer and a photocurable resin layer pattern for etching were formed.
- the front plate on which the transparent electrode layer and the photocurable resin layer pattern for etching are formed is immersed in an etching tank containing ITO etchant (hydrochloric acid, potassium chloride aqueous solution, liquid temperature 30 ° C.), treated for 100 seconds, and etched resist.
- ITO etchant hydroochloric acid, potassium chloride aqueous solution, liquid temperature 30 ° C.
- the exposed transparent electrode layer not covered with the layer was dissolved and removed to obtain a front plate with a transparent electrode layer pattern with an etching resist layer pattern.
- the front plate with the transparent electrode layer pattern with the etching resist layer pattern is immersed in a dedicated resist stripping solution, the photocurable resin layer for etching is removed, and the mask layer and the first transparent electrode pattern A front plate formed was obtained.
- the photosensitive resin composition of Example 5 was applied and dried (film thickness: 1 ⁇ m, 90 ° C., 120 seconds) to form a photosensitive resin composition layer.
- the distance between the exposure mask (quartz exposure mask having an insulating layer pattern) surface and the photosensitive resin composition layer was set to 30 ⁇ m, and pattern exposure was performed at an exposure amount of 50 mJ / cm 2 (i-line).
- the film was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 15 seconds by immersion and further rinsed with ultrapure water for 10 seconds.
- a post-bake treatment at 220 ° C. for 45 minutes was performed to obtain a front plate on which a mask layer, a first transparent electrode pattern, and an insulating layer pattern were formed.
- the first transparent electrode pattern, the insulating layer pattern formed using the photosensitive resin composition of Example 5 a transparent electrode layer, A front plate on which an etching resist pattern was formed was obtained (post-baking treatment; 130 ° C. for 30 minutes). Further, etching was performed in the same manner as the formation of the first transparent electrode pattern, and the etching resist layer was removed to form the mask layer, the first transparent electrode pattern, and the photosensitive resin composition of Example 5. A front plate on which an insulating layer pattern and a second transparent electrode pattern were formed was obtained.
- the photosensitive resin composition of Example 5 was applied to the front plate formed up to the conductive element different from the first and second transparent electrode patterns and dried (film thickness 1 ⁇ m). , 90 ° C. for 120 seconds) to obtain a photosensitive resin composition film. Furthermore, the distance between the exposure mask (quartz exposure mask having a protective layer pattern) surface and the photosensitive resin composition layer was set to 50 ⁇ m, and exposure was performed at an exposure amount of 50 mJ / cm 2 (i-line).
- a liquid crystal display device manufactured by the method described in Japanese Patent Application Laid-Open No. 2009-47936 is bonded to the previously manufactured front plate, and an image display device including a capacitive input device as a constituent element is manufactured by a known method. did.
- Example 118 Using the photosensitive resin composition of Example 62 for the insulator 5 described in Japanese Patent No. 5318289, a touch panel display device was produced in the same manner as the method described in Japanese Patent No. 5318289.
- the photosensitive resin composition of the present invention having a high refractive index, the difference in refractive index from the detection electrode can also be suppressed, so that the pattern of the insulator 5 is less visible and has excellent display characteristics. A device was obtained.
- Example 119 Using the photosensitive resin composition of Example 111 for the protective layer 7 in addition to the insulator 5 described in Japanese Patent No. 5318289, a touch panel display device is produced in the same manner as the method described in Japanese Patent No. 5318289. did. Since both the insulator 5 and the protective layer 7 can have a high refractive index, the pattern of the insulator 5 is further less visible, and a display device with very good visibility is obtained.
- Example 120 Using the photosensitive resin composition of Example 37 for the insulating layer 14 described in Japanese Patent No. 5036913, an input device (touch panel input device) was produced in the same manner as the method described in Japanese Patent No. 5036913.
- An input device with very good visibility in which the electrode pattern is difficult to be visually recognized is obtained by preventing the flickering of the color in the insulating layer portion from being visually observed and further suppressing the difference in refractive index from the detection electrode.
- TFT thin film transistor
- 2 wiring
- 3 insulating film
- 4 planarization film
- 5 first electrode
- 6 glass substrate
- 7 contact hole
- 8 insulating film
- 10 liquid crystal display device
- 12 Backlight unit
- 14 15: Glass substrate
- 16 TFT
- 17 Cured film
- 18 Contact hole
- 19 ITO transparent electrode
- 20 Liquid crystal
- 22 Color filter
- 30 Capacitive input device 31: front plate, 32: mask layer, 33: first transparent electrode pattern, 33a: pad portion, 33b: connection portion, 34: second transparent electrode pattern, 35: insulating layer
- 36 conductive element
- 37 Transparent protective layer
- 38 Opening
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Abstract
Description
更に詳しくは、液晶表示装置、有機EL表示装置、集積回路素子、固体撮像素子などの電子部品の平坦化膜、保護膜や層間絶縁膜の形成に好適な、感光性樹脂組成物及びそれを用いた硬化膜の製造方法に関する。
これら光学部材は、高屈折率にするために、酸化チタンなどの金属酸化物粒子を添加することが検討されている(下記特許文献1参照)。
また、従来の感光性樹脂組成物としては、特許文献2又は3に記載の感光性樹脂組成物が知られている。
<1>(成分A)金属酸化物粒子、(成分B)下記式(I)で表される化合物、(成分C)溶剤、(成分D)酸基が酸分解性基で保護された基を有する構成単位を含む重合体、及び、(成分E)光酸発生剤、を含有することを特徴とする感光性樹脂組成物、
<3>成分Bの含有量が、成分Dの含有量100質量部に対して、1~200質量部である、上記<1>又は<2>に記載の感光性樹脂組成物、
<4>成分Aの平均一次粒子径が50nm以下である、上記<1>~<3>のいずれか1つに記載の感光性樹脂組成物、
<5>(成分F)分散剤を更に含有する、上記<1>~<4>のいずれか1つに記載の感光性樹脂組成物、
<6>成分Dが、下記(1)及び(2)で表される重合体成分の少なくとも一方を満たす、上記<1>~<5>のいずれか1つに記載の感光性樹脂組成物、
(1)(a1)酸基が酸分解性基で保護された基を有する構成単位及び(a2)架橋性基を有する構成単位を有する重合体
(2)(a1)酸基が酸分解性基で保護された基を有する構成単位を有する重合体、及び、(a2)架橋性基を有する構成単位を有する重合体
<7>R1及びR2がそれぞれ独立に、ヒドロキシ基、カルボキシ基、又は、ヒドロキシ基、カルボキシ基、エポキシ基及びオキセタニル基よりなる群から選ばれる少なくとも1種の基を有する一価の有機基である、上記<1>~<6>のいずれか1つに記載の感光性樹脂組成物、
<8>成分Bが、下記式(II)で表される化合物である、上記<1>~<7>のいずれか1つに記載の感光性樹脂組成物、
(a)上記<1>~<8>のいずれか1つに記載の感光性樹脂組成物を基板上に塗布する塗布工程
(b)塗布された樹脂組成物から溶剤を除去する溶剤除去工程
(c)溶剤が除去された樹脂組成物を熱処理する熱処理工程
<10>少なくとも工程(1)~(4)をこの順に含むことを特徴とする樹脂パターン製造方法、
(1)上記<1>~<8>のいずれか1つに記載の感光性樹脂組成物を基板上に塗布する塗布工程
(2)塗布された樹脂組成物から溶剤を除去する溶剤除去工程
(3)溶剤が除去された樹脂組成物を活性光線によりパターン状に露光する露光工程
(4)露光された樹脂組成物を水性現像液により現像する現像工程
<11>上記<9>に記載の硬化物の製造方法、又は、上記<10>に記載の樹脂パターン製造方法により得られた硬化物、
<12>上記<1>~<8>のいずれか1つに記載の感光性樹脂組成物を硬化してなる硬化膜、
<13>層間絶縁膜である、上記<12>に記載の硬化膜、
<14>上記<12>又は<13>に記載の硬化膜を有する液晶表示装置、
<15>上記<12>又は<13>に記載の硬化膜を有する有機EL表示装置、
<16>上記<12>又は<13>に記載の硬化膜を有するタッチパネル表示装置。
なお、本願明細書において「~」とはその前後に記載される数値を下限値及び上限値として含む意味で使用される。
また、本発明において、「(成分A)金属酸化物粒子」等を、単に「成分A」等ともいい、「(a1)酸基が酸分解性基で保護された基を有する構成単位」等を、単に「構成単位(a1)」等ともいう。
更に、本明細書における基(原子団)の表記において、置換及び無置換を記していない表記は、置換基を有さないものと共に置換基を有するものをも包含するものである。例えば「アルキル基」とは、置換基を有さないアルキル基(無置換アルキル基)のみならず、置換基を有するアルキル基(置換アルキル基)をも包含するものである。
本発明において、「質量部」及び「質量%」はそれぞれ、「重量部」及び「重量%」と同義である。
また、本発明において、好ましい態様の組み合わせは、より好ましい。
本発明の感光性樹脂組成物は、熱により硬化する性質を有する樹脂組成物であることが好ましい。
また、本発明の感光性樹脂組成物は、ポジ型感光性樹脂組成物であることが好ましく、化学増幅型のポジ型感光性樹脂組成物(化学増幅ポジ型感光性樹脂組成物)であることがより好ましい。
本発明の感光性樹脂組成物は、活性光線に感応する光酸発生剤として1,2-キノンジアジド化合物を含まない方が好ましい。1,2-キノンジアジド化合物は、逐次型光化学反応によりカルボキシ基を生成するが、その量子収率は必ず1以下である。
これに対して、本発明で使用する(成分E)光酸発生剤は、活性光線に感応して生成される酸が、成分A中の保護された酸基の脱保護に対して触媒として作用するので、1個の光量子の作用で生成した酸が、多数の脱保護反応に寄与し、量子収率は1を超え、例えば、10の数乗のような大きい値となり、いわゆる化学増幅の結果として、高感度が得られる。
本発明者らが鋭意検討を行った結果、金属酸化物粒子を用いる場合、金属酸化物粒子自体の比誘電率が極めて高いことから、形成後の膜の比誘電率が極めて高くなってしまい、例えば配線層間の絶縁部材として用いた場合に配線遅延などの原因となる恐れがあることを見いだした。また、金属酸化物粒子を含有させることにより、形成後の膜のヘイズ値も高く(透明性が悪化)させる恐れがあることも見いだした。
本発明者等は詳細な検討の結果、成分A~成分Eを含有する感光性樹脂組成物とすることにより、得られる硬化物が高屈折率であり、比誘電率が低く、透明性に優れることを見いだし、本発明を完成するに至ったものである。
以下、本発明の樹脂組成物について詳細に説明する。
本発明の樹脂組成物は、屈折率や光透過性を調節することを目的として、金属酸化物粒子を含有する。金属酸化物粒子は、透明性が高く、光透過性を有するため、高屈折率で、透明性に優れたポジ型感光性樹脂組成物が得られる。
成分Aは、当該粒子を除いた材料からなる樹脂組成物の屈折率より屈折率が高いものであることが好ましく、具体的には、400~750nmの波長を有する光における屈折率が1.50以上の粒子がより好ましく、屈折率が1.70以上の粒子が更に好ましく、1.90以上の粒子が特に好ましい。
ここで、400~750nmの波長を有する光における屈折率が1.50以上であるとは、上記範囲の波長を有する光における平均屈折率が1.50以上であることを意味し、上記範囲の波長を有する全ての光における屈折率が1.50以上であることを要しない。また、平均屈折率は、上記範囲の波長を有する各光に対する屈折率の測定値の総和を、測定点の数で割った値である。
光透過性で屈折率の高い金属酸化物粒子としては、Be、Mg、Ca、Sr、Ba、Sc、Y、La、Ce、Gd、Tb、Dy、Yb、Lu、Ti、Zr、Hf、Nb、Mo、W、Zn、B、Al、Si、Ge、Sn、Pb、Sb、Bi、Te等の原子を含む酸化物粒子が好ましく、酸化チタン、チタン複合酸化物、酸化亜鉛、酸化ジルコニウム、インジウム/スズ酸化物、アンチモン/スズ酸化物がより好ましく、酸化チタン、チタン複合酸化物、酸化ジルコニウムが更に好ましく、酸化チタン、酸化ジルコニウムが特に好ましく、酸化チタンが最も好ましい。酸化チタンとしては、特に屈折率の高いルチル型が好ましい。これら金属酸化物粒子は、分散安定性付与のために表面を有機材料で処理することもできる。
本発明の樹脂組成物における金属酸化物粒子の含有量は、樹脂組成物により得られる光学部材に要求される屈折率や、光透過性等を考慮して、適宜決定すればよいが、本発明の樹脂組成物の全固形分に対して、5~80質量%とすることが好ましく、10~70質量%とすることがより好ましく、15~60質量%とすることが更に好ましく、20~50質量%とすることが特に好ましい。
上記分散液の調製に使用される溶剤としては、例えば、後述する(成分C)溶剤のほか、1-プロパノール、2-プロパノール、1-ブタノール、2-ブタノール、2-メチル-2-プロパノール、1-ペンタノール、2-ペンタノール、3-ペンタノール、3-メチル-1-ブタノール、2-メチル-2-ブタノール、ネオペンタノール、シクロペンタノール、1-ヘキサノール、シクロヘキサノール等のアルコール類等を挙げることができる。
これらの溶剤は、1種単独又は2種以上を混合して使用することができる。
本発明の感光性樹脂組成物は、(成分B)下記式(I)で表される化合物を含有する。
また、合成及び比誘電率の観点から、Ar1とAr2とは同じ基であることが好ましい。
Ar1及びAr2はそれぞれ独立に、芳香環上に置換基を有していてもよい。
上記置換基としては、ハロゲン原子、アルキル基、アルケニル基、アリール基、アルコキシ基、アリーロキシ基、アルキルチオ基、及び、アリールチオ基が好ましく例示でき、ハロゲン原子、アルキル基、及び、アリール基がより好ましく例示でき、アルキル基、及び、アリール基が更に好ましく例示できる。
また、上記置換基同士が結合して、脂環又は芳香環を形成してもよい。
屈折率及び比誘電率の観点から、R1及びR2はそれぞれ独立に、ヒドロキシ基、カルボキシ基、又は、ヒドロキシ基、カルボキシ基、エポキシ基及びオキセタニル基よりなる群から選ばれる少なくとも1種の基を有する一価の有機基であることが好ましく、ヒドロキシ基、又は、ヒドロキシ基、エポキシ基及びオキセタニル基よりなる群から選ばれる少なくとも1種の基を有する一価の有機基であることがより好ましく、エポキシ基及びオキセタニル基よりなる群から選ばれる少なくとも1種の基を有する一価の有機基であることが更に好ましく、エポキシ基を有する一価の有機基であることが特に好ましい。
また、R1及びR2としては、感度の観点では、ヒドロキシ基、又は、ヒドロキシ基を有する一価の有機基が好ましく、透明性の観点では、エポキシ基又はオキセタニル基を有する一価の有機基が好ましい。
更に、R1とR2とは、合成上の観点から、同一の基であることが特に好ましい。
また、上記一価の有機基におけるヒドロキシ基、カルボキシ基、エポキシ基及びオキセタニル基以外の部分構造としては、アルキレン基、エーテル結合、チオエーテル結合、カルボニル基、アミド結合、及び、これらを組み合わせた構造が好ましく挙げられる。
上記一価の有機基は、エーテル結合、アルキレンオキシ基又はポリアルキレンオキシ基を有する基であることが好ましく、エーテル結合又はアルキレンオキシ基を有することがより好ましい。
R1及びR2における上記一価の有機基の炭素数は、0~60であることが好ましく、0~40であることがより好ましく、0~20であることが更に好ましい。
また、屈折率及び比誘電率の観点から、R1及びR2はそれぞれ独立に、ヒドロキシ基、グリシジルオキシ基、3-アルキル-3-オキセタニルメチルオキシ基、グリシジルオキシアルキレンオキシ基、又はグリシジルオキシポリアルキレンオキシ基であることが好ましく、ヒドロキシ基、グリシジルオキシ基、又は、グリシジルオキシアルキレンオキシ基であることがより好ましく、グリシジルオキシ基、又は、グリシジルオキシアルキレンオキシ基であることが更に好ましく、グリシジルオキシアルキレンオキシ基であることが特に好ましい。
上記R3及びR4における一価の置換基としては、ハロゲン原子、アルキル基、アリール基、アルコキシ基、アリーロキシ基、アルキルチオ基、及び、アリールチオ基が好ましく例示でき、ハロゲン原子、アルキル基、アルコキシ基がより好ましく例示でき、アルキル基が更に好ましく例示できる。
R3及びR4における上記一価の有機基の炭素数は、0~40であることが好ましく、0~30であることがより好ましく、0~20であることが更に好ましい。
p及びqはそれぞれ独立に、0~4の整数を表し、0~2の整数であることが好ましく、0又は2であることがより好ましく、0であることが特に好ましい。
また、異なるR3同士及び異なるR4同士が結合して脂環又は芳香環を形成してもよい。上記環を形成する場合、芳香環を形成することが好ましく、フルオレン環とともに以下の環を形成することがより好ましい。
式(I)で表される化合物の分子量は、現像液への溶解性及び光学特性の観点から、分子量は、1,000未満であることが好ましく、400以上1,000未満であることがより好ましく、400~800であることが更に好ましく、400~600であることが特に好ましい。
R5及びR6はそれぞれ独立に、水素原子、又は、ヒドロキシ基、エポキシ基及びオキセタニル基よりなる群から選ばれる少なくとも1種の基を有する一価の有機基であることが好ましく、エポキシ基及びオキセタニル基よりなる群から選ばれる少なくとも1種の基を有する一価の有機基であることがより好ましく、エポキシ基を有する一価の有機基であることが更に好ましい。
更に、R5とR6とは、合成上の観点から、同一の基であることが特に好ましい。
また、R5及びR6の上記一価の有機基におけるヒドロキシ基、カルボキシ基、エポキシ基及びオキセタニル基以外の部分構造としては、アルキレン基、エーテル結合、チオエーテル結合、カルボニル基、アミド結合、及び、これらを組み合わせた構造が好ましく挙げられる。
R5及びR6における上記一価の有機基の炭素数は、0~60であることが好ましく、0~40であることがより好ましく、0~20であることが更に好ましい。
また、屈折率及び比誘電率の観点から、R5及びR6はそれぞれ独立に、水素原子、グリシジル基、3-アルキル-3-オキセタニルメチル基、グリシジルオキシアルキル基、又は、グリシジルポリアルキレンオキシアルキル基であることが好ましく、ヒドロキシ基、グリシジル基、又は、グリシジルオキシアルキル基であることがより好ましく、グリシジル基、又は、グリシジルオキシアルキル基であることが更に好ましく、グリシジルオキシアルキル基であることが特に好ましい。
式(III)~式(VI)におけるR5及びR6は、式(II)におけるR5及びR6とそれぞれ同義であり、好ましい態様も同様である。
式(III)~式(VI)におけるR7及びR8はそれぞれ独立に、一価の置換基を表し、ハロゲン原子、アルキル基、アルケニル基、アリール基、アルコキシ基、アリーロキシ基、アルキルチオ基、又は、アリールチオ基であることが好ましく、ハロゲン原子、アルキル基、又は、アリール基であることがより好ましく、アルキル基、及び、アリール基であることが更に好ましい。
式(III)~式(VI)におけるm及びnはそれぞれ独立に、0~4の整数を表し、0~2の整数であることが好ましく、0又は1であることがより好ましく、0であることが更に好ましい。
式(III)~式(VI)におけるm’及びn’はそれぞれ独立に、0~6の整数を表し、0~2の整数であることが好ましく、0又は1であることがより好ましく、0であることが更に好ましい。
中でも式(I)で表される化合物としては、以下の化合物が好ましく挙げられる。
例えば、式(I)におけるR1及びR2がヒドロキシ基の化合物を合成又は準備し、当該ヒドロキシ基から公知の方法により、ヒドロキシ基、カルボキシ基、エポキシ基及びオキセタニル基よりなる群から選ばれる少なくとも1種の基を有する一価の有機基を誘導することにより簡便に合成することができる。
また、例えば、特開2009-210668号公報に記載された方法によっても好適に合成することができる。
以下に式(I)で表される化合物の合成の一例を示す。例えば、上記具体例におけるエポキシフルオレン化合物であれば、対応するヒドロキシフルオレン化合物を準備し、エピクロロヒドリンによりグリシジル基を導入し合成する方法等が好適に挙げられる。
9,9-ビス(ヒドロキシフェニル)フルオレン(BPF:大阪ガスケミカル(株)製)13g、2-ブロモエタノール35g及び水酸化ナトリウム3gを水12g及び1,4-ジオキサン3gとともに還流冷却装置を備えた300mlの三口フラスコにいれ、激しく撹拌した。続いてヒーター温120℃で5時間加熱撹拌し、その後室温(25℃)に戻した。フラスコの水酸化ナトリウム水溶液を除去し、試料を水で5回洗浄した。下記構造式(x)で示される化合物を16.2g得た。
FAB-MS(ポジティブモード)〔高速原子衝撃質量分析装置、Fast Atom Bombardment Mass Spectrometry〕で上記化合物の分子量を測定したところ、439であった。
本発明の感光性樹脂組成物における式(I)で表される化合物の含有量は、成分Dの全含有量100質量部に対し、1~200質量部であることが好ましく、5~150質量部であることがより好ましく、10~150質量部であることが更に好ましく、50~120質量部であることが特に好ましい。上記態様であると、得られる硬化物の屈折率がより高く、比誘電率がより低く、透明性により優れる。
本発明の感光性樹脂組成物は、(成分C)溶剤を含有する。本発明の感光性樹脂組成物は、本発明の必須成分と、更に後述の任意の成分を(成分C)溶剤に溶解した溶液として調製されることが好ましい。
本発明の感光性樹脂組成物に使用される溶剤としては、公知の溶剤を用いることができ、エチレングリコールモノアルキルエーテル類、エチレングリコールジアルキルエーテル類、エチレングリコールモノアルキルエーテルアセテート類、プロピレングリコールモノアルキルエーテル類、プロピレングリコールジアルキルエーテル類、プロピレングリコールモノアルキルエーテルアセテート類、ジエチレングリコールジアルキルエーテル類、ジエチレングリコールモノアルキルエーテルアセテート類、ジプロピレングリコールモノアルキルエーテル類、ジプロピレングリコールジアルキルエーテル類、ジプロピレングリコールモノアルキルエーテルアセテート類、エステル類、ケトン類、アミド類、ラクトン類等が例示できる。また、本発明の感光性樹脂組成物に使用される溶剤の具体例としては特開2011-221494号公報の段落0174~0178に記載の溶剤、特開2012-194290号公報の段落0167~0168に記載の溶剤も挙げられ、これらの内容は本願明細書に組み込まれる。
これら溶剤は、1種単独で又は2種以上を混合して使用することができる。本発明に用いることができる溶剤は、1種単独、又は、2種を併用することが好ましい。
沸点130℃以上160℃未満の溶剤としては、プロピレングリコールモノメチルエーテルアセテート(沸点146℃)、プロピレングリコールモノエチルエーテルアセテート(沸点158℃)、プロピレングリコールメチル-n-ブチルエーテル(沸点155℃)、プロピレングリコールメチル-n-プロピルエーテル(沸点131℃)が例示できる。
沸点160℃以上の溶剤としては、3-エトキシプロピオン酸エチル(沸点170℃)、ジエチレングリコールメチルエチルエーテル(沸点176℃)、プロピレングリコールモノメチルエーテルプロピオネート(沸点160℃)、ジプロピレングリコールメチルエーテルアセテート(沸点213℃)、3-メトキシブチルエーテルアセテート(沸点171℃)、ジエチレングリコールジエチエルエーテル(沸点189℃)、ジエチレングリコールジメチルエーテル(沸点162℃)、プロピレングリコールジアセテート(沸点190℃)、ジエチレングリコールモノエチルエーテルアセテート(沸点220℃)、ジプロピレングリコールジメチルエーテル(沸点175℃)、1,3-ブチレングリコールジアセテート(沸点232℃)が例示できる。
これらの中でも、溶剤としては、プロピレングリコールモノアルキルエーテルアセテート類が好ましく、プロピレングリコールモノメチルエーテルアセテートが特に好ましい。
本発明の感光性樹脂組成物は、(成分D)酸基が酸分解性基で保護された基を有する構成単位を有する重合体を含有する。
なお、本発明において、「酸基が酸分解性基で保護された基を有する構成単位」を「(a1)酸基が酸分解性基で保護された基を有する構成単位」ともいう。
本発明の感光性樹脂組成物は、下記(1)及び(2)の少なくとも一方を満たす重合体を含む重合体成分を含有することが好ましい。
(1)(a1)酸基が酸分解性基で保護された基を有する構成単位及び(a2)架橋性基を有する構成単位を有する重合体
(2)(a1)酸基が酸分解性基で保護された基を有する構成単位を有する重合体、及び、(a2)架橋性基を有する構成単位を有する重合体
本発明の感光性樹脂組成物は、更に、これら以外の重合体を含んでいてもよい。本発明における成分Dは、特に述べない限り、上記(1)及び/又は(2)に加え、必要に応じて添加される他の重合体を含めたものを意味するものとする。
本発明の感光性樹脂組成物は、硬化後における透明性(ヘイズ)及び未露光部の残膜率の観点からは、成分Dとして、上記(1)を満たす成分を含むことが好ましい。
一方、分子設計の自由度の観点からは、本発明の感光性樹脂組成物は、成分Dとして、上記(2)を満たす成分を含むことが好ましい。
なお、上記(1)を満たす成分を含有する場合であっても、更に、(a1)酸基が酸分解性基で保護された基を有する構成単位を有する重合体及び/又は(a2)架橋性基を有する構成単位を有する重合体を含有していてもよい。
また、上記(2)を満たす成分を含有する場合であっても、(a1)酸基が酸分解性基で保護された基を有する構成単位及び(a2)架橋性基を有する構成単位を有する重合体に該当するものを少なくとも含有する場合は、上記(1)を満たす成分を含有する場合に該当するものとする。
なお、「(メタ)アクリル酸及び/又はそのエステルに由来する構成単位」を「アクリル系構成単位」ともいう。また、「(メタ)アクリル酸」は、「メタクリル酸及び/又はアクリル酸」を意味するものとする。
成分Dは、(a1)酸基が酸分解性基で保護された基を有する構成単位を少なくとも有する重合体を含む。成分Dが構成単位(a1)を有する重合体を含むことにより、極めて高感度な感光性樹脂組成物とすることができる。
本発明における「酸基が酸分解性基で保護された基」は、酸基及び酸分解性基として公知のものを使用でき、特に限定されない。具体的な酸基としては、カルボキシル基、及び、フェノール性水酸基が好ましく挙げられる。また、酸分解性基としては、酸により比較的分解しやすい基(例えば、後述する式(a1-10)等で表される基のエステル構造、テトラヒドロピラニルエステル基、又は、テトラヒドロフラニルエステル基等のアセタール系官能基)や酸により比較的分解しにくい基(例えば、tert-ブチルエステル基等の第三級アルキルエステル基、tert-ブチルカーボネート基等の第三級アルキルカーボネート基)を用いることができる。
以下、酸分解性基で保護された保護カルボキシル基を有する構成単位(a1-1)と、酸分解性基で保護された保護フェノール性水酸基を有する構成単位(a1-2)について、順にそれぞれ説明する。
上記酸分解性基で保護された保護カルボキシル基を有する構成単位(a1-1)は、カルボキシル基を有する構成単位のカルボキシル基が、以下で詳細に説明する酸分解性基によって保護された保護カルボキシル基を有する構成単位である。
上記酸分解性基で保護された保護カルボキシル基を有する構成単位(a1-1)に用いることができる上記カルボキシル基を有する構成単位としては、特に制限はなく公知の構成単位を用いることができる。例えば、不飽和モノカルボン酸、不飽和ジカルボン酸、不飽和トリカルボン酸などの、分子中に少なくとも1個のカルボキシル基を有する不飽和カルボン酸等に由来する構成単位(a1-1-1)や、エチレン性不飽和基と酸無水物由来の構造とを共に有する構成単位(a1-1-2)が挙げられる。
以下、上記カルボキシル基を有する構成単位として用いられる(a1-1-1)分子中に少なくとも1個のカルボキシル基を有する不飽和カルボン酸等に由来する構成単位と、(a1-1-2)エチレン性不飽和基と酸無水物由来の構造とを共に有する構成単位について、それぞれ順に説明する。
上記分子中に少なくとも1個のカルボキシル基を有する不飽和カルボン酸等に由来する構成単位(a1-1-1)として本発明で用いられる不飽和カルボン酸としては以下に挙げるようなものが用いられる。すなわち、不飽和モノカルボン酸としては、例えば、アクリル酸、メタクリル酸、クロトン酸、α-クロロアクリル酸、けい皮酸、2-(メタ)アクリロイロキシエチルコハク酸、2-(メタ)アクリロイロキシエチルヘキサヒドロフタル酸、2-(メタ)アクリロイロキシエチルフタル酸などが挙げられる。また、不飽和ジカルボン酸としては、例えば、マレイン酸、フマル酸、イタコン酸、シトラコン酸、メサコン酸などが挙げられる。また、カルボキシル基を有する構成単位を得るために用いられる不飽和多価カルボン酸は、その酸無水物であってもよい。具体的には、無水マレイン酸、無水イタコン酸、無水シトラコン酸などが挙げられる。また、不飽和多価カルボン酸は、多価カルボン酸のモノ(2-メタクリロイロキシアルキル)エステルであってもよく、例えば、コハク酸モノ(2-アクリロイロキシエチル)、コハク酸モノ(2-メタクリロイロキシエチル)、フタル酸モノ(2-アクリロイロキシエチル)、フタル酸モノ(2-メタクリロイロキシエチル)などが挙げられる。更に、不飽和多価カルボン酸は、その両末端ジカルボキシポリマーのモノ(メタ)アクリレートであってもよく、例えば、ω-カルボキシポリカプロラクトンモノアクリレート、ω-カルボキシポリカプロラクトンモノメタクリレートなどが挙げられる。また、不飽和カルボン酸としては、アクリル酸-2-カルボキシエチルエステル、メタクリル酸-2-カルボキシエチルエステル、マレイン酸モノアルキルエステル、フマル酸モノアルキルエステル、4-カルボキシスチレン等も用いることができる。
中でも、現像性の観点から、上記分子中に少なくとも1個のカルボキシル基を有する不飽和カルボン酸等に由来する構成単位(a1-1-1)を形成するためには、アクリル酸、メタクリル酸、2-(メタ)アクリロイロキシエチルコハク酸、2-(メタ)アクリロイロキシエチルヘキサヒドロフタル酸、2-(メタ)アクリロイロキシエチルフタル酸、又は、不飽和多価カルボン酸の無水物等を用いることが好ましく、アクリル酸、メタクリル酸、2-(メタ)アクリロイロキシエチルヘキサヒドロフタル酸、を用いることがより好ましい。
上記分子中に少なくとも1個のカルボキシル基を有する不飽和カルボン酸等に由来する構成単位(a1-1-1)は、1種単独で構成されていてもよいし、2種以上で構成されていてもよい。
エチレン性不飽和基と酸無水物由来の構造とを共に有する構成単位(a1-1-2)は、エチレン性不飽和基を有する構成単位中に存在する水酸基と酸無水物とを反応させて得られたモノマーに由来する単位であることが好ましい。
上記酸無水物としては、公知のものが使用でき、具体的には、無水マレイン酸、無水コハク酸、無水イタコン酸、無水フタル酸、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、無水クロレンド酸等の二塩基酸無水物;無水トリメリット酸、無水ピロメリット酸、ベンゾフェノンテトラカルボン酸無水物、ビフェニルテトラカルボン酸無水物などの酸無水物が挙げられる。これらの中では、現像性の観点から、無水フタル酸、テトラヒドロ無水フタル酸、又は、無水コハク酸が好ましい。
上記酸無水物の水酸基に対する反応率は、現像性の観点から、好ましくは10~100モル%、より好ましくは30~100モル%である。
上記酸分解性基で保護された保護カルボキシル基を有する構成単位(a1-1)に用いることができる上記酸分解性基としては上述の酸分解性基を用いることができる。
これらの酸分解性基の中でもカルボキシル基がアセタールの形で保護された保護カルボキシル基であることが、感光性樹脂組成物の基本物性、特に感度やパターン形状、コンタクトホールの形成性、感光性樹脂組成物の保存安定性の観点から好ましい。更に酸分解性基の中でもカルボキシル基が下記式(a1-10)で表されるアセタールの形で保護された保護カルボキシル基であることが、感度の観点からより好ましい。なお、カルボキシル基が下記式(a1-10)で表されるアセタールの形で保護された保護カルボキシル基である場合、保護カルボキシル基の全体としては、-(C=O)-O-CR101R102(OR103)の構造となっている。
上記直鎖状又は分岐鎖状のアルキル基としては、炭素数1~12であることが好ましく、炭素数1~6であることがより好ましく、炭素数1~4であることが更に好ましい。具体的には、メチル基、エチル基、n-プロピル基、i-プロピル基、n-ブチル基、i-ブチル基、sec-ブチル基、tert-ブチル基、n-ペンチル基、ネオペンチル基、n-ヘキシル基、テキシル基(2,3-ジメチル-2-ブチル基)、n-ヘプチル基、n-オクチル基、2-エチルヘキシル基、n-ノニル基、n-デシル基等を挙げることができる。
上記ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が例示され、これらの中でも、フッ素原子又は塩素原子が好ましい。
また、上記アリール基としては、炭素数6~20のアリール基が好ましく、炭素数6~12のアリール基がより好ましい。具体的には、フェニル基、α-メチルフェニル基、ナフチル基等が例示でき、アリール基で置換されたアルキル基全体、すなわち、アラルキル基としては、ベンジル基、α-メチルベンジル基、フェネチル基、ナフチルメチル基等が例示できる。
上記アルコキシ基としては、炭素数1~6のアルコキシ基が好ましく、炭素数1~4のアルコキシ基がより好ましく、メトキシ基又はエトキシ基が更に好ましい。
また、上記アルキル基がシクロアルキル基である場合、上記シクロアルキル基は置換基として炭素数1~10の直鎖状又は分岐鎖状のアルキル基を有していてもよく、アルキル基が直鎖状又は分岐鎖状のアルキル基である場合には、置換基として炭素数3~12のシクロアルキル基を有していてもよい。
これらの置換基は、上記置換基で更に置換されていてもよい。
R3は、アルキル基又はアリール基を表し、炭素数1~10のアルキル基が好ましく、1~6のアルキル基がより好ましい。
Xは、単結合又はアリーレン基を表し、単結合が好ましい。
L1はカルボニル基が好ましい。
R122~R128は、水素原子が好ましい。
上記酸分解性基で保護された保護フェノール性水酸基を有する構成単位(a1-2)は、フェノール性水酸基を有する構成単位が、以下で詳細に説明する酸分解性基によって保護された保護フェノール性水酸基を有する構成単位である。
上記フェノール性水酸基を有する構成単位としては、ヒドロキシスチレン系構成単位やノボラック系の樹脂における構成単位が挙げられるが、これらの中では、ヒドロキシスチレン又はα-メチルヒドロキシスチレンに由来する構成単位が、感度の観点から好ましい。また、フェノール性水酸基を有する構成単位として、下記式(a1-20)で表される構成単位も、感度の観点から好ましい。
また、R221は単結合又は二価の連結基を表す。単結合である場合には、感度を向上させることができ、更に硬化膜の透明性を向上させることができるので好ましい。R221の二価の連結基としてはアルキレン基が例示でき、炭素数1~12のアルキレン基が好ましく、炭素数1~8のアルキレン基がより好ましく、炭素数1~3のアルキレン基が更に好ましい。R221がアルキレン基である場合の具体例としては、メチレン基、エチレン基、プロピレン基、イソプロピレン基、n-ブチレン基、イソブチレン基、tert-ブチレン基、ペンチレン基、イソペンチレン基、ネオペンチレン基、ヘキシレン基等が挙げられる。中でも、R221が単結合、メチレン基、エチレン基、1,2-プロピレン基、1,3-プロピレン基、又は、2-ヒドロキシ-1,3-プロピレン基であることが好ましい。また、上記二価の連結基は、置換基を有していてもよく、置換基としては、ハロゲン原子、水酸基、アルコキシ基等が挙げられる。また、aは1~5の整数を表すが、本発明の効果の観点や、製造が容易であるという点から、aは1又は2であることが好ましく、aが1であることがより好ましい。
また、ベンゼン環における水酸基の結合位置は、R221と結合している炭素原子を基準(1位)としたとき、4位に結合していることが好ましい。
R222はそれぞれ独立に、ハロゲン原子又は炭素数1~5の直鎖若しくは分岐鎖状のアルキル基を表す。具体的には、フッ素原子、塩素原子、臭素原子、メチル基、エチル基、プロピル基、イソプロピル基、n-ブチル基、イソブチル基、tert-ブチル基、ペンチル基、イソペンチル基、ネオペンチル基等が挙げられる。中でも製造が容易であるという点から、塩素原子、臭素原子、メチル基又はエチル基であることが好ましい。
また、bは0又は1~4の整数を表す。
上記酸分解性基で保護された保護フェノール性水酸基を有する構成単位(a1-2)に用いることができる上記酸分解性基としては、上記酸分解性基で保護された保護カルボキシル基を有する構成単位(a1-1)に用いることができる上記酸分解性基と同様に、公知のものを使用でき、特に限定されない。酸分解性基の中でもアセタールで保護された保護フェノール性水酸基を有する構成単位であることが、感光性樹脂組成物の基本物性、特に感度やパターン形状、感光性樹脂組成物の保存安定性、コンタクトホールの形成性の観点から好ましい。更に、酸分解性基の中でもフェノール性水酸基が上記式(a1-10)で表されるアセタールの形で保護された保護フェノール性水酸基であることが、感度の観点からより好ましい。なお、フェノール性水酸基が上記式(a1-10)で表されるアセタールの形で保護された保護フェノール性水酸基である場合、保護フェノール性水酸基の全体としては、-Ar-O-CR101R102(OR103)の構造となっている。なお、Arはアリーレン基を表す。
これらの中で、4-ヒドロキシフェニルメタクリレートの1-アルコキシアルキル保護体、4-ヒドロキシフェニルメタクリレートのテトラヒドロピラニル保護体が透明性の観点から好ましい。
上記構成単位(a1)を有する重合体が、実質的に、構成単位(a2)を有しない場合、構成単位(a1)の含有量は、構成単位(a1)を有する重合体中、20~100モル%が好ましく、30~90モル%がより好ましい。
上記構成単位(a1)を有する重合体が、下記構成単位(a2)を有する場合、構成単位(a1)の含有量は、構成単位(a1)と構成単位(a2)とを有する重合体中、感度の観点から3~70モル%が好ましく、10~60モル%がより好ましい。また、特に上記構成単位(a1)が、カルボキシル基がアセタールの形で保護された保護カルボキシル基を有する構成単位である場合、20~50モル%が好ましい。
なお、本発明において、「構成単位」の含有量をモル比で規定する場合、当該「構成単位」は「モノマー単位」と同義であるものとする。また、本発明において当該「モノマー単位」は、高分子反応等により重合後に修飾されていてもよい。以下においても同様である。
成分Dは、架橋性基を有する構成単位(a2)を有する重合体を含有する。上記架橋性基は、加熱処理で硬化反応を起こす基であれば特に限定はされない。好ましい架橋性基を有する構成単位の態様としては、エポキシ基、オキセタニル基、-NH-CH2-O-R(Rは水素原子又は炭素数1~20のアルキル基を表す。)で表される基及びエチレン性不飽和基よりなる群から選ばれた少なくとも1つを含む構成単位が挙げられ、エポキシ基、オキセタニル基、及び、-NH-CH2-O-R(Rは水素原子又は炭素数1~20のアルキル基を表す。)で表される基よりなる群から選ばれた少なくとも1種であることが好ましい。その中でも、本発明の感光性樹脂組成物は、上記成分Dが、エポキシ基及びオキセタニル基のうち少なくとも1つを含む構成単位を含むことがより好ましい。より詳細には、以下のものが挙げられる。
成分Dは、エポキシ基及び/又はオキセタニル基を有する構成単位(構成単位(a2-1))を有する重合体を含有することが好ましい。3員環の環状エーテル基はエポキシ基とも呼ばれ、4員環の環状エーテル基はオキセタニル基とも呼ばれる。
上記エポキシ基及び/又はオキセタニル基を有する構成単位(a2-1)は、1つの構成単位中にエポキシ基又はオキセタニル基を少なくとも1つ有していればよく、1つ以上のエポキシ基及び1つ以上オキセタニル基、2つ以上のエポキシ基、又は、2つ以上のオキセタニル基を有していてもよく、特に限定されないが、エポキシ基及び/又はオキセタニル基を合計1~3つ有することが好ましく、エポキシ基及び/又はオキセタニル基を合計1又は2つ有することがより好ましく、エポキシ基又はオキセタニル基を1つ有することが更に好ましい。
オキセタニル基を有する構成単位を形成するために用いられるラジカル重合性単量体の具体例としては、例えば、特開2001-330953号公報の段落0011~0016に記載のオキセタニル基を有する(メタ)アクリル酸エステルなどが挙げられ、これらの内容は本願明細書に組み込まれる。
上記エポキシ基及び/又はオキセタニル基を有する構成単位(a2-1)を形成するために用いられるラジカル重合性単量体の具体例としては、メタクリル酸エステル構造を含有するモノマー、アクリル酸エステル構造を含有するモノマーであることが好ましい。
上記架橋性基を有する構成単位(a2)の1つとして、エチレン性不飽和基を有する構成単位(a2-2)が挙げられる(以下、「構成単位(a2-2)」ともいう。)。上記エチレン性不飽和基を有する構成単位(a2-2)としては、側鎖にエチレン性不飽和基を有する構成単位が好ましく、末端にエチレン性不飽和基を有し、炭素数3~16の側鎖を有する構成単位がより好ましい。
本発明で用いる共重合体は、-NH-CH2-O-R(Rは水素原子又は炭素数1~20のアルキル基を表す。)で表される基を有する構成単位(a2-3)も好ましい。構成単位(a2-3)を有することで、緩やかな加熱処理で硬化反応を起こすことができ、諸特性に優れた硬化膜を得ることができる。ここで、Rは炭素数1~20のアルキル基が好ましく、炭素数1~9のアルキル基がより好ましく、炭素数1~4のアルキル基が更に好ましい。また、アルキル基は、直鎖、分岐又は環状のアルキル基のいずれであってもよいが、直鎖又は分岐のアルキル基であることが好ましい。構成単位(a2)は、下記式(a2-30)で表される基を有する構成単位であることがより好ましい。
R32の具体例としては、メチル基、エチル基、n-ブチル基、i-ブチル基、シクロヘキシル基、及び、n-ヘキシル基を挙げることができる。中でも、i-ブチル基、n-ブチル基、メチル基が好ましい。
上記構成単位(a2)を有する重合体が、実質的に、構成単位(a1)を有しない場合、構成単位(a2)の含有量は、構成単位(a2)を有する重合体中、5~90モル%が好ましく、20~80モル%がより好ましい。
上記構成単位(a2)を有する重合体が、上記構成単位(a1)を有する場合、単構成単位(a2)の含有量は、構成単位(a1)と構成単位(a2)を有する重合体中、薬品耐性の観点から3~70モル%が好ましく、10~60モル%がより好ましい。
本発明では、更に、いずれの態様にかかわらず、成分Dの全構成単位中、構成単位(a2)を3~70モル%含有することが好ましく、10~60モル%含有することがより好ましい。
上記の数値の範囲内であると、感光性樹脂組成物から得られる硬化膜の透明性及び薬品耐性が良好となる。
本発明において、成分Dは、上記構成単位(a1)及び/又は(a2)に加えて、これら以外の他の構成単位(a3)を有していてもよい。これらの構成単位は、上記重合体成分(1)及び/又は(2)が含んでいてもよい。また、上記重合体成分(1)又は(2)とは別に、実質的に構成単位(a1)及び構成単位(a2)を含まずに他の構成単位(a3)を有する重合体成分を有していてもよい。上記重合体成分(1)又は(2)とは別に、実質的に構成単位(a1)及び構成単位(a2)を有さずに他の構成単位(a3)を有する重合体成分を含む場合、重合体成分の配合量は、全重合体成分中、60質量%以下であることが好ましく、40質量%以下であることがより好ましく、20質量%以下であることが更に好ましい。
本発明で用いられる酸基としては、カルボン酸基、スルホンアミド基、ホスホン酸基、スルホン酸基、フェノール性水酸基、スルホンアミド基、スルホニルイミド基、並びに、これらの酸基の酸無水物基、及び、これらの酸基を中和し塩構造とした基等が例示され、カルボン酸基及び/又はフェノール性水酸基が好ましい。上記塩としては、特に制限はないが、アルカリ金属塩、アルカリ土類金属塩、及び、有機アンモニウム塩が好ましく例示できる。
本発明で用いられる酸基を含む構成単位は、スチレンに由来する構成単位や、ビニル化合物に由来する構成単位、(メタ)アクリル酸及び/又はそのエステルに由来する構成単位であることがより好ましい。例えば、特開2012-88459号公報の段落0021~0023及び段落0029~0044に記載の化合物を用いることができ、この内容は本願明細書に組み込まれる。中でも、p-ヒドロキシスチレン、(メタ)アクリル酸、マレイン酸、無水マレイン酸に由来する構成単位が好ましい。
このような重合体としては、側鎖にカルボキシル基を有する樹脂が好ましい。例えば、特開昭59-44615号、特公昭54-34327号、特公昭58-12577号、特公昭54-25957号、特開昭59-53836号、特開昭59-71048号の各公報に記載されているような、メタクリル酸共重合体、アクリル酸共重合体、イタコン酸共重合体、クロトン酸共重合体、マレイン酸共重合体、部分エステル化マレイン酸共重合体等、並びに側鎖にカルボキシル基を有する酸性セルロース誘導体、水酸基を有するポリマーに酸無水物を付加させたもの等が挙げられ、更に側鎖に(メタ)アクリロイル基を有する高分子重合体も好ましいものとして挙げられる。
その他にも、特開平7-207211号公報、特開平8-259876号公報、特開平10-300922号公報、特開平11-140144号公報、特開平11-174224号公報、特開2000-56118号公報、特開2003-233179号公報、特開2009-52020号公報等に記載の公知の高分子化合物を使用することができ、これらの内容は本願明細書に組み込まれる。
これらの重合体は、1種類のみ含んでいてもよいし、2種類以上含んでいてもよい。
-第1の実施形態-
重合体成分(1)が、更に、1種又は2種以上のその他の構成単位(a3)を有する態様。
-第2の実施形態-
重合体成分(2)の(a1)酸基が酸分解性基で保護された基を有する構成単位を有する重合体が、更に、1種又は2種以上のその他の構成単位(a3)を有する態様。
-第3の実施形態-
重合体成分(2)の(a2)架橋性基を有する構成単位を有する重合体が、更に、1種又は2種以上のその他の構成単位(a3)を有する態様。
-第4の実施形態-
上記第1~第3の実施形態のいずれかにおいて、その他の構成単位(a3)として、少なくとも酸基を含む構成単位をいずれかの重合体に有する態様。
-第5の実施形態-
上記重合体成分(1)又は(2)とは別に、更に、実質的に構成単位(a1)及び構成単位(a2)を有さずに他の構成単位(a3)を有する重合体を有する態様。
-第6の実施形態-
上記第1~第5の実施形態の2以上の組み合わせからなる態様。
成分Dにおける重合体の分子量は、ポリスチレン換算重量平均分子量で、好ましくは1,000~200,000、より好ましくは2,000~50,000の範囲である。上記の数値の範囲内であると、諸特性が良好である。数平均分子量Mnと重量平均分子量Mwとの比(分散度、Mw/Mn)は1.0~5.0が好ましく、1.5~3.5がより好ましい。
なお、本発明における重量平均分子量や数平均分子量の測定は、ゲルパーミエーションクロマトグラフィ法により測定することが好ましい。本発明におけるゲルパーミエーションクロマトグラフィ法による測定は、HLC-8020GPC(東ソー(株)製)を用い、カラムとしてTSKgel Super HZ M-H、TSK gel Super HZ4000、TSKgel SuperHZ200(東ソー(株)製、4.6mmID×15cm)を、溶離液としてTHF(テトラヒドロフラン)を用いることが好ましい。
また、成分Dにおける重合体の合成法についても、様々な方法が知られているが、一例を挙げると、少なくとも上記構成単位(a1)及び上記構成単位(a3)を形成するために用いられるラジカル重合性単量体を含むラジカル重合性単量体混合物を有機溶剤中、ラジカル重合開始剤を用いて重合することにより合成することができる。また、いわゆる高分子反応で合成することもできる。
本発明の感光性樹脂組成物は、(成分E)光酸発生剤を含有する。本発明で使用される光酸発生剤(「成分E」ともいう。)としては、波長300nm以上、好ましくは波長300~450nmの活性光線に感応し、酸を発生する化合物が好ましいが、その化学構造に制限されるものではない。また、波長300nm以上の活性光線に直接感応しない光酸発生剤についても、増感剤と併用することによって波長300nm以上の活性光線に感応し、酸を発生する化合物であれば、増感剤と組み合わせて好ましく用いることができる。本発明で使用される光酸発生剤としては、pKaが4以下の酸を発生する光酸発生剤が好ましく、pKaが3以下の酸を発生する光酸発生剤がより好ましく、pKaが2以下の酸を発生する光酸発生剤が最も好ましい。
R21のアルキル基としては、炭素数1~10の、直鎖状又は分岐状アルキル基が好ましい。R21のアルキル基は、炭素数6~11のアリール基、炭素数1~10のアルコキシ基、又は、シクロアルキル基(7,7-ジメチル-2-オキソノルボルニル基などの有橋式脂環基を含む、好ましくはビシクロアルキル基等)で置換されてもよい。
R21のアリール基としては、炭素数6~11のアリール基が好ましく、フェニル基又はナフチル基がより好ましい。R21のアリール基は、炭素数1~10のアルキル基、炭素数1~10のアルコキシ基又はハロゲン原子で置換されてもよい。
Xとしてのアルコキシ基は、炭素数1~4の直鎖状又は分岐状アルコキシ基が好ましい。
Xとしてのハロゲン原子は、塩素原子又はフッ素原子が好ましい。
m4は、0又は1が好ましい。上記式(E2)中、m4が1であり、Xがメチル基であり、Xの置換位置がオルト位であり、R42が炭素数1~10の直鎖状アルキル基、7,7-ジメチル-2-オキソノルボルニルメチル基、又は、p-トルイル基である化合物が特に好ましい。
X1としては、炭素数1~5のアルコキシ基が好ましく、メトキシ基がより好ましい。
n4としては、0~2の整数が好ましく、0又は1が特に好ましい。
X101は-O-、-S-、-NH-、-NR105-、-CH2-、-CR106H-、又は、-CR105R107-を表し、R105~R107はアルキル基、又は、アリール基を表す。
R121~R124はそれぞれ独立に、水素原子、ハロゲン原子、アルキル基、アルケニル基、アルコキシ基、アミノ基、アルコキシカルボニル基、アルキルカルボニル基、アリールカルボニル基、アミド基、スルホ基、シアノ基、又は、アリール基を表す。R121~R124のうち2つは、それぞれ互いに結合して環を形成してもよい。
R121~R124としてはそれぞれ独立に、水素原子、ハロゲン原子、又は、アルキル基が好ましく、また、R121~R124のうち少なくとも2つが互いに結合してアリール基を形成する態様もまた、好ましく挙げられる。中でも、R121~R124がいずれも水素原子である態様が感度の観点から好ましい。
既述の官能基は、いずれも、更に置換基を有していてもよい。
アルキル基の炭素数は、好ましくは3~10である。特にアルキル基が分岐構造を有する場合、炭素数3~6のアルキル基が好ましく、環状構造を有する場合、炭素数5~7のアルキル基が好ましい。アルキル基としては、例えば、プロピル基、イソプロピル基、n-ブチル基、s-ブチル基、イソブチル基、tert-ブチル基、ペンチル基、イソペンチル基、ネオペンチル基、1,1-ジメチルプロピル基、ヘキシル基、2-エチルヘキシル基、シクロヘキシル基、オクチル基などが挙げられ、好ましくは、イソプロピル基、tert-ブチル基、ネオペンチル基、シクロヘキシル基である。
アリール基の炭素数は、好ましくは6~12であり、より好ましくは6~8であり、更に好ましくは6~7である。上記アリール基としては、フェニル基、ナフチル基などが挙げられ、好ましくは、フェニル基である。
Re1が表すアルキル基及びアリール基は、置換基を有していてもよい。置換基としては、例えばハロゲン原子(フッ素原子、塩素原子、臭素原子、ヨウ素原子)、直鎖、分岐又は環状のアルキル基(例えばメチル基、エチル基、プロピル基など)、アルケニル基、アルキニル基、アリール基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、カルバモイル基、シアノ基、カルボキシル基、水酸基、アルコキシ基、アリールオキシ基、アルキルチオ基、アリールチオ基、ヘテロ環オキシ基、アシルオキシ基、アミノ基、ニトロ基、ヒドラジノ基、ヘテロ環基などが挙げられる。また、これらの基によって更に置換されていてもよい。好ましくは、ハロゲン原子、メチル基である。
かさ高い置換基の中でも、イソプロピル基、tert-ブチル基、ネオペンチル基、シクロヘキシル基が好ましく、tert-ブチル基、シクロヘキシル基がより好ましい。
アリール基としては、炭素数6~10のアリール基が好ましい。上記アリール基としては、フェニル基、ナフチル基、p-トルイル基(p-メチルフェニル基)などが挙げられ、好ましくは、フェニル基、p-トルイル基である。
ヘテロアリール基としては、例えば、ピロール基、インドール基、カルバゾール基、フラン基、チオフェン基などが挙げられる。
Re2が表すアルキル基、アリール基、及びヘテロアリール基は、置換基を有していてもよい。置換基としては、Re1が表すアルキル基及びアリール基が有していてもよい置換基と同義である。
Re2は、アルキル基又はアリール基が好ましく、アリール基がより好ましく、フェニル基がより好ましい。フェニル基の置換基としてはメチル基が好ましい。
Re3~Re6のうち、Re3とRe4、Re4とRe5、又は、Re5とRe6が結合して環を形成してもよく、環としては、脂環又は芳香環を形成していることが好ましく、ベンゼン環がより好ましい。
Re3~Re6は、水素原子、アルキル基、ハロゲン原子(フッ素原子、塩素原子、臭素原子)、又は、Re3とRe4、Re4とRe5、若しくは、Re5とRe6が結合してベンゼン環を構成していることが好ましく、水素原子、メチル基、フッ素原子、塩素原子、臭素原子、又は、Re3とRe4、Re4とRe5、若しくは、Re5とRe6が結合してベンゼン環を構成していることがより好ましい。
Re3~Re6の好ましい態様は以下の通りである。
(態様1)少なくとも2つは水素原子である。
(態様2)アルキル基、アリール基、又は、ハロゲン原子の数は、1つ以下である。
(態様3)Re3とRe4、Re4とRe5、又は、Re5とRe6が結合してベンゼン環を構成している。
(態様4)上記態様1と2を満たす態様、及び/又は、上記態様1と3を満たす態様。
本発明の感光性樹脂組成物は、(成分F)分散剤を含有することが好ましい。分散剤を含有することにより、成分Aの樹脂組成物中での分散性をより向上させることができる。
分散剤としては、公知の分散剤を用いることができ、例えば、公知の顔料分散剤を適宜選択して用いることができる。
また、分散剤としては、高分子分散剤を好ましく用いることができる。なお、高分子分散剤とは、分子量(重量平均分子量)が1,000以上の分散剤である。
酸基としては、カルボン酸基(カルボキシ基)、スルホン酸基、リン酸基、フェノール性水酸基などが挙げられ、金属酸化物粒子への吸着力と分散性との観点から、カルボン酸基、スルホン酸基及びリン酸基よりなる群から選ばれた少なくとも1種であることが好ましく、カルボン酸基が特に好ましい。上記分散剤における酸基は、これらを1種単独で、又は、2種以上を組み合わせて有していてもよい。
成分Sにおける酸基は、式(S)のいずれの構造が有していてもよい。具体的には例えば、酸基は、上記式(S)におけるA2に含まれてもよく、また、P2で示される高分子骨格中に含まれてもよく、A2及びP2の両方に含まれてもよいが、効果の観点からは、A2に含まれることが好ましい。
なお、以下、この金属酸化物粒子に対する吸着能を有する部分構造(上記構造及び官能基)を、適宜、「吸着部位」と総称して、説明する。
また、本発明において、「吸着部位を少なくとも1種含む1価の有機基」は、前述の吸着部位と、1個から200個までの炭素原子、0個から20個までの窒素原子、0個から100個までの酸素原子、1個から400個までの水素原子、及び、0個から40個までの硫黄原子から成り立つ連結基と、が結合してなる1価の有機基である。なお、吸着部位自体が1価の有機基を構成しうる場合には、吸着部位そのものがA2で表される一価の有機基であってもよい。
まず、上記A2を構成する吸着部位について以下に説明する。
式(a2)中、R13及びR14はそれぞれ独立に、炭素数1から20までのアルキル基、炭素数6以上のアリール基、炭素数7以上のアラルキル基を表す。
特に、アミノ基(-NH2)、置換イミノ基(-NHR8、-NR9R10、ここで、R8、R9及びR10はそれぞれ独立に、炭素数1から5までのアルキル基、フェニル基、ベンジル基を表す。)、上記式(a1)で表されるグアニジル基(式(a1)中、R11及びR12はそれぞれ独立に、炭素数1から5までのアルキル基、フェニル基、ベンジル基を表す。)、上記式(a2)で表されるアミジニル基(式(a2)中、R13及びR14は各々独立に、炭素数1から5までのアルキル基、フェニル基、ベンジル基を表す。)などが好ましく用いられる。
中でも、有機色素構造、複素環構造、酸基、塩基性窒素原子を有する基、ウレア基、及び、炭素数4以上の炭化水素基よりなる群から選択された部分構造が好ましく、酸基が特に好ましい。
(a+1)価の連結基としては、1個から100個までの炭素原子、0個から10個までの窒素原子、0個から50個までの酸素原子、1個から200個までの水素原子、及び、0個から20個までの硫黄原子から成り立つ基が含まれ、無置換でも置換基を更に有していてもよい。
R4及びR5における2価の連結基としては、1個から100個までの炭素原子、0個から10個までの窒素原子、0個から50個までの酸素原子、1個から200個までの水素原子、及び、0個から20個までの硫黄原子から成り立つ基が含まれ、無置換であっても、置換基を更に有していてもよい。
上記R3で表される(m+n)価の連結基としては、1個から60個までの炭素原子、0個から10個までの窒素原子、0個から50個までの酸素原子、1個から100個までの水素原子、及び、0個から20個までの硫黄原子から成り立つ基が含まれ、無置換であっても、置換基を更に有していてもよい。
また、上記式(S)中、nは2~9を表す。nとしては、2~8が好ましく、2~7がより好ましく、3~6が特に好ましい。
ポリマーの中でも、高分子骨格を構成するには、ビニルモノマーの重合体若しくは共重合体、エステル系ポリマー、エーテル系ポリマー、ウレタン系ポリマー、アミド系ポリマー、エポキシ系ポリマー、シリコーン系ポリマー、及び、これらの変性物又は共重合体〔例えば、ポリエーテル/ポリウレタン共重合体、ポリエーテル/ビニルモノマーの重合体の共重合体など(ランダム共重合体、ブロック共重合体、グラフト共重合体のいずれであってもよい。)を含む。〕よりなる群から選択された少なくとも1種が好ましく、ビニルモノマーの重合体若しくは共重合体、エステル系ポリマー、エーテル系ポリマー、ウレタン系ポリマー、及び、これらの変性物又は共重合体よりなる群から選択された少なくとも1種がより好ましく、ビニルモノマーの重合体又は共重合体が更に好ましく、アクリル樹脂((メタ)アクリルモノマーの重合体又は共重合体)が特に好ましい。
更には、上記ポリマーは、有機溶媒に可溶であることが好ましい。また、成分Sは、有機溶媒に可溶であることが好ましい。有機溶媒との親和性が低いと、例えば、分散媒との親和性が弱まり、分散安定化に十分な、金属酸化物粒子表面において成分Sにより形成される吸着層を確保できなくなることがある。
上記高分子骨格を構成する酸基を有するポリマーとしては、例えば、酸基を有する、ポリアミドアミンとその塩、ポリカルボン酸とその塩、高分子量不飽和酸エステル、変性ポリウレタン、変性ポリエステル、変性ポリ(メタ)アクリレート、(メタ)アクリル系共重合体、ナフタレンスルホン酸ホルマリン縮合物)、及び、ポリオキシエチレンアルキルリン酸エステル、ポリオキシエチレンアルキルアミン、アルカノールアミン、顔料誘導体等を挙げることができる。これらの中でも、(メタ)アクリル酸共重合体が好ましい。
ここで、「酸基」とは、上記A2の説明において「酸基」として挙げたものを同様に挙げることができ、好ましくは、カルボキシ基である。
以下、これらのビニルモノマーの好ましい例について説明する。
ビニルエステル類の例としては、ビニルアセテート、ビニルクロロアセテート、ビニルプロピオネート、ビニルブチレート、ビニルメトキシアセテート、及び、安息香酸ビニルなどが挙げられる。
マレイン酸ジエステル類の例としては、マレイン酸ジメチル、マレイン酸ジエチル、及び、マレイン酸ジブチルなどが挙げられる。
フマル酸ジエステル類の例としては、フマル酸ジメチル、フマル酸ジエチル、及び、フマル酸ジブチルなどが挙げられる。
イタコン酸ジエステル類の例としては、イタコン酸ジメチル、イタコン酸ジエチル、及び、イタコン酸ジブチルなどが挙げられる。
ビニルケトン類の例としては、メチルビニルケトン、エチルビニルケトン、プロピルビニルケトン、フェニルビニルケトンなどが挙げられる。
オレフィン類の例としては、エチレン、プロピレン、イソブチレン、ブタジエン、イソプレンなどが挙げられる。
マレイミド類の例としては、マレイミド、ブチルマレイミド、シクロヘキシルマレイミド、フェニルマレイミドなどが挙げられる。
上記酸基を有するビニルモノマーの例としては、カルボキシ基を有するビニルモノマーやスルホン酸基を有するビニルモノマーが挙げられる。
カルボキシ基を有するビニルモノマーとして、(メタ)アクリル酸、ビニル安息香酸、マレイン酸、マレイン酸モノアルキルエステル、フマル酸、イタコン酸、クロトン酸、桂皮酸、アクリル酸ダイマーなどが挙げられる。また、2-ヒドロキシエチル(メタ)アクリレートなどの水酸基を有する単量体と無水マレイン酸や無水フタル酸、シクロヘキサンジカルボン酸無水物のような環状無水物との付加反応物、ω-カルボキシポリカプロラクトンモノ(メタ)アクリレートなども利用できる。また、カルボキシ基の前駆体として無水マレイン酸、無水イタコン酸、無水シトラコン酸などの無水物含有モノマーを用いてもよい。なお、これらの中では、共重合性やコスト、溶解性などの観点から(メタ)アクリル酸が特に好ましい。
高分子骨格P2が酸基を含むビニルモノマー由来のモノマー単位を含む場合、酸基を有するビニルモノマー由来のモノマー単位の高分子骨格中の含有量は、質量換算で、高分子骨格の全体に対し、3質量%~40質量%であることが好ましく、5質量%~20質量%の範囲であることがより好ましい。
R3:上記具体例(1)、(2)、(10)、(11)、(16)又は(17)
R4:単結合、又は、下記の構造単位若しくは該構造単位が組み合わさって構成される「1個から10個までの炭素原子、0個から5個までの窒素原子、0個から10個までの酸素原子、1個から30個までの水素原子、及び、0個から5個までの硫黄原子」から成り立つ2価の連結基(置換基を有していてもよく、該置換基としては、例えば、メチル基、エチル基等の炭素数1から20までのアルキル基、フェニル基、ナフチル基等の炭素数6から16までのアリール基、水酸基、アミノ基、カルボキシ基、スルホンアミド基、N-スルホニルアミド基、アセトキシ基等の炭素数1から6までのアシルオキシ基、メトキシ基、エトキシ基等の炭素数1から6までのアルコキシ基、塩素原子、臭素原子等のハロゲン原子、メトキシカルボニル基、エトキシカルボニル基、シクロヘキシルオキシカルボニル基等の炭素数2から7までのアルコキシカルボニル基、シアノ基、t-ブチルカーボネート基等の炭酸エステル基等が挙げられる。)
なお、下記基中、R12は水素原子又はメチル基を表し、Lは1又は2を表す。
m:0.5~3
n:3~6
成分Sは、例えば、特許第5036269号公報や特許第5171005号公報に記載の方法を参照して合成することができる。
本発明の感光性樹脂組成物における分散剤の含有量は、感光性樹脂組成物の全固形分に対して、5~70質量%の範囲が好ましく、10~50質量%の範囲がより好ましい。
本発明の感光性樹脂組成物は、必要に応じ、(成分G)架橋剤を含有することが好ましい。架橋剤を添加することにより、本発明の感光性樹脂組成物により得られる硬化膜をより強固な膜とすることができる。
架橋剤としては、熱によって架橋反応が起こるものであれば制限はない(ただし、成分Dを除く。)。すなわち、架橋剤としては熱架橋剤が好適に使用される。例えば、以下に述べる分子内に2個以上のエポキシ基又はオキセタニル基を有する化合物、アルコキシメチル基含有架橋剤、少なくとも1個のエチレン性不飽和二重結合を有する化合物、又は、ブロックイソシアネート化合物等を添加することができる。中でも、分子内に2個以上のエポキシ基又はオキセタニル基を有する化合物が好ましく、分子内に2個以上のエポキシ基を有する化合物がより好ましい。
本発明の感光性樹脂組成物中における架橋剤の添加量は、感光性樹脂組成物の全固形分100質量部に対し、0.01~50質量部であることが好ましく、0.1~30質量部であることがより好ましく、0.5~20質量部であることが更に好ましい。この範囲で添加することにより、機械的強度及び耐溶剤性に優れた硬化膜が得られる。架橋剤は複数を併用することもでき、その場合は架橋剤を全て合算して含有量を計算する。
分子内に2個以上のエポキシ基を有する化合物の具体例としては、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、脂肪族エポキシ樹脂等を挙げることができる。
これらは1種単独又は2種以上を組み合わせて使用することができる。
また、オキセタニル基を含む化合物は、単独で又はエポキシ基を含む化合物と混合して使用することが好ましい。
本発明の感光性樹脂組成物では、架橋剤として、ブロックイソシアネート化合物も好ましく採用できる。ブロックイソシアネート化合物は、ブロックイソシアネート基を有する化合物であれば特に制限はないが、硬化性の観点から、1分子内に2以上のブロックイソシアネート基を有する化合物であることが好ましい。
なお、本発明におけるブロックイソシアネート基とは、熱によりイソシアネート基を生成することが可能な基であり、例えば、ブロック剤とイソシアネート基とを反応させイソシアネート基を保護した基が好ましく例示できる。また、上記ブロックイソシアネート基は、90℃~250℃の熱によりイソシアネート基を生成することが可能な基であることが好ましい。
また、ブロックイソシアネート化合物としては、その骨格は特に限定されるものではなく、1分子中にイソシアネート基を2個有するものであればどのようなものでもよく、脂肪族、脂環族又は芳香族のポリイソシアネートであってよいが、例えば2,4-トリレンジイソシアネート、2,6-トリレンジイソシアネート、イソホロンジイソシアネート、1,6-ヘキサメチレンジイソシアネート、1,3-トリメチレンジイソシアネート、1,4-テトラメチレンジイソシアネート、2,2,4-トリメチルヘキサメチレンジイソシアネート、2,4,4-トリメチルヘキサメチレンジイソシアネート、1,9-ノナメチレンジイソシアネート、1,10-デカメチレンジイソシアネート、1,4-シクロヘキサンジイソシアネート、2,2’-ジエチルエーテルジイソシアネート、ジフェニルメタン-4,4’-ジイソシアネート、o-キシレンジイソシアネート、m-キシレンジイソシアネート、p-キシレンジイソシアネート、メチレンビス(シクロヘキシルイソシアネート)、シクロヘキサン-1,3-ジメチレンジイソシアネート、シクロヘキサン-1,4-ジメチレレンジイソシアネート、1,5-ナフタレンジイソシアネート、p-フェニレンジイソシアネート、3,3’-メチレンジトリレン-4,4’-ジイソシアネート、4,4’-ジフェニルエーテルジイソシアネート、テトラクロロフェニレンジイソシアネート、ノルボルナンジイソシアネート、水素化1,3-キシリレンジイソシアネート、水素化1,4-キシリレンジイソシアネート等のイソシアネート化合物及びこれらの化合物から派生するプレポリマー型の骨格の化合物を好適に用いることができる。これらの中でも、トリレンジイソシアネート(TDI)やジフェニルメタンジイソシアネート(MDI)、ヘキサメチレンジイソシアネート(HDI)、イソホロンジイソシアネート(IPDI)が特に好ましい。
上記ブロックイソシアネート化合物のブロック構造を形成するブロック剤としては、オキシム化合物、ラクタム化合物、フェノール化合物、アルコール化合物、アミン化合物、活性メチレン化合物、ピラゾール化合物、メルカプタン化合物、イミダゾール系化合物、イミド系化合物等を挙げることができる。これらの中でも、オキシム化合物、ラクタム化合物、フェノール化合物、アルコール化合物、アミン化合物、活性メチレン化合物、ピラゾール化合物から選ばれるブロック剤が特に好ましい。
上記ラクタム化合物としては、ε-カプロラクタム、γ-ブチロラクタム等が例示できる。
上記フェノール化合物としては、フェノール、ナフトール、クレゾール、キシレノール、ハロゲン置換フェノール等が例示できる。
上記アルコール化合物としては、メタノール、エタノール、プロパノール、ブタノール、シクロヘキサノール、エチレングリコールモノアルキルエーテル、プロピレングリコールモノアルキルエーテル、乳酸アルキル等が例示できる。
上記アミン化合物としては、1級アミン及び2級アミンが挙げられ、芳香族アミン、脂肪族アミン、脂環族アミンいずれでもよく、アニリン、ジフェニルアミン、エチレンイミン、ポリエチレンイミン等が例示できる。
上記活性メチレン化合物としては、マロン酸ジエチル、マロン酸ジメチル、アセト酢酸エチル、アセト酢酸メチル等が例示できる。
上記ピラゾール化合物としては、ピラゾール、メチルピラゾール、ジメチルピラゾール等が例示できる。
上記メルカプタン化合物としては、アルキルメルカプタン、アリールメルカプタン等が例示できる。
本発明の感光性樹脂組成物は、(成分H)アルコキシシラン化合物(単に「シラン化合物」ともいう。)を含有してもよい。アルコキシシラン化合物を用いると、本発明の感光性樹脂組成物により形成された膜と基板との密着性を向上できたり、本発明の感光性樹脂組成物により形成された膜の性質を調整することができる。本発明の感光性樹脂組成物に用いることができる(成分H)アルコキシシラン化合物は、基材となる無機物、例えば、シリコン、酸化シリコン、窒化シリコン等のシリコン化合物、金、銅、モリブデン、チタン、アルミニウム等の金属と絶縁膜との密着性を向上させる化合物であることが好ましい。具体的には、公知のシランカップリング剤等も有効である。
シランカップリング剤としては、例えば、γ-アミノプロピルトリメトキシシラン、γ-アミノプロピルトリエトキシシラン、γ-グリシドキシプロピルトリアルコキシシラン、γ-グリシドキシプロピルアルキルジアルコキシシラン、γ-メタクリロキシプロピルトリアルコキシシラン、γ-メタクリロキシプロピルアルキルジアルコキシシラン、γ-クロロプロピルトリアルコキシシラン、γ-メルカプトプロピルトリアルコキシシラン、β-(3,4-エポキシシクロヘキシル)エチルトリアルコキシシラン、ビニルトリアルコキシシランが挙げられる。これらのうち、γ-グリシドキシプロピルトリアルコキシシランやγ-メタクリロキシプロピルトリアルコキシシランがより好ましく、γ-グリシドキシプロピルトリアルコキシシランが更に好ましく、3-グリシドキシプロピルトリメトキシシランが特に好ましい。これらは1種単独又は2種以上を組み合わせて使用することができる。
(R1)4-n-Si-(OR2)n
式中、R1は反応性基を有さない炭素数1~20の炭化水素基であり、R2は炭素数1~3のアルキル基又はフェニル基であり、nは1~3の整数である。
具体例として以下の化合物を挙げることができる。なお、Phはフェニル基を表す。
本発明の感光性樹脂組成物におけるアルコキシシラン化合物の含有量は、感光性樹脂組成物中の全固形分100質量部に対して、0.1~30質量部が好ましく、0.5~20質量部がより好ましい。
本発明の感光性樹脂組成物は、(成分E)光酸発生剤との組み合わせにおいて、その分解を促進させるために、増感剤を含有することが好ましい。増感剤は、活性光線又は放射線を吸収して電子励起状態となる。電子励起状態となった増感剤は、光酸発生剤と接触して、電子移動、エネルギー移動、発熱などの作用が生じる。これにより光酸発生剤は化学変化を起こして分解し、酸を生成する。好ましい増感剤の例としては、以下の化合物類に属しており、かつ350nmから450nmの波長域のいずれかに吸収波長を有する化合物を挙げることができる。
これら増感剤の中でも、多核芳香族類、アクリドン類、スチリル類、ベーススチリル類、クマリン類が好ましく、多核芳香族類がより好ましい。多核芳香族類の中でもアントラセン誘導体が最も好ましい。
また、増感剤は、1種単独で使用してもよいし、2種以上を併用することもできる。
本発明の感光性樹脂組成物は、(成分J)塩基性化合物を含有してもよい。
(成分J)塩基性化合物としては、化学増幅レジストで用いられるものの中から任意に選択して使用することができる。例えば、脂肪族アミン、芳香族アミン、複素環式アミン、第四級アンモニウムヒドロキシド、カルボン酸の第四級アンモニウム塩等が挙げられる。これらの具体例としては、特開2011-221494号公報の段落0204~0207に記載の化合物が挙げられる。
芳香族アミンとしては、例えば、アニリン、ベンジルアミン、N,N-ジメチルアニリン、ジフェニルアミンなどが挙げられる。
複素環式アミンとしては、例えば、ピリジン、2-メチルピリジン、4-メチルピリジン、2-エチルピリジン、4-エチルピリジン、2-フェニルピリジン、4-フェニルピリジン、N-メチル-4-フェニルピリジン、4-ジメチルアミノピリジン、イミダゾール、ベンズイミダゾール、4-メチルイミダゾール、2-フェニルベンズイミダゾール、2,4,5-トリフェニルイミダゾール、ニコチン、ニコチン酸、ニコチン酸アミド、キノリン、8-オキシキノリン、ピラジン、ピラゾール、ピリダジン、プリン、ピロリジン、ピペリジン、ピペラジン、モルホリン、4-メチルモルホリン、N-シクロヘキシル-N’-[2-(4-モルホリニル)エチル]チオ尿素、1,5-ジアザビシクロ[4.3.0]-5-ノネン、1,8-ジアザビシクロ[5.3.0]-7-ウンデセンなどが挙げられる。
第四級アンモニウムヒドロキシドとしては、例えば、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラ-n-ブチルアンモニウムヒドロキシド、テトラ-n-ヘキシルアンモニウムヒドロキシドなどが挙げられる。
カルボン酸の第四級アンモニウム塩としては、例えば、テトラメチルアンモニウムアセテート、テトラメチルアンモニウムベンゾエート、テトラ-n-ブチルアンモニウムアセテート、テトラ-n-ブチルアンモニウムベンゾエートなどが挙げられる。
これらの中でも、複素環式アミンが好ましく、2,4,5-トリフェニルイミダゾール、及び/又は、N-シクロヘキシル-N’-[2-(4-モルホリニル)エチル]チオ尿素が特に好ましい。
本発明の感光性樹脂組成物における塩基性化合物の含有量は、感光性樹脂組成物中の全固形分100質量部に対して、0.001~3質量部であることが好ましく、0.005~1質量部であることがより好ましい。
本発明の感光性樹脂組成物は、(成分K)界面活性剤を含有してもよい。
(成分K)界面活性剤としては、アニオン系、カチオン系、ノニオン系又は両性のいずれでも使用することができるが、好ましい界面活性剤は、ノニオン界面活性剤である。本発明の組成物に用いられる界面活性剤としては、例えば、特開2012-88459号公報の段落0201~0205に記載のものや、特開2011-215580号公報の段落0185~0188に記載のものを用いることができ、これらの記載は本願明細書に組み込まれる。
ノニオン系界面活性剤の例としては、ポリオキシエチレン高級アルキルエーテル類、ポリオキシエチレン高級アルキルフェニルエーテル類、ポリオキシエチレングリコールの高級脂肪酸ジエステル類、シリコーン系、フッ素系界面活性剤を挙げることができる。また、以下商品名で、KP-341、X-22-822(信越化学工業(株)製)、ポリフローNo.99C(共栄社化学(株)製)、エフトップ(三菱マテリアル電子化成(株)製)、メガファック(DIC(株)製)、フロラードノベックFC-4430(住友スリーエム(株)製)、サーフロンS-242(AGCセイミケミカル(株)製)、PolyFoxPF-6320(OMNOVA社製)、SH-8400(東レ・ダウコーニングシリコーン(株)製)、フタージェントFTX-218G((株)ネオス製)等の各シリーズを挙げることができる。
また、界面活性剤として、下記式(K-1)で表される構成単位A及び構成単位Bを含み、テトラヒドロフラン(THF)を溶媒とした場合のゲルパーミエーションクロマトグラフィで測定されるポリスチレン換算の重量平均分子量(Mw)が1,000以上10,000以下である共重合体を好ましい例として挙げることができる。
本発明の感光性樹脂組成物における界面活性剤の添加量は、感光性樹脂組成物中の全固形分100質量部に対して、10質量部以下であることが好ましく、0.001~10質量部であることがより好ましく、0.01~3質量部であることが更に好ましい。
本発明の感光性樹脂組成物は、(成分L)2つ以上の窒素原子を有する複素環化合物を含有することが好ましい。成分Lが無機粒子の表面に吸着することで、無機粒子同士の静電反発や立体的な反発を引き起こし、特に組成物を塗布・乾燥した際の無機粒子の凝集を防ぐため、ヘイズが小さくなると推定される。なお、成分Lに該当する化合物の一部は、上記成分Jにも該当する。
成分Lとしては、2つ以上の窒素原子を有する以外は特に制限はないが、複素環の環員として2つ以上の窒素原子を有する複素環化合物であることが好ましく、1,3位に窒素原子を少なくとも有する複素環構造を有する化合物であることがより好ましく、1,3位に窒素原子を少なくとも有する5員又は6員複素環構造を有する化合物であることが更に好ましい。上記態様であると、無機粒子の分散性により優れ、ヘイズがより小さい硬化物が得られる。
なお、「1,3位に窒素原子を少なくとも有する複素環構造」とは、複素環中に炭素原子の両側に窒素原子が結合した構造であればよく、正式な命名法における複素環上の1位及び3位でなくともよい。
成分Lが有する窒素原子の数は、2つ以上であり、2~6であることが好ましく、2~4であることがより好ましい。また、成分Lは、複素環の環員として、窒素原子を2~4つ有していることが好ましく、2つ又は3つ有していることがより好ましく、2つ有していることが更に好ましい。
成分Lにおける複素環は、飽和複素環であっても、不飽和複素環であってもよく、芳香族複素環であってもよい。
また、成分Lにおける複素環は、更に他の環と縮合していてもよい。また、上記他の環としては、複素環だけでなく、脂肪族環であっても、芳香環であってもよい。
また、成分Lとしては、下記式(L-a)で表される化合物であることが好ましい。
また、Ra1及びRa2における一価の有機基の炭素数は、0~20であることが好ましく、0~8であることがより好ましく、0であることが特に好ましい。
また、Ra1とRa2とが結合して形成する二価の有機基としては、オキソ基、チオキソ基、アルキリデン基等が例として挙げられる。これらの中でも、チオキソ基が特に好ましい。
Ra1及びRa2はそれぞれ独立に、水素原子又はメルカプト基であることが特に好ましく、また、Ra1とRa2とが結合して二価の有機基を形成する場合は、チオキソ基であることが特に好ましい。
Ra3及びRa4における一価の有機基の炭素数は、0~20であることが好ましく、1~10であることがより好ましく、4~8であることが更に好ましい。
Ra3及びRa4はそれぞれ独立に、水素原子、アルキル基又はアリール基であることが好ましく、水素原子、メチル基、モルフォリノメチル基又はフェニル基であることがより好ましく、水素原子、メチル基又はフェニル基であることが更に好ましく、水素原子又はメチル基であることが特に好ましい。
二価の連結基としては、式(L-a)中の炭素原子と2つの窒素原子とともに5員複素環又は6員複素環を形成する基であれば、特に制限はないが、その環員が、炭素原子及び/又は窒素原子から形成される基であることが好ましく、前述した複素環構造の具体例を形成する基であることがより好ましい。中でも、ベンゾイミダゾール構造を形成する基、すなわち、1,2-フェニレン基、イミダゾリジン構造を形成する基、すなわち、1,2-エチレン基、1,1-ジメチル-1,2-エチレン基、又は、エテン-1,2-ジイル基であることが更に好ましく、1,2-エチレン基、1,1-ジメチル-1,2-エチレン基、又は、エテン-1,2-ジイル基であることが特に好ましい。
また、式(L-a-1)又は式(L-a-2)におけるLa2及びLa3は、上記式(L-a)におけるLa1と同義であり、好ましい態様も同様である。
成分Lの好ましい具体例(AF-1~AF-14)を以下に示す。ただし、本発明においては、これらに制限されるものではない。
本発明の感光性樹脂組成物における成分Lの含有量は、本発明の感光性樹脂組成物の全固形分に対して、0.1~20質量%であることが好ましく、0.5~15質量%であることがより好ましく、0.5~10質量%であることが更に好ましい。上記範囲であると、無機粒子の分散性により優れ、ヘイズがより小さい硬化物が得られる。
本発明の感光性樹脂組成物には、上記成分に加えて、必要に応じて、酸化防止剤、紫外線吸収剤、金属不活性化剤、酸増殖剤、現像促進剤、可塑剤、熱ラジカル発生剤、熱酸発生剤、増粘剤、及び、有機又は無機の沈殿防止剤などの公知の添加剤を加えることができる。また、これらの化合物としては、例えば特開2012-88459号公報の段落0201~0224の記載も参酌でき、これらの内容は本願明細書に組み込まれる。
本発明の感光性樹脂組成物は、酸化防止剤を含有することが好ましい。酸化防止剤としては、公知の酸化防止剤を含有することができる。酸化防止剤を添加することにより、硬化膜の着色を防止できる、又は、分解による膜厚減少を低減でき、また、耐熱透明性に優れるという利点がある。
このような酸化防止剤としては、例えば、リン系酸化防止剤、アミド類、ヒドラジド類、ヒンダードアミン系酸化防止剤、イオウ系酸化防止剤、フェノール系酸化防止剤、アスコルビン酸類、硫酸亜鉛、糖類、亜硝酸塩、亜硫酸塩、チオ硫酸塩、ヒドロキシルアミン誘導体等を挙げることができる。これらの中では、硬化膜の着色、膜厚減少の観点から特にフェノール系酸化防止剤、ヒンダードアミン系酸化防止剤、リン系酸化防止剤、アミド系酸化防止剤、ヒドラジド系酸化防止剤、イオウ系酸化防止剤が好ましく、フェノール系酸化防止剤が最も好ましい。これらは1種単独で用いてもよいし、2種以上を混合してもよい。
具体例としては、特開2005-29515号公報の段落0026~0031、特開2011-227106号公報の段落0106~0116に記載の化合物を挙げることができ、これらの内容は本願明細書に組み込まれる。
酸化防止剤の市販品としては、例えば、アデカスタブAO-15、アデカスタブAO-18、アデカスタブAO-20、アデカスタブAO-23、アデカスタブAO-30、アデカスタブAO-37、アデカスタブAO-40、アデカスタブAO-50、アデカスタブAO-51、アデカスタブAO-60、アデカスタブAO-70、アデカスタブAO-80、アデカスタブAO-330、アデカスタブAO-412S、アデカスタブAO-503、アデカスタブA-611、アデカスタブA-612、アデカスタブA-613、アデカスタブPEP-4C、アデカスタブPEP-8、アデカスタブPEP-8W、アデカスタブPEP-24G、アデカスタブPEP-36、アデカスタブPEP-36Z、アデカスタブHP-10、アデカスタブ2112、アデカスタブ260、アデカスタブ522A、アデカスタブ1178、アデカスタブ1500、アデカスタブC、アデカスタブ135A、アデカスタブ3010、アデカスタブTPP、アデカスタブCDA-1、アデカスタブCDA-6、アデカスタブZS-27、アデカスタブZS-90、アデカスタブZS-91(以上、(株)ADEKA製)、イルガノックス245FF、イルガノックス1010FF、イルガノックス1010、イルガノックスMD1024、イルガノックス1035FF、イルガノックス1035、イルガノックス1098、イルガノックス1330、イルガノックス1520L、イルガノックス3114、イルガノックス1726、イルガフォス168、イルガモッド295(BASF社製)、チヌビン405(BASF社製)などが挙げられる。中でも、アデカスタブAO-60、アデカスタブAO-80、イルガノックス1726、イルガノックス1035、イルガノックス1098、チヌビン405を好適に使用することができる。
また、酸化防止剤以外の添加剤として、「高分子添加剤の新展開」((株)日刊工業新聞社)に記載の各種紫外線吸収剤や、金属不活性化剤等を本発明の感光性樹脂組成物に添加してもよい。
本発明の感光性樹脂組成物は、感度向上を目的に、酸増殖剤を用いてもよい。
本発明に用いることができる酸増殖剤は、酸触媒反応によって更に酸を発生して反応系内の酸濃度を上昇させることができる化合物であり、酸が存在しない状態では安定に存在する化合物である。
このような酸増殖剤の具体例としては、特開2011-221494号公報の段落0226~0228に記載の酸増殖剤が挙げられ、この内容は本願明細書に組み込まれる。
本発明の感光性樹脂組成物は、現像促進剤を含有することができる。
現像促進剤としては、現像促進効果のある任意の化合物を使用できるが、カルボキシル基、フェノール性水酸基、及び、アルキレンオキシ基よりなる群から選ばれた少なくとも1種の構造を有する化合物であることが好ましく、カルボキシル基又はフェノール性水酸基を有する化合物がより好ましく、フェノール性水酸基を有する化合物が最も好ましい。
現像促進剤としては、特開2012-042837号公報の段落0171~0172の記載を参酌でき、この内容は本願明細書に組み込まれる。
本発明の感光性樹脂組成物における現像促進剤の添加量は、感度と残膜率の観点から、感光性樹脂組成物の全固形分100質量部に対し、0~30質量部が好ましく、0.1~20質量部がより好ましく、0.5~10質量部であることが最も好ましい。
また、現像促進剤の分子量は、100~2,000が好ましく、150~1,500がより好ましく、150~1,000が更に好ましい。
本発明の樹脂組成物は、可塑剤を含有してもよい。
可塑剤としては、例えば、ジブチルフタレート、ジオクチルフタレート、ジドデシルフタレート、ポリエチレングリコール、グリセリン、ジメチルグリセリンフタレート、酒石酸ジブチル、アジピン酸ジオクチル、トリアセチルグリセリンなどが挙げられる。
本発明の樹脂組成物における可塑剤の含有量は、成分Aの含有量100質量部に対して、0.1~30質量部であることが好ましく、1~10質量部であることがより好ましい。
各成分を所定の割合でかつ任意の方法で混合撹拌し、溶解又は分散して感光性樹脂組成物を調製する。例えば、成分を、それぞれ予め溶剤に溶解又は分散させた液とした後、これらを所定の割合で混合して樹脂組成物を調製することもできる。以上のように調製した組成物は、例えば孔径0.2μmのフィルター等を用いてろ過した後に、使用に供することもできる。
なお、本発明において、(成分A)金属酸化物粒子、(成分C)溶剤、及び、(成分F)分散剤を含有する金属酸化物粒子分散物を予め調製し、金属酸化物粒子分散物と、成分B、成分D及び成分E、並びに、任意の成分とを添加し感光性樹脂組成物を調製することが特に好ましい。
次に、本発明の樹脂パターン製造方法を説明する。
本発明の樹脂パターン製造方法は、以下の(1)~(4)の工程を含むことが好ましく、以下の(1)~(5)の工程を含むことがより好ましい。
(1)本発明の感光性樹脂組成物を基板上に塗布する塗布工程;
(2)塗布された樹脂組成物から溶剤を除去する溶剤除去工程;
(3)溶剤が除去された樹脂組成物を活性光線によりパターン状に露光する露光工程;
(4)露光された樹脂組成物を水性現像液により現像する現像工程;
(5)現像された樹脂組成物を熱処理する熱処理工程。
以下に各工程を順に説明する。
上記の基板としては、無機基板、樹脂、樹脂複合材料、ITO、Cu基板、ポリエチレンテレフタレート、セルローストリアセテート(TAC)などのプラスチック基板が挙げられる。
無機基板としては、例えばガラス、石英、シリコーン、シリコンナイトライド、及び、それらのような基板上にモリブデン、チタン、アルミ、銅などを蒸着した複合基板が挙げられる。
樹脂としては、ポリブチレンテレフタレート、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンナフタレート、ポリスチレン、ポリカーボネート、ポリスルホン、ポリエーテルスルホン、ポリアリレート、アリルジグリコールカーボネート、ポリアミド、ポリイミド、ポリアミドイミド、ポリエーテルイミド、ポリベンズアゾール、ポリフェニレンサルファイド、ポリシクロオレフィン、ノルボルネン樹脂、ポリクロロトリフルオロエチレン等のフッ素樹脂、液晶ポリマー、アクリル樹脂、エポキシ樹脂、シリコーン樹脂、アイオノマー樹脂、シアネート樹脂、架橋フマル酸ジエステル樹脂、環状ポリオレフィン、芳香族エーテル樹脂、マレイミド-オレフィン樹脂、セルロース、エピスルフィド樹脂等の合成樹脂からなる基板が挙げられる。
これらの基板は、上記の形態のまま用いられる場合は少なく、最終製品の形態によって、例えばTFT素子のような多層積層構造が形成されている場合が通常である。
本発明者らが鋭意検討した結果、基板の表面の全部又は一部がITO(酸化インジウムスズ、Indium Tin Oxide)である場合、ITO上への現像残渣の発生が特に顕著であることを見いだした。本発明の感光性樹脂組成物は、基板の表面の全部又は一部がITOである場合であっても、現像残渣の発生を抑制することができるという、極めて顕著な効果を有するものである。
塗布膜厚は特に限定されるものではなく、用途に応じた膜厚で塗布することができるが、0.5~10μmの範囲で使用されることが好ましい。
例えば、インクジェット方式による塗布条件は、感光性樹脂組成物の組成や、製造する塗膜の種類などによって適宜選択すればよい。塗布膜の厚さを調節するためには、液状の感光性樹脂組成物の吐出量や同一部分への吐出回数を調整すればよい。また、感光性樹脂組成物を塗布する形状や位置についても、所望に応じ、適宜選択すればよい。インクジェット方式の塗布に用いられる装置としては、特に制限はなく、公知のインクジェット塗布装置を適用すればよい。
具体的には、オンデマンドインクジェット塗布装置IJ-DESK-S、IJ-DESK-H((株)ピーエムティー製)、ダイマディックス・マテリアル・プリンターDMP2831、DMP-3000(FUJIFILM Dimatix社製)などが挙げられる。
インク供給系は、例えば、本発明の感光性樹脂組成物を含む元タンク、供給配管、インクジェットヘッド直前の組成物供給タンク、フィルター、ピエゾ型のインクジェットヘッドからなる。ピエゾ型のインクジェットヘッドは、好ましくは1~100pl、より好ましくは8~30plのマルチサイズドットを、好ましくは320×320~4,000×4,000dpi(dot per inch)、より好ましくは400×400~1,600×1,600dpi、更に好ましくは720×720dpiの解像度で吐出できるよう駆動することができる。なお、本発明でいうdpiとは、2.54cm当たりのドット数を表す。
塗布膜厚は特に限定されるものではなく、用途に応じた膜厚で塗布することができるが、0.5~10μmの範囲で使用されることが好ましい。
なお、(1)の塗布工程と(2)の溶剤除去工程とは、この順に行っても、同時に行っても、交互に繰り返してもよい。例えば、(1)の塗布工程におけるインクジェット塗布が全て終了した後、(2)の溶剤除去工程を行ってもよいし、基板を加熱しておき、(1)の塗布工程におけるインクジェット塗布方式による感光性樹脂組成物の吐出を行いながら溶剤除去を行ってもよい。
中でも、(1)の塗布工程におけるインクジェット塗布が全て終了した後、(2)の溶剤除去工程を行うことが好ましい。
活性光線による露光光源としては、低圧水銀灯、高圧水銀灯、超高圧水銀灯、ケミカルランプ、LED光源、エキシマレーザー発生装置などを用いることができ、g線(436nm)、i線(365nm)、h線(405nm)などの波長300nm以上450nm以下の波長を有する活性光線が好ましく使用できる。また、必要に応じて長波長カットフィルター、短波長カットフィルター、バンドパスフィルターのような分光フィルターを通して照射光を調整することもできる。
露光装置としては、ミラープロジェクションアライナー、ステッパー、スキャナー、プロキシミティ、コンタクト、マイクロレンズアレイ、レーザー露光など各種方式の露光機を用いることができる。
酸触媒の生成した領域において、上記の加水分解反応を加速させるために、露光後加熱処理:Post Exposure Bake(以下、「PEB」ともいう。)を行うことができる。PEBにより、酸分解性基からのカルボキシル基又はフェノール性水酸基の生成を促進させることができる。PEBを行う場合の温度は、30℃以上130℃以下であることが好ましく、40℃以上110℃以下がより好ましく、50℃以上100℃以下が特に好ましい。
但し、本発明における酸分解性基は、酸分解の活性化エネルギーが低く、露光による酸発生剤由来の酸により容易に分解し、酸基、例えば、カルボキシル基又はフェノール性水酸基を生じるため、必ずしもPEBを行うことなく、現像によりポジ画像を形成することもできる。
現像工程で使用する現像液には、塩基性化合物が含まれることが好ましい。塩基性化合物としては、例えば、水酸化リチウム、水酸化ナトリウム、水酸化カリウムなどのアルカリ金属水酸化物類;炭酸ナトリウム、炭酸カリウムなどのアルカリ金属炭酸塩類;重炭酸ナトリウム、重炭酸カリウムなどのアルカリ金属重炭酸塩類;テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、コリンヒドロキシド等のアンモニウムヒドロキシド類;ケイ酸ナトリウム、メタケイ酸ナトリウムなどの水溶液を使用することができる。また、上記アルカリ類の水溶液にメタノールやエタノールなどの水溶性有機溶剤や界面活性剤を適当量添加した水溶液を現像液として使用することもできる。
好ましい現像液として、テトラエチルアンモニウムヒドロキシドの0.4質量%水溶液、0.5質量%水溶液、0.7質量%水溶液、又は、2.38質量%水溶液を挙げることができる。
現像液のpHは、好ましくは10.0~14.0である。
現像時間は、好ましくは30~500秒間であり、また、現像の手法は液盛り法、ディップ法等のいずれでもよい。現像後は、流水洗浄を30~300秒間行い、所望のパターンを形成させることができる。
現像の後に、リンス工程を行うこともできる。リンス工程では、現像後の基板を純水などで洗うことで、付着している現像液除去、現像残渣除去を行う。リンス方法は公知の方法を用いることができる。例えばシャワーリンスやディップリンスなどを挙げることができる。
熱処理工程(ポストベーク)の前に、比較的低温でベークを行った後に熱処理工程を行うこともできる(ミドルベーク工程の追加)。ミドルベークを行う場合は、90~150℃で1~60分加熱した後に、200℃以上の高温でポストベークすることが好ましい。また、ミドルベーク、ポストベークを3段階以上の多段階に分けて加熱することもできる。このようなミドルベーク、ポストベークの工夫により、パターンのテーパー角を調整することができる。これらの加熱は、ホットプレート、オーブン、赤外線ヒーターなど、公知の加熱方法を使用することができる。
なお、ポストベークに先立ち、パターンを形成した基板に活性光線により全面再露光(ポスト露光)した後、ポストベークすることにより未露光部分に存在する光酸発生剤から酸を発生させ、架橋工程を促進する触媒として機能させることができ、膜の硬化反応を促進することができる。ポスト露光工程を含む場合の好ましい露光量としては、100~3,000mJ/cm2が好ましく、100~500mJ/cm2が特に好ましい。
本発明の硬化膜は、本発明の感光性樹脂組成物を硬化して得られた膜である。
本発明の硬化膜は、層間絶縁膜として好適に用いることができる。また、本発明の硬化膜は、本発明の硬化物の製造方法又は本発明の樹脂パターン製造方法により得られた膜であることが好ましい。
本発明の感光性樹脂組成物により、絶縁性に優れ、高温でベークされた場合においても高い透明性を有する層間絶縁膜が得られる。本発明の感光性樹脂組成物を用いてなる層間絶縁膜は、高い透明性を有し、硬化膜物性に優れるため、有機EL表示装置や液晶表示装置、タッチパネル表示装置の用途に有用である。
本発明の硬化物は、本発明の感光性樹脂組成物を硬化して得られた硬化物であり、上記のように、その形状は、膜でなくともよく、任意の形状であればよい。
また、本発明の硬化物は、少なくとも、本発明の感光性樹脂組成物から少なくとも一部の溶剤を除去して硬度が上昇した硬化物であればよいが、本発明の感光性樹脂組成物から溶剤を除去し、熱硬化して得られた硬化物であることが好ましい。
本発明の硬化物の製造方法は、特に制限はないが、少なくとも以下の工程(a)~(c)をこの順に含むことが好ましい。
(a)本発明の感光性樹脂組成物を基板上に塗布する塗布工程;
(b)塗布された樹脂組成物から溶剤を除去する溶剤除去工程;
(c)溶剤が除去された樹脂組成物を熱処理する熱処理工程
工程(c)は、熱処理する対象が工程(b)で得られた溶剤が除去された樹脂組成物であること以外は、上記熱処理工程と同様の工程であり、上記熱処理工程における加熱温度、加熱時間、加熱手段等の好ましい態様も同様に好ましい。
また、本発明の硬化物は、例えば、後述するような、液晶表示装置又は有機EL装置等における平坦化膜や層間絶縁膜、カラーフィルターの保護膜、液晶表示装置における液晶層の厚みを一定に保持するためのスペーサー、MEMS(Micro Electro Mechanical Systems)デバイスの構造部材等に好適に用いることができる。
本発明の液晶表示装置は、本発明の硬化物を具備することを特徴とする。
本発明の液晶表示装置としては、本発明の感光性樹脂組成物を用いて形成される平坦化膜や層間絶縁膜を有すること以外は特に制限されず、様々な構造をとる公知の液晶表示装置を挙げることができる。
例えば、本発明の液晶表示装置が具備するTFT(Thin-Film Transistor)の具体例としては、アモルファスシリコン-TFT、低温ポリシリコン-TFT、酸化物半導体TFT等が挙げられる。本発明の硬化膜は電気特性に優れるため、これらのTFTに組み合わせて好ましく用いることができる。
また、本発明の液晶表示装置が取りうる液晶駆動方式としてはTN(Twisted Nematic)方式、VA(Vertical Alignment)方式、IPS(In-Plane-Switching)方式、FFS(Fringe Field Switching)方式、OCB(Optically Compensated Bend)方式などが挙げられる。
パネル構成においては、COA(Color Filter on Array)方式の液晶表示装置でも本発明の硬化膜を用いることができ、例えば、特開2005-284291号公報に記載の有機絶縁膜(115)や、特開2005-346054号公報に記載の有機絶縁膜(212)として用いることができる。
また、本発明の液晶表示装置が取りうる液晶配向膜の具体的な配向方式としてはラビング配向法、光配向方などが挙げられる。また、特開2003-149647号公報や特開2011-257734号公報に記載のPSA(Polymer Sustained Alignment)技術によってポリマー配向支持されていてもよい。
また、本発明の感光性樹脂組成物及び本発明の硬化物は、上記用途に限定されず種々の用途に使用することができる。例えば、平坦化膜や層間絶縁膜以外にも、カラーフィルターの保護膜や、液晶表示装置における液晶層の厚みを一定に保持するためのスペーサーや固体撮像素子においてカラーフィルター上に設けられるマイクロレンズ等に好適に用いることができる。
バックライトの光源としては、特に限定されず公知の光源を用いることができる。例えば白色LED、青色・赤色・緑色などの多色LED、蛍光灯(冷陰極管)、有機ELなどを挙げることができる。
また、液晶表示装置は、3D(立体視)型のものとしたり、タッチパネル型のものとしたりすることも可能である。更にフレキシブル型にすることも可能であり、特開2011-145686号公報に記載の第2相間絶縁膜(48)や、特開2009-258758号公報に記載の相間絶縁膜(520)として用いることができる。
本発明の有機EL表示装置は、本発明の硬化物を具備することを特徴とする。
本発明の有機EL表示装置としては、本発明の感光性樹脂組成物を用いて形成される光取り出し層、平坦化膜や層間絶縁膜を有すること以外は特に制限されず、様々な構造をとる公知の各種有機EL表示装置や液晶表示装置を挙げることができる。
例えば、本発明の有機EL表示装置が具備するTFT(Thin-Film Transistor)の具体例としては、アモルファスシリコン-TFT、低温ポリシリコン-TFT、酸化物半導体TFT(例えば、インジウムガリウム亜鉛酸化物(IGZO)やインジウム亜鉛酸化物(IZO))等が挙げられる。本発明の硬化膜は電気特性に優れるため、これらのTFTに組み合わせて好ましく用いることができる。
図2は、有機EL表示装置の一例の構成概念図である。ボトムエミッション型の有機EL表示装置における基板の模式的断面図を示し、平坦化膜4を有している。
ガラス基板6上にボトムゲート型のTFT1を形成し、このTFT1を覆う状態でSi3N4から成る絶縁膜3が形成されている。絶縁膜3に、ここでは図示を省略したコンタクトホールを形成した後、このコンタクトホールを介してTFT1に接続される配線2(高さ1.0μm)が絶縁膜3上に形成されている。配線2は、TFT1間、又は、後の工程で形成される有機EL素子とTFT1とを接続するためのものである。
更に、配線2の形成による凹凸を平坦化するために、配線2による凹凸を埋め込む状態で絶縁膜3上に平坦化層4が形成されている。
平坦化膜4上には、ボトムエミッション型の有機EL素子が形成されている。すなわち、平坦化膜4上に、ITOからなる第一電極5が、コンタクトホール7を介して配線2に接続させて形成されている。また、第一電極5は、有機EL素子の陽極に相当する。
第一電極5の周縁を覆う形状の絶縁膜8が形成されており、この絶縁膜8を設けることによって、第一電極5とこの後の工程で形成する第二電極との間のショートを防止することができる。
更に、図2には図示していないが、所望のパターンマスクを介して、正孔輸送層、有機発光層、電子輸送層を順次蒸着して設け、次いで、基板上方の全面にAlから成る第二電極を形成し、封止用ガラス板と紫外線硬化型エポキシ樹脂を用いて貼り合わせることで封止し、各有機EL素子にこれを駆動するためのTFT1が接続されてなるアクティブマトリックス型の有機EL表示装置が得られる。
本発明のタッチパネル表示装置は、本発明の硬化物を有する静電容量型入力装置を具備する。また、本発明の静電容量型入力装置は、本発明の膜を有することを特徴とする。
本発明の静電容量型入力装置は、前面板と、上記前面板の非接触側に、少なくとも下記(1)~(5)の要素を有し、下記(4)が本発明の感光性樹脂組成物を熱処理した、好ましくは熱硬化した熱処理物であることが好ましい。
(1)マスク層
(2)複数のパッド部分が接続部分を介して第一の方向に延在して形成された複数の第一の透明電極パターン
(3)上記第一の透明電極パターンと電気的に絶縁され、上記第一の方向に交差する方向に延在して形成された複数のパッド部分からなる複数の第二の透明電極パターン
(4)上記第一の透明電極パターンと上記第二の透明電極パターンとを電気的に絶縁する絶縁層
(5)上記第一の透明電極パターン及び上記第二の透明電極パターンの少なくとも一方に電気的に接続され、上記第一の透明電極パターン及び上記第二の透明電極パターンとは別の導電性要素
本発明の静電容量型入力装置は、更に上記(1)~(5)の要素の全て又は一部を覆うように透明保護層を設置することが好ましく、上記透明保護層が本発明の硬化膜であることがより好ましい。
本発明の静電容量型入力装置には、図4に示すように、前面板31の一部の領域(図4においては入力面以外の領域)を覆うようにマスク層32が設けられている。更に、前面板31には、図4に示すように一部に開口部38を設けることができる。開口部38には、押圧によるメカニカルなスイッチを設置することができる。
本発明の製造方法によって得られる静電容量型入力装置、及び、当該静電容量型入力装置を構成要素として備えたタッチパネル表示装置は、「最新タッチパネル技術」(2009年7月6日発行(株)テクノタイムズ)、三谷雄二監修、“タッチパネルの技術と開発”、(株)シーエムシー出版(2004,12)、FPD International 2009 Forum T-11講演テキストブック、Cypress Semiconductor Corporation アプリケーションノートAN2292等に開示されている構成を適用することができる。
本発明のタッチパネルは、絶縁層の全部又は一部が本発明の樹脂組成物の熱処理物からなるタッチパネルである。また、本発明のタッチパネルは、透明基板、ITO電極及び絶縁層を少なくとも有することが好ましい。
本発明のタッチパネル表示装置は、本発明のタッチパネルを有するタッチパネル表示装置であることが好ましい。
また、本発明のタッチパネルの製造方法は、透明基板、ITO電極及び絶縁層を有するタッチパネルの製造方法であって、ITO電極に接するように、本発明のインクジェット塗布用感光性樹脂組成物をインクジェット塗布方式により塗布する工程、上記樹脂組成物上に所定形状の開口パターンを有するマスクを載置し、活性エネルギー線照射を行い露光する工程、露光後の樹脂組成物を現像する工程、及び、現像後の樹脂組成物を加熱して、絶縁層を製造する工程、を含むことが好ましい。
上記ITO電極に接するように、本発明のインクジェット塗布用感光性樹脂組成物をインクジェット塗布方式により塗布する工程におけるインクジェット塗布は、上述した塗布工程と同様に行うことができ、好ましい態様も同様である。また、上記工程においては、塗布された本発明の感光性樹脂組成物の少なくとも一部が、ITO電極に接していればよい。
上記樹脂組成物上に所定形状の開口パターンを有するマスクを載置し、活性エネルギー線照射を行い露光する工程、露光後の樹脂組成物を現像する工程は、上述した露光工程と同様に行うことができ、好ましい態様も同様である。
上記現像後の樹脂組成物を加熱して、絶縁層を製造する工程は、上述した熱処理工程と同様に行うことができ、好ましい態様も同様である。
また、本発明のタッチパネルにおけるITO電極パターンの一例としては、上述した図5に示すパターンが好ましく挙げられる。
-分散液Iの組成-
酸化チタン:25.0%(石原産業(株)製TTO-51(C))
分散剤1(下記化合物の固形分30%PGMEA溶液):固形分として7.5%
PGMEA(プロピレングリコールモノメチルエーテルアセテート、昭和電工(株)製):67.5%
上記組成の分散液組成物を寿技研工業(株)製ウルトラアペックスミルにて、0.05mmジルコニアビーズ充填率75%、周速12m/sec、循環流量180g/minで150min循環させて分散し、分散液Iを得た。
なお、下記化合物中、L=5.5、m=0.5、n1:n2=86.5質量%:13.5質量%である。
表1に記載されたように酸化チタン及び/又は分散剤を変更した以外は、上記分散液Iの調製と同様にして、分散液II~IVをそれぞれ調製した。
・分散剤2:BYK-111:固形分95%、DISPERBYK-111、ビックケミー・ジャパン(株)製
・分散剤3:下記化合物の固形分30%PGMEA溶液、Mw15,000、酸価140mgKOH/g
<ポジ型感光性樹脂組成物の調製>
下記組成にて、配合し混合して均一な溶液とした後、0.2μmのポアサイズを有するポリエチレン製フィルターを用いてろ過して、実施例1のポジ型感光性樹脂組成物を調製した。
-組成-
・プロピレングリコールモノメチルエーテルアセテート(PGMEA):36.0%
・重合体D-1(固形分40%PGMEA溶液):12.0%
・下記化合物B-1:5.0%
・光酸発生剤E-1(下記化合物):0.7%
・3-グリシドキシプロピルトリメトキシシラン(H-1、KBM-403、信越化学工業(株)製):0.5%
・CMTU(J-1、下記化合物、東洋化成工業(株)製、0.2%PGMEA溶液)3.0%
・下記化合物K-1の2.0%PGMEA溶液:1.5%
・下記化合物L-2:0.3%
・分散液I:41.0%
2-ナフトール(10g)、クロロベンゼン(30mL)の懸濁溶液に塩化アルミニウム(10.6g)、2-クロロプロピオニルクロリド(10.1g)を添加し、混合液を40℃に加熱して2時間反応させた。氷冷下、反応液に4NHCl水溶液(60mL)を滴下し、酢酸エチル(50mL)を添加して分液した。有機層に炭酸カリウム(19.2g)を加え、40℃で1時間反応させた後、2NHCl水溶液(60mL)を添加して分液し、有機層を濃縮後、結晶をジイソプロピルエーテル(10mL)でリスラリーし、ろ過、乾燥してケトン化合物(6.5g)を得た。
得られたケトン化合物(3.0g)、メタノール(30mL)の懸濁溶液に酢酸(7.3g)、50質量%ヒドロキシルアミン水溶液(8.0g)を添加し、加熱還流した。放冷後、水(50mL)を加え、析出した結晶をろ過、冷メタノール洗浄後、乾燥してオキシム化合物(2.4g)を得た。
得られたオキシム化合物(1.8g)をアセトン(20mL)に溶解させ、氷冷下トリエチルアミン(1.5g)、p-トルエンスルホニルクロリド(2.4g)を添加し、室温(25℃)に昇温して1時間反応させた。反応液に水(50mL)を添加し、析出した結晶をろ過後、メタノール(20mL)でリスラリーし、ろ過、乾燥してE-1の化合物(上述の構造)(2.3g)を得た。
なお、E-1の1H-NMRスペクトル(300MHz、CDCl3)は、δ=8.3(d,1H),8.0(d,2H),7.9(d,1H),7.8(d,1H),7.6(dd,1H),7.4(dd,1H),7.3(d,2H),7.1(d,1H),5.6(q,1H),2.4(s,3H),1.7(d,3H)であった。
MATHF:メタクリル酸テトラヒドロフラン-2-イル(合成品)
MAEVE:メタクリル酸1-エトキシエチル(和光純薬工業(株)製)
MAA:メタクリル酸(和光純薬工業(株)製)
GMA:グリシジルメタクリレート(和光純薬工業(株)製)
OXE-30:メタクリル酸(3-エチルオキセタン-3-イル)メチル(大阪有機化学工業(株)製)
MMA:メタクリル酸メチル(和光純薬工業(株)製)
St:スチレン(和光純薬工業(株)製)
メタクリル酸(86g、1mol)を15℃に冷却しておき、カンファースルホン酸(4.6g,0.02mol)添加した。その溶液に、2-ジヒドロフラン(71g、1mol、1.0当量)を滴下した。1時間撹拌した後に、飽和炭酸水素ナトリウム(500mL)を加え、酢酸エチル(500mL)で抽出し、硫酸マグネシウムで乾燥後、不溶物をろ過後40℃以下で減圧濃縮し、残渣の黄色油状物を減圧蒸留して沸点(bp.)54~56℃/3.5mmHg留分のメタクリル酸テトラヒドロフラン-2-イル(MATHF)125gを無色油状物として得た(収率80%)。
メタクリル酸テトラヒドロフラン-2-イル(0.65モル当量)、
メタクリル酸(0.15モル当量)、
メタクリル酸メチル(0.20モル当量)を合計で100部、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(PGMEA)(120部)の混合溶液を窒素気流下、70℃に加熱した。この混合溶液を撹拌しながら、ラジカル重合開始剤V-601(ジメチル 2,2’-アゾビス(2-メチルプロピオネート))、和光純薬工業(株)製、12.0部)及びPGMEA(80部)の混合溶液を3.5時間かけて滴下した。滴下が終了してから、70℃で2時間反応させることにより重合体P1のPGMEA溶液を得た。更にPGMEAを添加して固形分濃度40質量%に調整した。
得られた重合体P1のゲルパーミエーションクロマトグラフィ(GPC)により測定した重量平均分子量(Mw)は、15,000であった。
モノマー組成を表2のように変更した以外は、重合体D-1と同様の方法により、重合体D-2~D-5のPGMEA溶液をそれぞれ得た。更にPGMEAを添加して固形分濃度40質量%に調整した。
得られた実施例1の感光性樹脂組成物を使用し、以下の評価を行った。評価結果を表3に示す。
得られた感光性樹脂組成物を、スピナーを用いてシリコンウエハ基板上に塗布し、80℃で120秒乾燥することによって厚さ0.7μmの膜を形成した。この基板を、超高圧水銀灯を用いて200mJ/cm2(i線で測定)で露光し、その後オーブンにて230℃分で60分加熱した。
エリプソメーターVUV-VASE(ジェー・エー・ウーラム・ジャパン(株)製)を用いて、550nmでの硬化膜の屈折率を測定した。屈折率が高いほうが好ましく、1.70以上がより好ましい。
ベアウエハ(N型低抵抗)(SUMCO社製)上に、感光性樹脂組成物をスリット塗布した後、80℃にて2分間ホットプレート上でプリベークして膜厚0.7μmの感光性樹脂組成物層を形成した。得られた感光性樹脂組成物を、キヤノン(株)製PLA-501F露光機(超高圧水銀ランプ)で積算照射量が200mJ/cm2(照度:20mW/cm2)となるように露光し、この基板をオーブンにて230℃で1時間加熱することにより、硬化膜を得た。
この硬化膜について、CVmap92A(Four Dimensions Inc.社製)を用い、測定周波数1MHzで比誘電率を測定した。この値が低いほど好ましく、硬化膜の比誘電率は良好であるといえる。
100mm×100mmのガラス基板(商品名:XG、コーニング社製)上に、得られた感光性樹脂組成物をスピンコーターにて塗布し、80℃のホットプレート上で120秒乾燥(プリベーク)した。次に、ghi線高圧水銀灯露光機を用いて、エネルギー強度20mW/cm2、200mJ/cm2にて全面露光した。更に、塗布膜を230℃のオーブンで60分加熱処理(ポストベーク)を施した。膜厚はポストベーク後で1μmになるように最初の塗布膜厚を調整した。ポストベーク後のサンプルのヘイズを日本電色工業(株)製NDH-5000にて膜面を上にして、プラスチック製品試験方法(JIS K7136・JIS K7361・ASTM D1003)に準拠し、曇り度(ヘイズ値)を測定した。
なお、ヘイズ値とは、全光線透過光に対する拡散透過光の割合(%)で表される値を指す。ヘイズ値が小さいほど、透明性が高いことを表す。
感光性樹脂組成物の各成分を表3~表7に記載の成分に変更した以外は、実施例1におけるポジ型感光性樹脂組成物の調製と同様に、実施例2~114、及び、比較例1~34の感光性樹脂組成物をそれぞれ調製し、実施例1と同様な方法により評価した。評価結果を表3~表7に示す。
<式(I)で表される化合物>
B-2、B-4:下記化合物
B-3:下記化合物、大阪ガスケミカル(株)製BPE(9,9-ビス(4-ヒドロキシフェニル)フルオレン)
B-5:下記化合物、大阪ガスケミカル(株)製BPEF(ビスフェノキシエタノールフルオレン)
E-2:下記に示す構造(合成例を後述する。)
1-アミノ-2-ナフトール塩酸塩(東京化成工業(株)製)4.0gをN-メチルピロリドン(和光純薬工業(株)製)16gに懸濁させ、炭酸水素ナトリウム(和光純薬工業(株)製)3.4gを添加後、4,4-ジメチル-3-オキソ吉草酸メチル(和光純薬工業(株)製)4.9gを滴下し、窒素雰囲気下120℃で2時間加熱した。放冷後、反応混合液に水、酢酸エチルを添加して分液し、有機相を硫酸マグネシウムで乾燥し、ろ過、濃縮して粗E-2Aを得た。粗E-2Aをシリカゲルカラムクロマトグラフィーにより精製して、中間体E-2Aを1.7g得た。
E-2A(1.7g)とp-キシレン(6mL)とを混合し、p-トルエンスルホン酸一水和物(和光純薬工業(株)製)0.23gを添加して140℃で2時間加熱した。放冷後、反応混合液に水、酢酸エチルを添加して分液し、有機相を硫酸マグネシウムで乾燥後、ろ過、濃縮して粗E-2Bを得た。
THF(2mL)と粗E-2B全量を混合し、氷冷下2M塩酸/THF溶液6.0mL、次いで亜硝酸イソペンチル(和光純薬工業(株)製)(0.84g)を滴下し、室温まで昇温後2時間撹拌した。得られた反応混合物に水、酢酸エチルを添加して分液し、有機層を水で洗浄後、硫酸マグネシウムで乾燥し、ろ過、濃縮して中間体粗E-2Cを得た。
中間体粗E-2C全量をアセトン(10mL)と混合し、氷冷下でトリエチルアミン(和光純薬工業(株)製)(1.2g)、p-トルエンスルホニルクロリド(東京化成工業(株)製)(1.4g)を添加後、室温まで昇温して1時間撹拌した。得られた反応混合液に水、酢酸エチルを添加して分液し、有機相を硫酸マグネシウムで乾燥後、ろ過、濃縮して粗E-2を得た。粗E-2を冷メタノールでリスラリー後、ろ過、乾燥してE-2(1.2g)を得た。
G-1:jER157S65(ノボラック型エポキシ樹脂、(株)三菱ケミカルホールディングス製)
G-2:jER828(ビスフェノールA型エポキシ樹脂、(株)三菱ケミカルホールディングス製)
G-3:jER1007(ビスフェノールA型エポキシ樹脂、(株)三菱ケミカルホールディングス製)
H-2:ビス(トリエトキシシリルプロピル)テトラスルフィド(KBE-846(信越化学工業(株)製))
H-3:ヘキシルトリメトキシシラン(KBM-3063(信越化学工業(株)製))
<増感剤>
I-1:DBA(9,10-ジブトキシアントラセン、川崎化成工業(株)製)
<塩基性化合物>
J-2:1,5-ジアザビシクロ[4.3.0]-5-ノネン(東京化成工業(株)製、0.2%PGMEA溶液)
<その他添加剤>
L-1:下記化合物(2つ以上の窒素原子を有する複素環化合物)
特許第3321003号公報の図1に記載のアクティブマトリクス型液晶表示装置において、層間絶縁膜として硬化膜17を以下のようにして形成し、実施例115の液晶表示装置を得た。すなわち、実施例34の感光性樹脂組成物を基板上に塗布し、ホットプレート上でプリベーク(90℃/120秒)した後、マスク上から高圧水銀灯を用いてi線(365nm)を45mJ/cm2(照度20mW/cm2)照射した後、アルカリ水溶液にて現像してパターンを形成し、230℃/30分間の加熱処理を行い、層間絶縁膜として硬化膜17を形成した。
薄膜トランジスター(TFT)を用いた有機EL表示装置を以下の方法で作製した(図2参照)。
ガラス基板6上にボトムゲート型のTFT1を形成し、このTFT1を覆う状態でSi3N4から成る絶縁膜3を形成した。次に、この絶縁膜3に、ここでは図示を省略したコンタクトホールを形成した後、このコンタクトホールを介してTFT1に接続される配線2(高さ1.0μm)を絶縁膜3上に形成した。この配線2は、TFT1間、又は、後の工程で形成される有機EL素子とTFT1とを接続するためのものである。
感光性樹脂組成物を塗布する際の塗布性は良好で、露光、現像、焼成の後に得られた硬化膜には、しわやクラックの発生は認められなかった。更に、配線2の平均段差は500nm、作製した平坦化膜4の膜厚は2,000nmであった。
以下に述べる方法により本発明の高屈折率の感光性樹脂組成物を用いてタッチパネル表示装置を作製した。
[透明電極層の形成]
あらかじめマスク層が形成された強化処理ガラス(300mm×400mm×0.7mm)の前面板を、真空チャンバー内に導入し、SnO2含有率が10質量%のITOターゲット(インジウム:錫=95:5(モル比))を用いて、DCマグネトロンスパッタリング(条件:基材の温度250℃、アルゴン圧0.13Pa、酸素圧0.01Pa)により、厚さ40nmのITO薄膜を形成し、透明電極層を形成した前面板を得た。ITO薄膜の表面抵抗は80Ω/□であった。
次に、エッチングレジスト層パターンのついた透明電極層パターン付の前面板を、専用のレジスト剥離液に浸漬し、エッチング用光硬化性樹脂層を除去し、マスク層と第一の透明電極パターンとを形成した前面板を得た。
マスク層と第一の透明電極パターンとを形成した前面板の上に、実施例5の感光性樹脂組成物を塗布・乾燥(膜厚1μm、90℃120秒)し、感光性樹脂組成物層を得た。露光マスク(絶縁層用パターンを有す石英露光マスク)面と該感光性樹脂組成物層との間の距離を30μmに設定し、露光量50mJ/cm2(i線)でパターン露光した。
次に、2.38質量%のテトラメチルアンモニウムヒドロキシド水溶液により23℃で15秒間浸液盛り法にて現像し、更に超純水で10秒間リンスした。続いて220℃45分のポストベーク処理を行って、マスク層、第一の透明電極パターン、絶縁層パターンを形成した前面板を得た。
[透明電極層の形成]
上記第一の透明電極パターンの形成と同様にして、絶縁層パターンまで形成した前面板をDCマグネトロンスパッタリング処理し(条件:基材の温度50℃、アルゴン圧0.13Pa、酸素圧0.01Pa)、厚さ80nmのITO薄膜を形成し、透明電極層を形成した前面板を得た。ITO薄膜の表面抵抗は110Ω/□であった。
第一の透明電極パターンの形成と同様にして、市販のエッチングレジストを用いて、第一の透明電極パターン、実施例5の感光性樹脂組成物を用いて形成した絶縁層パターン、透明電極層、エッチングレジストパターンを形成した前面板を得た(ポストベーク処理;130℃30分間)。
更に、第一の透明電極パターンの形成と同様にして、エッチングし、エッチングレジスト層を除去することにより、マスク層、第一の透明電極パターン、実施例5の感光性樹脂組成物用いて形成した絶縁層パターン、第二の透明電極パターンを形成した前面板を得た。
上記第一、及び、第二の透明電極パターンの形成と同様にして、第一の透明電極パターン、実施例5の感光性樹脂組成物を用いて形成した絶縁層パターン、第二の透明電極パターンを形成した前面板をDCマグネトロンスパッタリング処理し、厚さ200nmのアルミニウム(Al)薄膜を形成した前面板を得た。
上記第一、及び、第二の透明電極パターンの形成と同様にして、市販のエッチングレジストを用いて、第一の透明電極パターン、実施例5の感光性樹脂組成物を用いて形成した絶縁層パターン、第二の透明電極パターン、エッチングレジストパターンを形成した前面板を得た(ポストベーク処理;130℃30分間)。
更に、第一の透明電極パターンの形成と同様にして、エッチング(30℃50秒間)し、エッチングレジスト層を除去(45℃200秒間)することにより、マスク層、第一の透明電極パターン、実施例5の感光性樹脂組成物を用いて形成した絶縁層パターン、第二の透明電極パターン、第一及び第二の透明電極パターンとは別の導電性要素を形成した前面板を得た。
絶縁層の形成と同様にして、上記第一及び第二の透明電極パターンとは別の導電性要素まで形成した前面板に、実施例5の感光性樹脂組成物を塗布・乾燥(膜厚1μm、90℃120秒)し、感光性樹脂組成物膜を得た。更に、露光マスク(保護層用パターンを有す石英露光マスク)面と該感光性樹脂組成物層との間の距離を50μmに設定し、露光量50mJ/cm2(i線)で露光し、現像、ポスト露光(1,000mJ/cm2)、ポストベーク処理を行って、マスク層、第一の透明電極パターン、実施例5の感光性樹脂組成物を用いて形成した絶縁層パターン、第二の透明電極パターン、第一及び第二の透明電極パターンとは別の導電性要素の全てを覆うように実施例5の感光性樹脂組成物を用いて形成した絶縁層(透明保護層)を積層した前面板を得た。
特開2009-47936号公報に記載の方法で製造した液晶表示素子に、先に製造した前面板を貼り合わせ、公知の方法で静電容量型入力装置を構成要素として備えた画像表示装置を作製した。
第一の透明電極パターン、第二の透明電極パターン、及び、これらとは別の導電性要素の、各々の導電性には問題がなく、一方で、第一の透明電極パターンと第二の透明電極パターンの間では絶縁性を有してあり、タッチパネルとして良好な表示特性が得られた。更に、第一及び第二の透明電極パターンは視認されにくく、表示特性に優れた画像表示装置が得られた。
特許第5318289号公報に記載の絶縁体5に、実施例62の感光性樹脂組成物を用いて、特許第5318289号公報に記載の方法と同様にタッチパネル表示装置を作製した。屈折率の高い本発明の感光性樹脂組成物を用いたことにより、検出電極との屈折率差も抑えることができるため、絶縁体5のパターンは、より視認されにくく、表示特性に優れた表示装置が得られた。
特許第5318289号公報に記載の上記絶縁体5に加え、保護層7に、実施例111の感光性樹脂組成物を用いて、特許第5318289号公報に記載の方法と同様にタッチパネル表示装置を作製した。絶縁体5及び保護層7ともに高屈折率化が可能なため、絶縁体5のパターンは更に視認されにくく、非常に視認性良好な表示装置が得られた。
特許第5036913号公報に記載の絶縁層14に、実施例37の感光性樹脂組成物を用いて、特許第5036913号公報に記載の方法と同様に入力装置(タッチパネル入力装置)を作製した。絶縁層部分での色のちらつきが目視されにくく、更に、検出電極との屈折率差も抑えられことにより、電極パターンが視認されにくい、非常に視認性良好な入力装置が得られた。
Claims (16)
- (成分A)金属酸化物粒子、
(成分B)下記式(I)で表される化合物、
(成分C)溶剤、
(成分D)酸基が酸分解性基で保護された基を有する構成単位を含む重合体、及び、
(成分E)光酸発生剤、を含有することを特徴とする
感光性樹脂組成物。
- 成分Bの分子量が1,000未満である、請求項1に記載の感光性樹脂組成物。
- 成分Bの含有量が、成分Dの含有量100質量部に対して、1~200質量部である、請求項1又は2に記載の感光性樹脂組成物。
- 成分Aの平均一次粒子径が50nm以下である、請求項1~3のいずれか1項に記載の感光性樹脂組成物。
- (成分F)分散剤を更に含有する、請求項1~4のいずれか1項に記載の感光性樹脂組成物。
- 成分Dが、下記(1)及び(2)で表される重合体成分の少なくとも一方を満たす、請求項1~5のいずれか1項に記載の感光性樹脂組成物。
(1)(a1)酸基が酸分解性基で保護された基を有する構成単位及び(a2)架橋性基を有する構成単位を有する重合体
(2)(a1)酸基が酸分解性基で保護された基を有する構成単位を有する重合体、及び、(a2)架橋性基を有する構成単位を有する重合体 - R1及びR2がそれぞれ独立に、ヒドロキシ基、カルボキシ基、又は、ヒドロキシ基、カルボキシ基、エポキシ基及びオキセタニル基よりなる群から選ばれる少なくとも1種の基を有する一価の有機基である、請求項1~6のいずれか1項に記載の感光性樹脂組成物。
- 少なくとも工程(a)~(c)をこの順に含むことを特徴とする硬化物の製造方法。
(a)請求項1~8のいずれか1項に記載の感光性樹脂組成物を基板上に塗布する塗布工程
(b)塗布された樹脂組成物から溶剤を除去する溶剤除去工程
(c)溶剤が除去された樹脂組成物を熱処理する熱処理工程 - 少なくとも工程(1)~(4)をこの順に含むことを特徴とする樹脂パターン製造方法。
(1)請求項1~8のいずれか1項に記載の感光性樹脂組成物を基板上に塗布する塗布工程
(2)塗布された樹脂組成物から溶剤を除去する溶剤除去工程
(3)溶剤が除去された樹脂組成物を活性光線によりパターン状に露光する露光工程
(4)露光された樹脂組成物を水性現像液により現像する現像工程 - 請求項9に記載の硬化物の製造方法、又は、請求項10に記載の樹脂パターン製造方法により得られた硬化物。
- 請求項1~8のいずれか1項に記載の感光性樹脂組成物を硬化してなる硬化膜。
- 層間絶縁膜である、請求項12に記載の硬化膜。
- 請求項12又は13に記載の硬化膜を有する液晶表示装置。
- 請求項12又は13に記載の硬化膜を有する有機EL表示装置。
- 請求項12又は13に記載の硬化膜を有するタッチパネル表示装置。
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CN105190437A (zh) | 2015-12-23 |
TW201447487A (zh) | 2014-12-16 |
JPWO2014199967A1 (ja) | 2017-02-23 |
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