WO2021085262A1 - ケイ素化合物、反応性材料、樹脂組成物、感光性樹脂組成物、硬化膜、硬化膜の製造方法、パターン硬化膜およびパターン硬化膜の製造方法 - Google Patents
ケイ素化合物、反応性材料、樹脂組成物、感光性樹脂組成物、硬化膜、硬化膜の製造方法、パターン硬化膜およびパターン硬化膜の製造方法 Download PDFInfo
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- WO2021085262A1 WO2021085262A1 PCT/JP2020/039508 JP2020039508W WO2021085262A1 WO 2021085262 A1 WO2021085262 A1 WO 2021085262A1 JP 2020039508 W JP2020039508 W JP 2020039508W WO 2021085262 A1 WO2021085262 A1 WO 2021085262A1
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- carbon atoms
- silicon compound
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- cured film
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- 150000003377 silicon compounds Chemical class 0.000 title claims abstract description 100
- 239000000463 material Substances 0.000 title claims abstract description 77
- 239000011342 resin composition Substances 0.000 title claims description 65
- 238000004519 manufacturing process Methods 0.000 title claims description 45
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 62
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 46
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 26
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 19
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 13
- 125000006165 cyclic alkyl group Chemical group 0.000 claims abstract description 10
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 6
- -1 polysiloxane Polymers 0.000 claims description 160
- 150000001875 compounds Chemical class 0.000 claims description 111
- 229920001296 polysiloxane Polymers 0.000 claims description 87
- 238000006243 chemical reaction Methods 0.000 claims description 51
- 229920005989 resin Polymers 0.000 claims description 41
- 239000011347 resin Substances 0.000 claims description 41
- 239000002904 solvent Substances 0.000 claims description 40
- 239000002253 acid Substances 0.000 claims description 34
- 239000003054 catalyst Substances 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 25
- 230000002378 acidificating effect Effects 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 11
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 6
- 125000004036 acetal group Chemical group 0.000 claims description 6
- 125000002252 acyl group Chemical group 0.000 claims description 6
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 6
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 claims description 6
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 claims description 6
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 6
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical group COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 5
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 4
- QMYGFTJCQFEDST-UHFFFAOYSA-N 3-methoxybutyl acetate Chemical compound COC(C)CCOC(C)=O QMYGFTJCQFEDST-UHFFFAOYSA-N 0.000 claims description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical class OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 3
- 229940116333 ethyl lactate Drugs 0.000 claims description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 3
- 150000002334 glycols Chemical class 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 229940043265 methyl isobutyl ketone Drugs 0.000 claims description 3
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- 238000000034 method Methods 0.000 description 27
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- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 26
- 239000000047 product Substances 0.000 description 21
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- 238000000576 coating method Methods 0.000 description 11
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- 238000005481 NMR spectroscopy Methods 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
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- 238000011156 evaluation Methods 0.000 description 9
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- 229910052710 silicon Inorganic materials 0.000 description 9
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
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- 230000000052 comparative effect Effects 0.000 description 6
- 125000003700 epoxy group Chemical group 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- DYHSDKLCOJIUFX-UHFFFAOYSA-N tert-butoxycarbonyl anhydride Chemical compound CC(C)(C)OC(=O)OC(=O)OC(C)(C)C DYHSDKLCOJIUFX-UHFFFAOYSA-N 0.000 description 6
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 5
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- 125000003566 oxetanyl group Chemical group 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
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- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 4
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- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 4
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- 125000001424 substituent group Chemical group 0.000 description 4
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
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- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
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- 150000002513 isocyanates Chemical class 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
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- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 3
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- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 3
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- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 2
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
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Classifications
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
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- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G77/04—Polysiloxanes
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- C08G77/08—Preparatory processes characterised by the catalysts used
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- 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
- G03F7/20—Exposure; Apparatus therefor
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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
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
- G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
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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
- G03F7/70—Microphotolithographic exposure; Apparatus therefor
- G03F7/70008—Production of exposure light, i.e. light sources
Definitions
- the present invention relates to a silicon compound, a reactive material, a resin composition, a photosensitive resin composition, a cured film, a method for producing a cured film, and a method for producing a pattern cured film and a pattern cured film.
- the polymer compound containing a siloxane bond has high heat resistance and transparency. Based on these characteristics, attempts have been made to apply polymer compounds containing siloxane bonds to, for example, coating materials for liquid crystal displays and organic EL displays, coating agents for image sensors, encapsulants in the semiconductor field, photosensitive resin compositions, and the like. Has been done. In addition, the polymer compound containing a siloxane bond has high oxygen plasma resistance. Therefore, a polymer compound containing a siloxane bond is also being studied as a hard mask material for, for example, a multilayer resist.
- Patent Document 1 describes a positive photosensitive resin containing a polysiloxane compound having a structure in which a group represented by -C (CF 3 ) 2 OX (X is a hydrogen atom or an acid unstable group) is substituted on a benzene ring. The composition is described.
- Paragraph 0106 of Patent Document 1 Example 3-1 describes a method for synthesizing a polysiloxane compound with respect to a polysiloxane compound (polymer) having a group represented by ⁇ C (CF 3 ) 2 OH. It is described that an acid instability group (t-butoxycarbonyl group) was introduced into the polymer by reacting di-tert-butyl carbonate.
- Patent Document 2 describes a production method including two specific steps as a method for producing a siloxane compound having a structure in which a group represented by -C (CF 3 ) 2 OH is substituted on a benzene ring.
- the present inventors have found that the conventional fluorine-containing siloxane compound has room for improvement in terms of storage stability, for example.
- the present inventors conducted various studies with the aim of providing a fluorine-containing siloxane compound having good storage stability.
- R 1 are each independently when a plurality of, C 1-10 straight, cyclic alkyl group, branched or 3 to 10 carbon atoms having 3 to 10 carbon atoms, straight-chain having 2 to 10 carbon atoms It is a branched alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms, and all or part of the hydrogen atom in the alkyl group or the alkenyl group may be substituted with a fluorine atom.
- R 2 is a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 to 4 carbon atoms independently of each other when there are a plurality of them, and all or a part of hydrogen atoms in the alkyl group are fluorine atoms.
- n is an integer from 1 to 5.
- the silicon compound described in The RA is at least one silicon compound selected from the group consisting of an alkyl group, an alkoxycarbonyl group, an acetal group, a silyl group and an acyl group.
- R 1 are each independently when a plurality of, C 1-10 straight, cyclic alkyl group, branched or 3 to 10 carbon atoms having 3 to 10 carbon atoms, straight-chain having 2 to 10 carbon atoms It is a branched alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms, and all or part of the hydrogen atom in the alkyl group or the alkenyl group may be substituted with a fluorine atom.
- R 2 is a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 to 4 carbon atoms independently of each other when there are a plurality of them, and all or a part of hydrogen atoms in the alkyl group are fluorine atoms.
- n is an integer from 1 to 5.
- the reactive material described in The RA is at least one of a reactive material selected from the group consisting of an alkyl group, an alkoxycarbonyl group, an acetal group, a silyl group and an acyl group.
- R 1 , R 2 , a, b, c and n are the same as those in the general formula (x).
- 6. Under acidic or basic catalysts. Alternatively, the silicon compound according to 2 or 3. ⁇ 5.
- the resin composition according to The solvent is propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, ethyl lactate, ⁇ -butyrolactone, diacetone alcohol, diglime, methylisobutylketone, 3-methoxybutyl acetate, 2-heptanone, N, N-dimethylformamide. , N, N-Dimethylacetamide, N-Methylpyrrolidone, glycols, glycol ethers and glycol ether esters.
- a photosensitive resin composition containing the resin composition according to the above and a photoacid generator.
- a method for producing a cured film which comprises a heating step of applying the resin composition according to No. 1 on a substrate and then heating at a temperature of 100 to 350 ° C.
- a film forming step of applying the photosensitive resin composition described in the above on a substrate to form a photosensitive resin film and The exposure step of exposing the photosensitive resin film and A developing step of developing the photosensitive resin film after exposure to form a patterned resin film, and A curing step of converting the pattern resin film into a pattern curing film by heating the pattern resin film, and A method for producing a pattern cured film including.
- a fluorine-containing siloxane compound having good storage stability is provided.
- XY in the description of the numerical range indicates X or more and Y or less unless otherwise specified.
- “1 to 5% by mass” means “1% by mass or more and 5% by mass or less”.
- the notation that does not indicate whether it is substituted or unsubstituted includes both those having no substituent and those having 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).
- the "cyclic alkyl group” includes not only a monocyclic structure but also a polycyclic structure. The same applies to the "cycloalkyl group”.
- the notation "(meth) acrylic” herein represents a concept that includes both acrylic and methacrylic.
- organic group as used herein means an atomic group obtained by removing one or more hydrogen atoms from an organic compound.
- the “monovalent organic group” represents an atomic group obtained by removing one hydrogen atom from an arbitrary organic compound.
- HFIP group the group represented by ⁇ C (CF 3 ) 2 OH may also be referred to as “HFIP group” by taking the acronym of hexafluoroisopropanol group.
- the silicon compound (silicon compound (X)) of the present embodiment is represented by the following general formula (x). Further, the reactive material of the present embodiment contains a silicon compound (X) represented by the following general formula (x).
- R 1 are each independently when a plurality of, C 1-10 straight, cyclic alkyl group, branched or 3 to 10 carbon atoms having 3 to 10 carbon atoms, straight-chain having 2 to 10 carbon atoms It is a branched alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms, and all or part of the hydrogen atom in the alkyl group or the alkenyl group may be substituted with a fluorine atom.
- R 2 is a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 to 4 carbon atoms independently of each other when there are a plurality of them, and all or a part of hydrogen atoms in the alkyl group are fluorine atoms.
- n is an integer from 1 to 5.
- the hydrogen atom (indicating acidity) of the HFIP group is protected by an acid instability group.
- hydrolysis and polycondensation of the -SiR 1 b (OR 2 ) c portion in the general formula (x) are suppressed, and it is considered that good storage stability can be obtained.
- Good storage stability is a highly desirable property in the industrial use of chemical materials.
- R 1 is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably a methyl group.
- R 2 is preferably a methyl group or an ethyl group in terms of availability of raw materials and cost.
- a is preferably 1.
- n is preferably 1 or 2, and more preferably 1.
- c is preferably 2 or 3.
- the group represented by -C (CF 3 ) 2 OR A is preferably the meta position with respect to the group represented by -SiR 1 b (OR 2 ) c. It is preferably present in. More specifically, the portion of the following group (2) in the general formula (x) can be any of the structures represented by the formulas (2A) to (2D), and among them, the formula (2A). ) Or the structure represented by the formula (2D) is preferable.
- the wavy line indicates that the intersecting line segment is a bond.
- Examples of the acid instability group of RA include those known as acid instability groups in the field of photosensitive resin compositions without particular limitation.
- examples of the acid instability group include an alkyl group, an alkoxycarbonyl group, an acetal group, a silyl group, and an acyl group.
- alkyl group tert-butyl group, tert-amyl group, 1,1-dimethylpropyl group, 1-ethyl-1-methylpropyl group, 1,1-dimethylbutyl group, allyl group, 1-pyrenylmethyl group, 5 -Dibenzosveryl group, triphenylmethyl group, 1-ethyl-1-methylbutyl group, 1,1-diethylpropyl group, 1,1-dimethyl-1-phenylmethyl group, 1-methyl-1-ethyl-1- Phenylmethyl group, 1,1-diethyl-1-phenylmethyl group, 1-methylcyclohexyl group, 1-ethylcyclohexyl group, 1-methylcyclopentyl group, 1-ethylcyclopentyl group, 1-isobornyl group, 1-methyladamantyl group , 1-Ethyl adamantyl group, 1-isopropyl adamantyl group, 1-iso
- the alkyl group is preferably a tertiary alkyl group, more preferably a group represented by ⁇ CR p R q R r (R p , R q and R r are independently linear or branched alkyl, respectively).
- R p , R q and R r are independently linear or branched alkyl, respectively.
- a group, a monocyclic or polycyclic cycloalkyl group, an aryl group or an aralkyl group, and two of R p , R q and R r may be bonded to form a ring structure).
- alkoxycarbonyl group examples include a tert-butoxycarbonyl group, a tert-amyloxycarbonyl group, a methoxycarbonyl group, an ethoxycarbonyl group, an i-propoxycarbonyl group and the like.
- acetal group examples include methoxymethyl group, ethoxyethyl group, butoxyethyl group, cyclohexyloxyethyl group, benzyloxyethyl group, phenethyloxyethyl group, ethoxypropyl group, benzyloxypropyl group, phenethyloxypropyl group and ethoxybutyl group.
- Examples thereof include an ethoxyisobutyl group.
- Examples of the silyl group include a trimethylsilyl group, an ethyldimethylsilyl group, a methyldiethylsilyl group, a triethylsilyl group, an i-propyldimethylsilyl group, a methyldi-i-propylsilyl group, a tri-i-propylsilyl group and tert-butyl.
- Examples thereof include a dimethylsilyl group, a methyldi-tert-butylsilyl group, a tri-tert-butylsilyl group, a phenyldimethylsilyl group, a methyldiphenylsilyl group and a triphenylsilyl group.
- acyl group examples include an acetyl group, a propionyl group, a butyryl group, a heptanoyl group, a hexanoyl group, a valeryl group, a pivaloyl group, an isovaleryl group, a laurylloyl group, a myritoyl group, a palmitoyl group, a stearoyl group, an oxalyl group, a malonyl group and a succinyl group.
- Phtaloyl group isophthaloyl group, terephthaloyl group, naphthoyl group, toluoil group, hydroatropoil group, atropoil group, cinnamoyl group, floyl group, tenoyl group, nicotinoyle group, isonicotinoyl group and the like.
- Some or all of the hydrogen atoms of the acid instability group may be substituted with fluorine atoms.
- Particularly preferable structures of RA include a structure represented by the following general formula (ALG-1) and a structure represented by the following general formula (ALG-2).
- R 11 is a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 21 carbon atoms.
- R 12 is a hydrogen atom, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms or 7 to 7 carbon atoms. It is an aralkyl group of 21.
- R 13 , R 14 and R 15 are independently linear alkyl groups having 1 to 10 carbon atoms, branched alkyl groups having 3 to 10 carbon atoms or cyclic alkyl groups having 3 to 10 carbon atoms, and having 6 to 20 carbon atoms. It is an aryl group or an aralkyl group having 7 to 21 carbon atoms. Two of R 13 , R 14 and R 15 may be combined with each other to form a ring structure.
- a silicon compound of 1 molecule (X) When in the general formula (x) n is 2 or more, a silicon compound of 1 molecule (X) will have a 2 or more R A. In this case, two or more RAs may be the same or different from each other. Further, the reactive material of the present embodiment, may include two or more different silicon compound having a R A chemical structure (X) from one another. Of course, the reactive material of the present embodiment may contain substantially only one kind of silicon compound (X).
- the combination of R 1 , R 2 , b and c is, for example, any of the combinations 1 to 6 shown in Table 1 below.
- Me represents a methyl group
- Et represents an ethyl group.
- the reactive material of the present embodiment can further contain a silicon compound (Y) represented by the following general formula (y).
- a silicon compound on the weight of (Y) was M Y, tables in ⁇ M Y / (M X + M Y) ⁇ ⁇ 100
- the ratio (mass%) of the silicon compound (Y) to be formed is preferably 1 ⁇ 10 -4 to 12%, more preferably 5 ⁇ 10 -4 to 10%, still more preferably 0.001 to 8%, particularly. It is preferably 0.01 to 5%.
- the silicon compound (Y) has an HFIP group that is not protected by an acid instability group. As a result, the silicon compound (Y) is acidic. It is considered that when an appropriate amount of the acidic silicon compound (Y) is contained in the reactive material, a good reactivity effect can be obtained while obtaining a storage stability effect.
- the silicon compound (Y) is considered to contribute to the reaction of the silicon compound (X), for example, polycondensation (formation of a siloxane bond by dehydration) as an acid catalyst. Therefore, by containing an appropriate amount of the silicon compound (Y) in the reactive material of the present embodiment, for example, when the reactive material of the present embodiment is used as a raw material monomer of a polysiloxane compound, the effect of storage stability can be obtained.
- silicon compound (X) / Method for producing reactive material The method for producing the silicon compound (X) / reactive material of the present embodiment is not particularly limited. A typical manufacturing method will be described below.
- a compound in which RA is a hydrogen atom in the general formula (x) is prepared.
- Such compounds are known and can be synthesized, for example, with reference to the method described in Patent Document 2 described above.
- an acid instability group is introduced into the compound in which RA is a hydrogen atom in the general formula (x).
- a method for introducing an acid instability group a known method for introducing an acid instability group into an alcohol compound can be adopted.
- an acid instability group can be introduced by reacting a dialkyl dicarbonate compound or an alkoxycarbonylalkyl halide with a compound in which RA is a hydrogen atom in the general formula (x) in a solvent in the presence of a base. ..
- a tert-butoxycarbonyl group which can be easily deprotected by heat treatment and is preferably used (in the above general formula (ALG-2), R 13 , R 14 and R 15).
- a method for introducing a group (which is a methyl group) will be described.
- di-tert-butyl dicarbonate having the same molar amount or more is added to the amount of HFIP groups present in the molecule of the compound in which RA is a hydrogen atom, and pyridine, triethylamine, N, N are added.
- a base such as dimethylaminopyridine
- the solvent that can be used is not particularly limited as long as it can dissolve the compound to be added to the above reaction system and does not adversely affect the reaction. Specifically, toluene, xylene, pyridine and the like are preferable.
- the reaction temperature and reaction time vary depending on the type of base used and the like, but usually the reaction temperature is room temperature or higher and 180 ° C. or lower, and the reaction time is 1 to 24 hours.
- a method for introducing a methoxymethyl group in the general formula (ALG-1), a group in which R 11 is a methyl group and R 12 is a hydrogen atom
- ALG-1 a group in which R 11 is a methyl group and R 12 is a hydrogen atom
- a strong base NaH or the like
- chloromethyl methyl ether having the same molar amount or more.
- the solvent that can be used at this time is not particularly limited, and any solvent that can dissolve the compound to be added to the reaction system and does not adversely affect the reaction can be used.
- a preferred solvent is tetrahydrofuran and the like.
- the reaction proceeds even at room temperature.
- a solvent toluene, diisopropyl ether, etc.
- simple distillation pressure of about 2.5 kPa, temperature of about 200 to 220 ° C. It is preferable to perform such as.
- R 11 is defined as the general formula (ALG-1)) is reacted in the presence of an acid catalyst (eg, paratoluenesulfonic acid).
- an acid catalyst eg, paratoluenesulfonic acid
- the solvent that can be used at this time is not particularly limited, and any solvent that can dissolve the compound to be added to the reaction system and does not adversely affect the reaction can be used.
- the reaction proceeds even at room temperature. After completion of the reaction, post-treatment such as washing or distillation may be performed.
- the polysiloxane compound of the present embodiment is produced by polycondensing the above-mentioned silicon compound (silicon compound (X)) or the above-mentioned reactive material under an acidic catalyst or a basic catalyst.
- the silicon compound (X) is hydrolyzed by the portion of "OR 2 " in the general formula (x) under an acidic catalyst or a basic catalyst. This results in a silanol group.
- a polysiloxane compound is obtained by dehydration condensation of two or more of the generated silanol groups.
- a polysiloxane compound can also be obtained by a condensation reaction between the generated silanol group and the "Si-OR 2" moiety.
- a reactive material (monomer) different from the silicon compound (X) or the silicon compound (Y) may be present in the reaction system. Thereby, a copolymer can be obtained. This will be explained later.
- Examples of a method for producing a polysiloxane compound having a structure in which an HFIP group is protected by an acid instability group include the following two production methods.
- -Production method 1 A reactive material having an unprotected HFIP group (for example, in the general formula (x), a compound in which RA is a hydrogen atom) is polycondensed to obtain a polymer or an oligomer. An acid instability group is then introduced into the polymer or oligomer.
- -Production method 2 A reactive material in which the HFIP group is previously protected with an acid instability group, such as silicon compound (X), is polycondensed.
- Example 3-1 of Patent Document 1 described above a polysiloxane compound having an acid instability group is produced as in the above-mentioned "Production method 1".
- the polysiloxane compound is produced as in Production Method 1
- an undesired by-product is produced, the final product is colored, and the polysiloxane compound has a large weight average molecular weight.
- the present inventors have conducted various studies to solve the above problems. Through the examination, it was surprisingly found that the above problem is unlikely to occur when the polysiloxane compound is produced as in the production method 2.
- the reactive material containing the silicon compound (X) of the present embodiment can be said to have good reactivity in that a polysiloxane compound having a larger weight average molecular weight can be obtained while having good storage stability.
- the weight average molecular weight of the polysiloxane compound of the present embodiment is preferably 1,000 to 100,000, more preferably 1,500 to 50,000. As described above, by using the reactive material of the present embodiment as a raw material and polycondensing the raw material under an acidic catalyst or a basic catalyst, a polysiloxane compound having a relatively large weight average molecular weight tends to be obtained. ..
- the polycondensation procedure and reaction conditions in producing the polysiloxane compound of the present embodiment known techniques for hydrolysis and condensation reaction of alkoxysilane can be appropriately applied.
- the polysiloxane compound of the present embodiment can be produced by the following procedures and conditions (1) to (4).
- a predetermined amount of the above-mentioned reactive material is sampled in a reaction vessel at room temperature (particularly, an atmospheric temperature without heating or cooling, usually about 15 to 30 ° C.).
- Water for hydrolysis, a catalyst for advancing the polycondensation reaction, and a reaction solvent, if desired, are added to the reaction vessel and appropriately stirred to prepare a reaction solution.
- the order of these additions is not particularly limited, and the reaction solution can be prepared by adding them in any order.
- a siloxane compound (monomer) that does not correspond to the silicon compound (X) or the silicon compound (Y) may be added into the reaction vessel. By doing so, a polysiloxane compound which is a copolymer can be produced.
- the amount of water used in the hydrolysis and condensation reactions is not particularly limited. From the viewpoint of reaction efficiency, it is preferably 0.5 to 5 times the total number of moles of hydrolyzable groups (OR 2 in the general formula (x)) contained in the raw material.
- Acid catalysts include hydrochloric acid, nitric acid, sulfuric acid, fluoric acid, phosphoric acid, acetic acid, oxalic acid, trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, camphorsulfonic acid, benzenesulfonic acid, tosylic acid, formic acid, and polyvalent. Examples thereof include carboxylic acid and its anhydride.
- Base catalysts include tetramethylammonium hydroxide, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine, diethanolamine, sodium hydroxide, hydroxide. Examples include potassium and sodium carbonate.
- the amount of the catalyst used is 1.0 ⁇ 10 -5 to 1.0 ⁇ 10 -1 with respect to the total number of moles of hydrolyzable groups (OR 2 in the general formula (x), etc.) contained in the raw material. It is preferably doubled.
- a reaction solvent may or may not be used.
- the type is not particularly limited. From the viewpoint of solubility in the raw material compound, water and the catalyst, a polar solvent is preferable, and an alcohol solvent is more preferable. Specific examples thereof include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, diacetone alcohol, propylene glycol monomethyl ether and the like.
- the reaction solvent may be a single solvent or a mixed solvent. When the reaction solvent is used, the amount used may be any amount necessary for the reaction to proceed in a uniform system.
- a copolymer can be obtained by adding a siloxane compound or a silane compound monomer that does not correspond to the silicon compound (X) or the silicon compound (Y) into the reaction vessel. ..
- siloxane compound or silane compound monomer that does not correspond to silicon compound (X) or silicon compound (Y) is also collectively referred to as "silicon compound (Z)".
- the silicon compound (Z) at least one selected from the group consisting of (i) a hydrolyzable alkoxysilyl group and (ii) an epoxy group, an oxetane group and (meth) acryloyl group in one molecule.
- a compound comprising a group can be preferably mentioned (hereinafter, this compound is also referred to as a silicon compound (Z1)).
- the polysiloxane compound of the present embodiment can be preferably applied to a thermosetting resin composition or the like. ..
- the silicon compound (Z1) is more specifically represented by the following general formula (z1).
- R 1 , R 2 , a, b and c are the same as in the general formula (x).
- Ry is a monovalent organic group having 2 to 30 carbon atoms, which contains any of an epoxy group, an oxetane group, and a (meth) acryloyl group.
- Ry contains an epoxy group or an oxetane group, for example, when the polysiloxane compound of the present embodiment is applied to a resin composition described later, the adhesion to various substrates such as silicon, glass, and resin is enhanced. Can be done.
- R y contains a (meth) acryloyl group, for example, when the polysiloxane compound of the present embodiment is used as a cured film described later, good solvent resistance can be obtained.
- R y contains an epoxy group or an oxetane group
- R y is preferably a group represented by the following formula (2a), (2b) or (2c).
- R g, R h and R i each independently represent a single bond or a divalent organic group.
- the dashed line represents the bond.
- examples of the divalent organic group include alkylene groups having 1 to 20 carbon atoms. This alkylene group may contain one or more sites forming an ether bond. When the number of carbon atoms is 3 or more, the alkylene group may be branched, or distant carbons may be connected to each other to form a ring. When there are two or more alkylene groups, oxygen may be inserted between carbons to form one or more sites forming an ether bond.
- R y contains a (meth) acryloyl group
- R y is preferably a group selected from the following formula (3a) or (4a).
- R j and R k each independently represent a single bond or a divalent organic group.
- the dashed line represents the bond.
- Preferred examples of when R j and R k is a divalent organic group include those described as preferable groups R g, R h and R i.
- silicon compound (Z1) examples include 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd., product name: KBM-403) and 3-glycidoxypropyltriethoxysilane (same product name).
- KBE-403 3-glycidoxypropylmethyldiethoxysilane (same, product name: KBE-402), 3-glycidoxypropylmethyldimethoxysilane (same, product name: KBM-402), 2- ( 3,4-Epylcyclohexyl) Ethyltrimethoxysilane (same, product name: KBM-303), 2- (3,4-epylcyclohexyl) ethyltriethoxysilane, 8-glycidoxyoctyltrimethoxysilane (same, product) Name: KBM-4803), [(3-ethyl-3-oxetanyl) methoxy] propyltrimethoxysilane, [(3-ethyl-3-oxetanyl) methoxy] propyltriethoxysilane and the like.
- silicon compound (Z1) examples include 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd., product name: KBM-503) and 3-methacryloxypropyltriethoxysilane (same product name).
- KBE-503 3-methacryloxypropylmethyldimethoxysilane (same, product name: KBM-502), 3-methacryloxypropylmethyldiethoxysilane (same, product name: KBE-502), 3-acryloxypropyl Examples thereof include trimethoxysilane (same product name: KBM-5103) and 8-methacryloxyoctyltrimethoxysilane (same product name: KBM-5803).
- Oligomers include silicate 40 (average pentamer, manufactured by Tama Chemical Industry Co., Ltd.), ethyl silicate 40 (average pentamer, manufactured by Corcote Co., Ltd.), and silicate 45 (average pentamer, manufactured by Tama Chemical Industry Co., Ltd.).
- M silicate 51 (average tetramer, manufactured by Tama Chemical Industry Co., Ltd.), methyl silicate 51 (average tetramer, manufactured by Corcote Co., Ltd.), methyl silicate 53A (average tetramer, manufactured by Corcote Co., Ltd.), ethyl silicate 48 (average tetramer, Corcote Co., Ltd.), EMS-485 (mixture of ethyl silicate and methyl silicate, manufactured by Corcote Co., Ltd.) and the like can be mentioned.
- silicon compound (Z) various alkoxysilanes and the like can be mentioned. Specifically, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldiphenoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, diethyldiphenoxysilane, dipropyldimethoxysilane, dipropyl.
- phenyltrimethoxysilane, phenyltriethoxysilane, methylphenyldimethoxysilane and methylphenyldiethoxysilane are preferably mentioned in terms of heat resistance and transparency when the polysiloxane compound is used as a cured film.
- dimethyldimethoxysilane and dimethyldiethoxysilane are preferably mentioned in terms of increasing the flexibility when the polysiloxane compound is formed into a cured film and preventing cracks and the like.
- the silicon compound (Z) When the silicon compound (Z) is used, only one type may be used, or two or more types may be used. When the silicon compound (Z) is used, the amount thereof may be appropriately adjusted according to the desired performance and the like. Specifically, when the silicon compound (Z) is used, the amount thereof is, for example, 1 to 50 mol% in all the polymerizable components (silicon compounds (X), (Y) and (Z)) used for polycondensation. , Preferably 5-40 mol%. When a silicon compound (Z1) is used, the amount thereof is preferably 1 to 50 mol%, more preferably 1 to 50 mol% of all the polymerizable components used for polycondensation in consideration of the balance between curability and other performance. It is 5 to 40 mol%.
- the charging ratio of the silicon compounds (X), (Y) and (Z) and the ratio of the structural units corresponding to each of the silicon compounds (X), (Y) and (Z) in the polysiloxane compound are , Can be regarded as about the same.
- the resin composition of the present embodiment contains the above-mentioned polysiloxane compound and a solvent.
- the resin composition of the present embodiment is the above-mentioned polysiloxane compound dissolved and / or dispersed in a solvent.
- a resin film can be formed by dissolving and / or dispersing a polysiloxane compound in a solvent to obtain a resin composition, applying the resin composition onto a substrate, and drying the solvent. Further, a cured film can be produced by heating the resin film.
- the solvent typically contains an organic solvent.
- Preferred usable solvents include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, ethyl lactate, ⁇ -butyrolactone, diacetone alcohol, diglime, methyl isobutyl ketone, 3-methoxybutyl acetate, 2-heptanone, N, Examples thereof include N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.
- glycols, glycol ethers, glycol ether esters and the like can also be mentioned as usable solvents.
- Specific examples thereof include Celtor (registered trademark) manufactured by Daicel Corporation and Highsolve (registered trademark) manufactured by Toho Chemical Industry Co., Ltd.
- the solvent may be a single solvent or a mixed solvent.
- the amount of the solvent used is not particularly limited, but the total solid content (components other than the volatile solvent) in the resin composition is usually 5 to 60% by mass, preferably 10 to 50% by mass. By appropriately adjusting the total solid content concentration, the ease of forming a thin film and the uniformity of the film thickness tend to be improved.
- the resin composition of the present embodiment may contain one or more additive components in addition to the polysiloxane compound and the solvent.
- an additive such as a surfactant can be blended for the purpose of improving coatability, leveling property, film forming property, storage stability, defoaming property and the like.
- a surfactant When a surfactant is used, only one surfactant may be used, or two or more surfactants may be used. When a surfactant is used, the amount thereof is usually 0.001 to 10 parts by mass with respect to 100 parts by mass of the polysiloxane compound.
- a curing agent can be used for the purpose of improving the chemical resistance of the cured film.
- the curing agent include a melamine curing agent, a urea resin curing agent, a polybasic acid curing agent, an isocyanate curing agent, and an epoxy curing agent.
- isocyanates such as isophorone diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate or diphenylmethane diisocyanate, and melamine resins such as alkylated melamine, methylol melamine and imino melamine or urea such as isocyanurates, blocked isocyanates or burettos thereof.
- melamine resins such as alkylated melamine, methylol melamine and imino melamine or urea such as isocyanurates, blocked isocyanates or burettos thereof.
- amino compounds such as resins, epoxy curing agents having two or more epoxy groups obtained by the reaction of polyhydric phenols such as bisphenol A with epichlorohydrin, and the like.
- a curing agent When a curing agent is used, only one curing agent may be used, or two or more curing agents may be used. When a curing agent is used, the amount thereof is usually 0.001 to 10 parts by mass with respect to 100 parts by mass of the polysiloxane compound.
- a method for producing a cured film using the resin composition of the present embodiment is, for example, A film forming step of applying the resin composition of the present embodiment on a substrate to form a resin film, and The curing process of heating the resin film to make it a cured film, Can be included.
- the film forming step and the curing step will be specifically described.
- the base material to which the resin composition is applied is not particularly limited. Depending on the application of the cured film formed, it is selected from silicon wafers, metal, glass, ceramic and plastic substrates.
- the coating method and coating device for film formation are not particularly limited. Known coating methods / devices such as spin coating, dip coating, spray coating, bar coating, applicator, inkjet, and roll coating can be applied.
- the solvent in the resin composition can be volatilized to obtain a resin film.
- a cured film can be obtained by further heat-treating the resin film formed in the film forming step.
- the temperature of the heat treatment is usually 100 to 350 ° C. Although it depends on the boiling point of the solvent, a more preferable temperature is 150 to 280 ° C.
- the processing speed can be increased by heating at an appropriately high temperature. On the other hand, if the heating temperature is not too high, the uniformity of the cured film can be improved.
- the photosensitive resin composition of the present embodiment contains the above-mentioned polysiloxane compound, a photoacid generator, and a solvent.
- the photosensitive resin composition of the present embodiment can be produced by further adding a photoacid generator to the above-mentioned resin composition.
- the photoacid generator is not particularly limited as long as it is a compound that generates an acid by irradiation with light such as ultraviolet rays.
- the acid generated by light irradiation acts on the acid instability group in the polysiloxane compound, so that the acid instability group is eliminated and an HFIP group is produced.
- the polysiloxane compound remains insoluble in the alkaline developer.
- a patterned resin film made of a photosensitive resin composition can be produced by utilizing such a change in solubility in an alkaline developer due to light irradiation. Further, a pattern cured film can be obtained by curing the pattern.
- the photoacid generator examples include a sulfonium salt, an iodonium salt, a sulfonyldiazomethane, an N-sulfonyloxyimide, and an oxime-O-sulfonate.
- the photoacid generator is not particularly limited as long as it generates an acid capable of desorbing an acid instability group.
- the photoacid generator may be used alone or in combination of two or more.
- photoacid generators include trade names: Irgacure PAG121, Irgacure PAG103, Irgacure CGI1380, Irgacure CGI725 (above, manufactured by BASF), and trade names: PAI-101, PAI-106, NAI-105, NAI-106.
- TAZ-110, TAZ-204 (all manufactured by Midori Chemical Co., Ltd.), Product names: CPI-200K, CPI-210S, CPI-101A, CPI-110A, CPI-100P, CPI-110P, CPI-100TF, CPI -110TF, HS-1, HS-1A, HS-1P, HS-1N, HS-1TF, HS-1NF, HS-1MS, HS-1CS, LW-S1, LW-S1NF (all manufactured by Sun Appro Co., Ltd.) , Trade name: TFE-triazine, TME-triazine or MP-triazine (all manufactured by Sanwa Chemical Co., Ltd.).
- the photoacid generators that can be used are not limited to these.
- photoacid generator When a photoacid generator is used, only one photoacid generator may be used, or two or more photoacid generators may be used.
- the amount of the photoacid generator is, for example, 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, when the polysiloxane compound is 100 parts by mass. By using an appropriate amount of the photoacid generator, it is possible to achieve both sufficient sensitivity and resolution and storage stability of the composition.
- the photosensitive resin composition of the present embodiment may contain one or more additive components as in the above-mentioned resin composition.
- additive components that can be added are also as described above.
- a sensitizer may be used as an additive component.
- the sensitizer preferably has light absorption for an exposure wavelength (for example, 365 nm (i line), 405 nm (h line), 436 nm (g line)) in the exposure process.
- the sensitizer is preferably a compound that vaporizes by heat treatment such as thermosetting, or a compound that fades by light irradiation such as bleaching exposure.
- the sensitizer examples include cumarin such as 3,3'-carbonylbis (diethylaminocoumarin), anthracene such as 9,10-anthracene, benzophenone, 4,4'-dimethoxybenzophenone, acetophenone, 4-methoxyacetophenone, and the like.
- Aromatic ketones such as benzaldehyde, biphenyl, 1,4-dimethylnaphthalene, 9-fluorenone, fluorene, phenanthrene, triphenylene, pyrene, anthracene, 9-phenylanthracene, 9-methoxyanthracene, 9,10-diphenylanthracene, 9,10 -Bis (4-methoxyphenyl) anthracene, 9,10-bis (triphenylsilyl) anthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-di Condensed aromatics such as butoxyanthracene, 9,10-dipentaoxyanthracene, 2-t-butyl-9,10-dibutoxyanthracene, and 9,10-bis (trimethylsilylethynyl) anthracene can be mentioned
- a sensitizer When a sensitizer is used, only one type may be used, or two or more types may be used. When a sensitizer is used, the blending amount thereof is usually 0.001 to 10 parts by mass with respect to 100 parts by mass of the polysiloxane compound.
- examples of the additive component include organic basic compounds (amine compounds, nitrogen-containing heterocyclic compounds) commonly used in photosensitive resin compositions containing an acid instability group.
- the amount of the solvent used can be the same as that of the above-mentioned resin composition.
- a pattern cured film can be produced by using the photosensitive resin composition of the present embodiment.
- the pattern cured film is, for example, A film forming step of applying a photosensitive resin composition onto a substrate to form a photosensitive resin film, and The exposure process for exposing the photosensitive resin film and A developing process for developing a photosensitive resin film after exposure to form a patterned resin film, A curing process that turns the pattern resin film into a pattern curing film by heating the pattern resin film, It can be manufactured by a series of steps including.
- the base material to which the photosensitive resin composition is applied is selected from, for example, a silicon wafer, a metal, a glass, a ceramic, and a plastic base material, depending on the use of the cured film to be formed.
- known coating methods such as spin coating, dip coating, spray coating, bar coating, applicator, inkjet or roll coater can be applied without particular limitation.
- the base material coated with the photosensitive resin composition is heated at, for example, 80 to 120 ° C. for about 30 seconds to 5 minutes to dry the solvent. By doing so, a photosensitive resin film can be obtained.
- the photosensitive resin film obtained in the film forming step is irradiated with light through a photomask for forming a target pattern.
- a known method / apparatus can be used for the exposure.
- the light source a light source having a wavelength in the range of 100 to 600 nm can be used. Specifically, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), and the like can be used. Exposure amount is usually 1 ⁇ 10000mJ / cm 2 or so, preferably from 10 ⁇ 5000mJ / cm 2 approximately.
- post-exposure heating can be performed before the development process.
- the post-exposure heating temperature is preferably 60 to 180 ° C.
- the post-exposure heating time is preferably 0.5 to 10 minutes.
- a film having a pattern shape (hereinafter, also referred to as "pattern resin film”) is produced by developing the photosensitive resin film after exposure obtained in the exposure process.
- pattern resin film By using an alkaline aqueous solution as a developing solution, the exposed portion of the photosensitive resin film after exposure is dissolved to form a patterned resin film.
- the developing solution is not particularly limited as long as it can remove the photosensitive resin film in the exposed portion.
- Specific examples thereof include an alkaline aqueous solution in which an inorganic alkali, a primary amine, a secondary amine, a tertiary amine, an alcohol amine, a quaternary ammonium salt, and a mixture thereof are dissolved. More specifically, alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, and tetramethylammonium hydroxide (abbreviation: TMAH) can be mentioned.
- TMAH tetramethylammonium hydroxide
- TMAH aqueous solution it is preferable to use a TMAH aqueous solution, and in particular, it is preferable to use a TMAH aqueous solution of 0.1% by mass or more and 5% by mass or less, more preferably 2% by mass or more and 3% by mass or less.
- the developing method known methods such as a dipping method, a paddle method, and a spraying method can be used.
- the development time is usually 0.1 to 3 minutes, preferably 0.5 to 2 minutes. After that, washing, rinsing, drying, etc. are performed as necessary to form a desired patterned film (pattern resin film) on the substrate.
- the final pattern cured film is obtained by heat-treating the pattern resin film obtained in the developing step.
- the alkoxy group and silanol group remaining as unreactive groups in the polysiloxane compound can be condensed.
- the photosensitive resin composition contains an epoxy group, an oxetane group, a methacryloyl group, an acryloyl group and the like, they can be sufficiently cured.
- the heating temperature is preferably 80 to 400 ° C, more preferably 100 to 350 ° C.
- the heating time is usually 1 to 90 minutes, preferably 5 to 60 minutes.
- the reactive material of the present embodiment can further contain the silicon compound (Y) represented by the following general formula (y).
- Y silicon compound represented by the following general formula (y).
- some of the embodiments of the present invention can also be regarded as the following "compositions”.
- Mass M X of the silicon compound contained in the composition (X) when the mass of the silicon compound (Y) was M Y, silicon represented by ⁇ M Y / (M X + M Y) ⁇ ⁇ 100
- the ratio (mass%) of compound (Y) is preferably 1 ⁇ 10 -4 to 12%, more preferably 5 ⁇ 10 -4 to 10%, even more preferably 0.001 to 8%, and particularly preferably 0.
- the definitions and preferred embodiments of the silicon compound (X) represented by the general formula (x) and the silicon compound (Y) represented by the general formula (y) are as described above.
- This composition may or may not contain any component other than the silicon compound (X) and the silicon compound (Y).
- Optional components include solvents (organic solvents, etc.), stabilizers, unavoidably contained water and impurities, and the like.
- HFA-Si Compound represented by the following chemical formula
- HFA-Si-MOM Compounds represented by the following chemical formulas
- HFA-Si-BOC Compound represented by the following chemical formula
- GC Gas Chromatography
- GPC Global Permeation Chromatography
- the obtained reactive material contains a small amount of HFA-Si, which is calculated by ⁇ amount of HFA-Si / (amount of HFA-Si-MOM + amount of HFA-Si) ⁇ x 100.
- the ratio of HFA-Si was 0.1% by mass.
- HFA-Si was synthesized according to the procedure described in Paragraph 0124 of International Publication No. 2019/167770, Example 5.
- Example 1 the reactive material produced in Synthesis Example 1-1 (containing 0.1% by mass of HFA-Si corresponding to the silicon compound (Y)) was prepared (this is referred to as “Sample 1”). ..
- Samples 2 to 5 were prepared by further adding HFA-Si to the reactive material of Sample 1.
- the ratio of ⁇ M Y / (M X + M Y) ⁇ silicon compound represented by ⁇ 100 (Y) are shown in Table given later.
- GC purity is the area of the chart obtained by gas chromatograph measurement, in the sample. Indicates the purity of HFA-Si-MOM.
- Synthesis Example 2-1 a polysiloxane compound having a relatively large Mw was obtained, but the Mw of the polysiloxane compound obtained in Comparative Synthesis Example 2-1 and Comparative Synthesis Example 2-2 was obtained in Synthesis Example 2-1. It was much smaller than Mw. From this, it can be said that the reactivity of the reactive material of the present embodiment is good, at least from the viewpoint of polymerizability. In addition to the above-mentioned evaluation results of the storage stability of the reactive material (the storage stability was good), the reactive material of the present embodiment has good storage stability and good reactivity. Was shown to be.
- the reactive material of the present embodiment can be preferably used as a raw material for a polysiloxane compound even under acidic conditions.
- Synthesis Example 2-1' Synthesis Examples 2-3 to 2-9: Synthesis of polysiloxane compound and preparation of solution composition
- Synthesis Example 2-1 a polysiloxane compound was obtained in the same manner except that KOH was used as the polymerization catalyst instead of TMAH (Synthesis Example 2-1').
- Synthesis Example 2-2 a polysiloxane compound was obtained in the same manner except that hydrochloric acid was used as the polymerization catalyst instead of acetic acid (Synthesis Example 2-3).
- Synthesis Example 2-1 a polysiloxane compound was obtained in the same manner except that the type of raw material and the charging ratio were changed as shown in the table below (Synthesis Examples 2-4 to 2-9).
- HFA-Si-MOM represents a reactive material containing HFA-Si-MOM obtained in Synthesis Example 1-1.
- the solution compositions P-1, P-1', and P-2 to P-9 were spin-coated on a silicon wafer manufactured by SUMCO Corporation, each having a diameter of 4 inches and a thickness of 525 ⁇ m, at a rotation speed of 500 rpm. Then, the silicon wafer was dried on a hot plate at 100 ° C. for 3 minutes. After that, it was calcined at 230 ° C. for 1 hour. In this way, a cured film of polysiloxane having a film thickness of 1 to 2 ⁇ m was obtained. When the presence or absence of tackiness was confirmed by touching the finger, no tackiness was observed in any of the membranes. That is, it was confirmed that the polysiloxane compound obtained by polycondensing the reactive material of the present embodiment under an acidic catalyst or a basic catalyst has no major problem in application to film formation and the like.
- the transmittance of light having a wavelength of 350 nm in terms of film thickness of 2 ⁇ m of the cured films obtained from P-1, P-1', P-2 to P-4, and P-9 is more than 90%.
- the polysiloxane compound obtained by polycondensing the reactive material of the present embodiment under an acidic catalyst or a basic catalyst is, for example, i-ray. It can be said that it can be preferably applied to a photosensitive resin composition applied to exposure, a coating material such as an organic EL or a liquid crystal display, and a CMOS image sensor.
- the photosensitive resin film was irradiated with light of 108 mJ / cm 2 through a photomask. Then, it was heat-treated on a hot plate at 150 ° C. for 1 minute. After the heat treatment, it was immersed in a 2.38 mass% TMAH aqueous solution for 1 minute for development, and then immersed in water for 30 seconds for washing. After washing, it was baked in an oven at 230 ° C. for 1 hour in the air. From the above, a pattern cured film in which a positive pattern was formed was obtained. A line-and-space pattern of 10 to 20 ⁇ m could be resolved in all five types of photosensitive resin compositions. That is, it can be said that the polysiloxane compound obtained by polycondensing the present reactive material is preferably applicable to the photosensitive resin composition.
- the silicon compound and the reactive material of the present embodiment are useful as a polymer synthetic raw material, a polymer modifier, a surface treatment agent for an inorganic compound, a coupling agent for various materials, an intermediate raw material for organic synthesis, and the like. Further, by adding a photosensitive agent to the resin composition containing the polysiloxane compound obtained by polycondensing the silicon compound or the reactive material of the present embodiment, a photosensitive resin composition that can be patterned by alkaline development is obtained. Is possible. Further, the cured film obtained from the resin composition or the photosensitive resin composition of the present embodiment has excellent transparency.
- the resin composition or the photosensitive resin composition of the present embodiment is used for a protective film for semiconductors, a protective film for organic EL and liquid crystal displays, a coating material for image sensors, a flattening material, a microlens material, and a touch panel. It is preferably used as an insulating protective film material, a liquid crystal display TFT flattening material, a core or clad forming material for an optical waveguide, an electron beam resist, an intermediate film for a multilayer resist, an underlayer film, an antireflection film, and the like.
- fine particles such as polytetrafluoroethylene, silica, titanium oxide, zirconium oxide, and magnesium fluoride can be used for the purpose of adjusting the refractive index. It can be mixed and used in proportion.
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Abstract
Description
また、シロキサン結合を含む高分子化合物は、高い酸素プラズマ耐性を有する。このため、シロキサン結合を含む高分子化合物は、例えば多層レジストのハードマスク材料としても検討されている。
この特許文献1の段落0106、実施例3-1には、ポリシロキサン化合物の合成方法として、-C(CF3)2OHで表される基を有するポリシロキサン化合物(ポリマー)に対して、二炭酸ジ-tert-ブチルを反応させることで、ポリマー中に酸不安定性基(t-ブトキシカルボニル基)を導入したことが記載されている。
本発明は、以下のように表される。
下記一般式(x)で表されるケイ素化合物。
R1は、複数ある場合はそれぞれ独立に、炭素数1~10の直鎖状、炭素数3~10の分岐状もしくは炭素数3~10の環状のアルキル基、炭素数2~10の直鎖状、炭素数3~10の分岐状もしくは炭素数3~10の環状のアルケニル基であり、アルキル基またはアルケニル基中の水素原子の全てまたは一部がフッ素原子により置換されていてもよく、
R2は、複数ある場合はそれぞれ独立に、炭素数1~4の直鎖状または炭素数3~4の分岐状のアルキル基であり、アルキル基中の水素原子の全てまたは一部がフッ素原子により置換されていてもよく、
RAは、酸不安定性基であり、
aは1~3の整数、bは0~2の整数、cは1~3の整数であり、a+b+c=4であり、
nは1~5の整数である。
1.に記載のケイ素化合物であって、
前記RAは、アルキル基、アルコキシカルボニル基、アセタール基、シリル基およびアシル基からなる群より選ばれる少なくともいずれかであるケイ素化合物。
下記一般式(x)で表されるケイ素化合物(X)を含む反応性材料。
R1は、複数ある場合はそれぞれ独立に、炭素数1~10の直鎖状、炭素数3~10の分岐状もしくは炭素数3~10の環状のアルキル基、炭素数2~10の直鎖状、炭素数3~10の分岐状もしくは炭素数3~10の環状のアルケニル基であり、アルキル基またはアルケニル基中の水素原子の全てまたは一部がフッ素原子により置換されていてもよく、
R2は、複数ある場合はそれぞれ独立に、炭素数1~4の直鎖状または炭素数3~4の分岐状のアルキル基であり、アルキル基中の水素原子の全てまたは一部がフッ素原子により置換されていてもよく、
RAは、酸不安定性基であり、
aは1~3の整数、bは0~2の整数、cは1~3の整数であり、a+b+c=4であり、
nは1~5の整数である。
3.に記載の反応性材料であって、
前記RAは、アルキル基、アルコキシカルボニル基、アセタール基、シリル基およびアシル基からなる群より選ばれる少なくともいずれかである反応性材料。
3.または4.に記載の反応性材料であって、
さらに、下記一般式(y)で表されるケイ素化合物(Y)を含み、
当該反応性材料中に含まれる、前記ケイ素化合物(X)の質量をMX、前記ケイ素化合物(Y)の質量をMYとしたとき、{MY/(MX+MY)}×100で表されるケイ素化合物(Y)の比率が、1×10-4~12質量%である反応性材料。
6.酸性触媒下または塩基性触媒下で、1.もしくは2に記載のケイ素化合物、または、3.~5.のいずれか1つに記載の反応性材料を重縮合することで得られるポリシロキサン化合物。
6.に記載のポリシロキサン化合物であって、
重量平均分子量が1,000~100,000であるポリシロキサン化合物。
6.または7.に記載のポリシロキサン化合物と、溶剤とを含む樹脂組成物。
8.に記載の樹脂組成物であって、
前記溶剤が、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテル、シクロヘキサノン、乳酸エチル、γ―ブチロラクトン、ジアセトンアルコール、ジグライム、メチルイソブチルケトン、酢酸3-メトキシブチル、2-ヘプタノン、N、N-ジメチルホルムアミド、N、N-ジメチルアセトアミド、N-メチルピロリドン、グリコール類、グリコールエーテル類およびグリコールエーテルエステル類からなる群から選ばれる少なくとも1種を含む樹脂組成物。
8.または9.に記載の樹脂組成物と、光酸発生剤とを含む感光性樹脂組成物。
8.または9.に記載の樹脂組成物の硬化膜。
8.または9.に記載の樹脂組成物を基材上に塗布した後、100~350℃の温度で加熱する加熱工程を含む硬化膜の製造方法。
10.に記載の感光性樹脂組成物のパターン硬化膜。
10.に記載の感光性樹脂組成物を基材上に塗布して感光性樹脂膜を形成する膜形成工程と、
前記感光性樹脂膜を露光する露光工程と、
露光後の前記感光性樹脂膜を現像して、パターン樹脂膜を形成する現像工程と、
前記パターン樹脂膜を加熱することによって前記パターン樹脂膜をパターン硬化膜にする硬化工程と、
を含むパターン硬化膜の製造方法。
14.に記載のパターン硬化膜の製造方法であって、
前記露光工程の露光に用いられる光の波長が100~600nmであるパターン硬化膜の製造方法。
本明細書において、「環状のアルキル基」は、単環構造だけでなく多環構造も含む。「シクロアルキル基」も同様である。
本明細書における「(メタ)アクリル」との表記は、アクリルとメタクリルの両方を包含する概念を表す。「(メタ)アクリレート」等の類似の表記についても同様である。
本明細書における「有機基」の語は、特に断りが無い限り、有機化合物から1つ以上の水素原子を除いた原子団のことを意味する。例えば、「1価の有機基」とは、任意の有機化合物から1つの水素原子を除いた原子団のことを表す。
本実施形態のケイ素化合物(ケイ素化合物(X))は、下記一般式(x)で表される。
また、本実施形態の反応性材料は、下記一般式(x)で表されるケイ素化合物(X)を含む。
R1は、複数ある場合はそれぞれ独立に、炭素数1~10の直鎖状、炭素数3~10の分岐状もしくは炭素数3~10の環状のアルキル基、炭素数2~10の直鎖状、炭素数3~10の分岐状もしくは炭素数3~10の環状のアルケニル基であり、アルキル基またはアルケニル基中の水素原子の全てまたは一部がフッ素原子により置換されていてもよく、
R2は、複数ある場合はそれぞれ独立に、炭素数1~4の直鎖状または炭素数3~4の分岐状のアルキル基であり、アルキル基中の水素原子の全てまたは一部がフッ素原子により置換されていてもよく、
RAは、酸不安定性基であり、
aは1~3の整数、bは0~2の整数、cは1~3の整数であり、a+b+c=4であり、
nは1~5の整数である。
原料の入手容易性やコストなどの点で、R1は好ましくは炭素数1~6のアルキル基、より好ましくはメチル基である。
同様に原料の入手容易性やコストなどの点で、R2は好ましくはメチル基またはエチル基である。
合成の容易性の点で、aは1が好ましい。
同様に合成の容易性の点で、nは1または2が好ましく、1がより好ましい。
cは、2または3が好ましい。2以上のOR2が存在することで、ケイ素化合物(X)を用いてポリシロキサン化合物(ポリマーまたはオリゴマー)を製造することができる。
ベンゼン環の反応性(配向性)の関係から、-C(CF3)2ORAで表される基は、好ましくは-SiR1 b(OR2)cで表される基に対してメタ位に存在することが好ましい。より具体的には、一般式(x)中の下記基(2)の部分は、式(2A)~式(2D)で表わされる構造のいずれかであることができるが、なかでも式(2A)または式(2D)で表される構造が好ましい。
アルキル基としては、tert-ブチル基、tert-アミル基、1,1-ジメチルプロピル基、1-エチル-1-メチルプロピル基、1,1-ジメチルブチル基、アリル基、1-ピレニルメチル基、5-ジベンゾスベリル基、トリフェニルメチル基、1-エチル-1-メチルブチル基、1,1-ジエチルプロピル基、1,1-ジメチル-1-フェニルメチル基、1-メチル-1-エチル-1-フェニルメチル基、1,1-ジエチル-1-フェニルメチル基、1-メチルシクロヘキシル基、1-エチルシクロヘキシル基、1-メチルシクロペンチル基、1-エチルシクロペンチル基、1-イソボルニル基、1-メチルアダマンチル基、1-エチルアダマンチル基、1-イソプロピルアダマンチル基、1-イソプロピルノルボルニル基、1-イソプロピル-(4-メチルシクロヘキシル)基等が挙げられる。アルキル基は好ましくは第3級アルキル基であり、より好ましくは-CRpRqRrで表される基である(Rp、RqおよびRrは、それぞれ独立に、直鎖または分岐アルキル基、単環または多環のシクロアルキル基、アリール基またはアラルキル基であり、Rp、RqおよびRrのうち2つが結合して環構造を形成してもよい)。
アルコキシカルボニル基としては、例えば、tert-ブトキシカルボニル基、tert-アミルオキシカルボニル基、メトキシカルボニル基、エトキシカルボニル基、i-プロポキシカルボニル基などが挙げられる。
アセタール基としては、メトキシメチル基、エトキシエチル基、ブトキシエチル基、シクロヘキシルオキシエチル基、ベンジルオキシエチル基、フェネチルオキシエチル基、エトキシプロピル基、ベンジルオキシプロピル基、フェネチルオキシプロピル基、エトキシブチル基、エトキシイソブチル基などが挙げられる。
シリル基としては、例えば、トリメチルシリル基、エチルジメチルシリル基、メチルジエチルシリル基、トリエチルシリル基、i-プロピルジメチルシリル基、メチルジ-i-プロピルシリル基、トリ-i-プロピルシリル基、tert-ブチルジメチルシリル基、メチルジ-tert-ブチルシリル基、トリ-tert-ブチルシリル基、フェニルジメチルシリル基、メチルジフェニルシリル基、トリフェニルシリル基などが挙げられる。
アシル基としては、例えば、アセチル基、プロピオニル基、ブチリル基、ヘプタノイル基、ヘキサノイル基、バレリル基、ピバロイル基、イソバレリル基、ラウリロイル基、ミリストイル基、パルミトイル基、ステアロイル基、オキサリル基、マロニル基、スクシニル基、グルタリル基、アジポイル基、ピペロイル基、スベロイル基、アゼラオイル基、セバコイル基、(メタ)アクリロイル基、プロピオロイル基、クロトノイル基、オレオイル基、マレオイル基、フマロイル基、メサコノイル基、カンホロイル基、ベンゾイル基、フタロイル基、イソフタロイル基、テレフタロイル基、ナフトイル基、トルオイル基、ヒドロアトロポイル基、アトロポイル基、シンナモイル基、フロイル基、テノイル基、ニコチノイル基、イソニコチノイル基などが挙げられる。
酸不安定性基の水素原子の一部又は全部は、フッ素原子で置換されていてもよい。
R11は、炭素数1~10の直鎖状、炭素数3~10の分岐状もしくは炭素数3~10の環状のアルキル基、炭素数6~20のアリール基または炭素数7~21のアラルキル基であり、
R12は、水素原子、炭素数1~10の直鎖状、炭素数3~10の分岐状もしくは炭素数3~10の環状のアルキル基、炭素数6~20のアリール基または炭素数7~21のアラルキル基である。
R13、R14およびR15は、それぞれ独立に、炭素数1~10の直鎖状、炭素数3~10の分岐状もしくは炭素数3~10の環状のアルキル基、炭素数6~20のアリール基または炭素数7~21のアラルキル基であり、
R13、R14およびR15のうち2つは、互いに結合して環構造を形成してもよい。
また、本実施形態の反応性材料は、互いに異なる化学構造のRAを有する2種以上のケイ素化合物(X)を含むものであってもよい。もちろん、本実施形態の反応性材料は、ケイ素化合物(X)として実質的に1種のみを含むものであってもよい。
本実施形態の反応性材料は、さらに下記一般式(y)で表されるケイ素化合物(Y)を含むことができる。このとき、反応性材料中に含まれるケイ素化合物(X)の質量をMX、ケイ素化合物(Y)の質量をMYとしたとき、{MY/(MX+MY)}×100で表されるケイ素化合物(Y)の比率(質量%)は、好ましくは1×10-4~12%、より好ましくは5×10-4~10%、さらにより好ましくは0.001~8%、特に好ましくは0.01~5%である。
ケイ素化合物(Y)は、酸触媒として、ケイ素化合物(X)の反応、例えば重縮合(脱水によるシロキサン結合の形成)に寄与すると考えられる。よって、本実施形態の反応性材料が適量のケイ素化合物(Y)を含むことにより、例えば本実施形態の反応性材料をポリシロキサン化合物の原料モノマーとして用いる場合に、貯蔵安定性の効果を得つつ、良好な重合性が得られると考えられる。また、例えば本実施形態の反応性材料をプライマーとして用いた場合、貯蔵安定性の効果を得つつ、良好な密着性や硬化性を示すと考えられる。
さらに、例えば本実施形態の反応性材料をポリシロキサン化合物の原料モノマーとして用いる場合には、ケイ素化合物(Y)は生成されるポリシロキサン化合物中に取り込まれると考えられる。このことは、ポリシロキサン化合物の合成後に触媒を除去する必要がないという利点につながると考えられる。
本実施形態のケイ素化合物(X)/反応性材料の製造方法は特に限定されない。典型的な製造方法を以下に説明する。
一般式(x)においてRAが水素原子である化合物の分子中に存在するHFIP基の量に対して、同モル量以上の二炭酸ジ-tert-ブチルを加え、ピリジン、トリエチルアミン、N,N-ジメチルアミノピリジン等の塩基存在下、溶媒に溶解させて反応させる。このようにして、tert-ブトキシカルボニル基を導入することができる。使用可能な溶媒は、上記の反応系に投入する化合物を溶解でき、反応に悪影響を与えるものでなければ特に限定されない。具体的には、トルエン、キシレン、ピリジンなどが好ましい。反応温度、反応時間は、使用する塩基の種類などによって異なるが、通常、反応温度は室温以上180℃以下、反応時間は1~24時間である。反応終了後、溶媒、塩基及び過剰量に加えた場合は二炭酸ジ-tert-ブチルを留去することによって、一般式(x)においてRAがtert-ブトキシカルボニル基であるケイ素化合物(X)を得ることができる。
一般式(x)においてRAが水素原子である化合物の分子中に存在するHFIP基の量に対して、同モル量以上の強塩基(NaH等)と、同モル量以上のクロロメチルメチルエーテルを加え、反応させる。このようにして、メトキシメチル基を導入することができる。このとき使用可能な溶媒は特に限定されず、反応系に投入する化合物を溶解でき、反応に悪影響を与えない任意の溶媒を用いることができる。好ましい溶媒はテトラヒドロフラン等である。反応は室温でも進行する。反応終了後、後処理として、水洗時に2層分離させるための溶媒(トルエン、ジイソプロピルエーテル等)の投入、水洗、食塩水による洗浄、単蒸留(圧力2.5kPa程度、温度200~220℃程度)などを行うことが好ましい。
一般式(x)においてRAが水素原子である化合物の分子中に存在するHFIP基の量に対して、同モル量以上のビニルアセタール(R11-O-CH=CH2で表される化合物、R11の定義は一般式(ALG-1)と同様)を、酸触媒(例えばパラトルエンスルホン酸)の存在下で反応させる。これにより、一般式(ALG-1)においてR12がメチル基である酸不安定性基を導入することができる。このとき使用可能な溶媒は特に限定されず、反応系に投入する化合物を溶解でき、反応に悪影響を与えない任意の溶媒を用いることができる。反応は室温でも進行する。反応終了後、洗浄、蒸留などの後処理を行ってもよい。
本実施形態のポリシロキサン化合物は、酸性触媒下または塩基性触媒下で、上記のケイ素化合物(ケイ素化合物(X))、または、上記の反応性材料を重縮合することで製造される。ケイ素化合物(X)は、酸性触媒下または塩基性触媒下で、一般式(x)中の「OR2」の部分が加水分解する。これによりシラノール基が生じる。発生したシラノール基の2以上が脱水縮合することによりポリシロキサン化合物が得られる。または、発生したシラノール基と「Si-OR2」部分の縮合反応によってもポリシロキサン化合物が得られる。
重縮合の際には、ケイ素化合物(X)やケイ素化合物(Y)とは異なる反応性材料(モノマー)を反応系中に存在させてもよい。これにより共重合体を得ることができる。これについては追って説明する。
・製造方法1:保護されていないHFIP基を有する反応性材料(例えば一般式(x)において、RAが水素原子である化合物)を重縮合してポリマーまたはオリゴマーを得る。その後、そのポリマーまたはオリゴマーに対して酸不安定性基を導入する。
・製造方法2:ケイ素化合物(X)のような、予めHFIP基が酸不安定性基で保護された反応性材料を重縮合する。
本発明者らは、上記問題の解決のために様々な検討を行った。検討を通じ、意外なことに、製造方法2のようにしてポリシロキサン化合物を製造すると、上記問題が生じにくいことを見出した。
上記(2)について補足すると、製造方法2のようにポリシロキサン化合物の製造前に原料のモノマーに酸不安定性基を導入するほうが、製造方法1よりも不純物(未反応物等)の除去が容易であり、このことは最終的なポリシロキサン化合物の透明性アップ等につながると考えられる。つまり、酸性触媒下または塩基性触媒下で、上記のケイ素化合物(ケイ素化合物(X))、または、上記の反応性材料を重縮合することで、高透明なポリシロキサン化合物を得やすい。
(2)加水分解のための水、重縮合反応を進行させるための触媒、および、所望により反応溶媒、を反応容器内に加え、適宜攪拌して反応溶液を調製する。これらの投入順序は特に限定されず、任意の順序で投入して反応溶液を調製することができる。この際、ケイ素化合物(X)やケイ素化合物(Y)に該当しないシロキサン化合物(モノマー)を反応容器内に加えてもよい。こうすることで、共重合体であるポリシロキサン化合物を製造することができる。
(3)(2)で調製した反応溶液を撹拌しながら加水分解および縮合反応を進行させる。触媒の種類にもよるが、反応に必要な時間は通常3~24時間、反応温度は通常室温(25℃)~200℃である。加熱する場合は、反応系中の未反応原料、水、反応溶媒および/または触媒が、反応系外へ留去されることを防ぐため、反応容器を閉鎖系にするか、コンデンサーなどの還流装置を取り付けて反応系を還流させることが好ましい。
(4)好ましくは、反応終了後に、反応系内に残存する水、生成するアルコール、触媒などを除去する。水、アルコールおよび触媒の除去は、抽出により行ってもよいし、トルエンなどの反応に悪影響を与えない溶媒を反応系内に加え、ディーン・スターク管を用いることで共沸除去してもよい。
酸触媒としては、塩酸、硝酸、硫酸、フッ酸、リン酸、酢酸、しゅう酸、トリフルオロ酢酸、メタンスルホン酸、トリフルオロメタンスルホン酸、カンファースルホン酸、ベンゼンスルホン酸、トシル酸、ギ酸、多価カルボン酸あるいはその無水物などが挙げられる。
塩基触媒としては、水酸化テトラメチルアンモニウム、トリエチルアミン、トリプロピルアミン、トリブチルアミン、トリペンチルアミン、トリヘキシルアミン、トリヘプチルアミン、トリオクチルアミン、ジエチルアミン、トリエタノールアミン、ジエタノールアミン、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム等が挙げられる。
触媒の使用量としては、原料に含まれる加水分解性基(一般式(x)中のOR2など)の全モル数に対して、1.0×10-5~1.0×10-1倍であることが好ましい。
反応溶媒を用いる場合、その種類は特に限定されない。原料化合物、水、触媒に対する溶解性の観点からは極性溶媒が好ましく、さらに好ましくはアルコール系溶媒である。具体的には、メタノール、エタノール、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、ジアセトンアルコール、プロピレングリコールモノメチルエーテル等が挙げられる。反応溶媒は単独溶媒であってもよいし混合溶媒であってもよい。反応溶媒を用いる場合の使用量については、反応が均一系で進行するのに必要な量であればよい。
前述のように、重縮合の際に、ケイ素化合物(X)やケイ素化合物(Y)とは異なる反応性材料(モノマー)を反応系中に1種または2種以上存在させて、共重合体を得てもよい。具体的には、上記の手順(2)において、ケイ素化合物(X)やケイ素化合物(Y)に該当しないシロキサン化合物またはシラン化合物モノマーを反応容器内に加えることで、共重合体を得ることができる。
以下、「ケイ素化合物(X)やケイ素化合物(Y)に該当しないシロキサン化合物またはシラン化合物モノマー」を総称して「ケイ素化合物(Z)」とも表記する。
本実施形態のポリシロキサン化合物中に、ケイ素化合物(Z1)に由来する構造単位が組み込まれることで、例えば本実施形態のポリシロキサン化合物を熱硬化性の樹脂組成物などに好ましく適用することができる。
R1、R2、a、bおよびcの定義および好ましい態様は、一般式(x)と同様であり、
Ryは、エポキシ基、オキセタン基、(メタ)アクリロイル基のいずれかを含む炭素数2~30の一価の有機基である。
Ryがエポキシ基またはオキセタン基を含むことで、例えば本実施形態のポリシロキサン化合物を後述の樹脂組成物等に適用した場合、シリコン、ガラス、樹脂などの各種基材との密着性を高めることができる。また、Ryが(メタ)アクリロイル基を含む場合、例えば本実施形態のポリシロキサン化合物を後述の硬化膜とするとき、良好な耐溶剤性が得られる。
RjおよびRkが二価の有機基である場合の好ましい例としては、Rg、RhおよびRiで好ましい基として挙げたものを挙げることができる。
また、ケイ素化合物(Z1)の具体例としては、3-メタクリロキシプロピルトリメトキシシラン(信越化学工業株式会社製、製品名:KBM-503)、3-メタクリロキシプロピルトリエトキシシラン(同、製品名:KBE-503)、3-メタクリロキシプロピルメチルジメトキシシラン(同、製品名:KBM-502)、3-メタクリロキシプロピルメチルジエトキシシラン(同、製品名:KBE-502)、3-アクリロキシプロピルトリメトキシシラン(同、製品名:KBM-5103)、8-メタクリロキシオクチルトリメトキシシラン(同、製品名:KBM-5803)なども挙げられる。
ケイ素化合物(Z)を用いる場合、その量については、所望の性能等に応じて適宜調整すればよい。具体的には、ケイ素化合物(Z)を用いる場合、その量は、重縮合に用いられる全ての重合性成分(ケイ素化合物(X)、(Y)および(Z))中、例えば1~50mol%、好ましくは5~40mol%である。
また、ケイ素化合物(Z1)を用いる場合、その量は、硬化性と他性能とのバランスなどを考慮し、重縮合に用いられる全ての重合性成分中、好ましくは1~50mol%、より好ましくは5~40mol%である。
なお、通常は、ケイ素化合物(X)、(Y)および(Z)の仕込み比と、ポリシロキサン化合物中におけるケイ素化合物(X)、(Y)および(Z)それぞれに対応する構造単位の比率は、おおよそ同程度とみなすことができる。
本実施形態の樹脂組成物は、上記のポリシロキサン化合物と、溶剤とを含む。換言すると、本実施形態の樹脂組成物は、上記のポリシロキサン化合物が、溶剤に溶解および/または分散したものである。ポリシロキサン化合物を溶媒に溶解および/または分散させて樹脂組成物とし、その樹脂組成物を基材上に塗布し、そして溶剤を乾燥させることで、樹脂膜を形成することができる。また、その樹脂膜を加熱することで硬化膜を製造することができる。
溶剤の使用量は特に限定されないが、樹脂組成物中の全固形分(揮発性溶剤以外の成分)が、通常5~60質量%、好ましくは10~50質量%となるように用いられる。全固形分濃度を適切に調整することで、薄膜の形成しやすさや、膜厚の均一性などが良化する傾向がある。
例えば、塗布性、レベリング性、成膜性、保存安定性または消泡性等を向上させる目的で、界面活性剤等の添加剤を配合することができる。具体的には、市販の界面活性剤である、DIC株式会社製の商品名メガファック、品番F142D、F172、F173もしくはF183、住友スリーエム株式会社製の商品名フロラード、品番、FC-135、FC-170C、FC-430もしくはFC-431、AGCセイミケミカル株式会社製の商品名サーフロン、品番S-112、S-113、S-131、S-141もしくはS-145、または東レ・ダウコーニングシリコーン株式会社製、商品名、SH-28PA、SH-190、SH-193、SZ-6032もしくはSF-8428が挙げられる。
(「メガファック」「フロラード」および「サーフロン」は、各社の登録商標である。)
界面活性剤を用いる場合、その量は、ポリシロキサン化合物100質量部に対して、通常0.001~10質量部である。
硬化剤を用いる場合、その量は、ポリシロキサン化合物100質量部に対して、通常、0.001~10質量部である。
本実施形態の樹脂組成物を基材上に塗布して樹脂膜を形成する膜形成工程と、
その樹脂膜を加熱することによって硬化膜にする硬化工程と、
を含むことができる。
以下、膜形成工程および硬化工程について具体的に説明する。
膜形成工程において、樹脂組成物を塗布する基材は特に限定されない。形成される硬化膜の用途に応じて、シリコンウェハ、金属、ガラス、セラミック、プラスチック製の基材から選択される。
膜形成の際の塗布方法や塗布装置は特に限定されない。スピンコート、ディップコート、スプレーコート、バーコート、アプリケーター、インクジェット、ロールコート等、公知の塗布方法/装置が適用可能である。
膜形成工程で形成された樹脂膜を更に加熱処理することで、硬化膜を得ることができる。加熱処理の温度は、通常100~350℃である。溶剤の沸点にもよるが、より好ましい温度は150~280℃である。適度に高い温度で加熱することで、処理スピードを上げることができる。一方、加熱温度が高すぎないことにより、硬化膜の均一性を向上させることができる。
本実施形態の感光性樹脂組成物は、上記ポリシロキサン化合物と、光酸発生剤と、溶剤とを含む。別の言い方として、上述の樹脂組成物に、更に光酸発生剤を加えることで、本実施形態の感光性樹脂組成物を製造することができる。
光照射により発生した酸がポリシロキサン化合物中の酸不安定性基に作用することで、酸不安定性基が脱離してHFIP基が産生する。これによりポリシロキサン化合物がアルカリ現像液に可溶となる。一方、光照射が無いと、ポリシロキサン化合物はアルカリ現像液に不溶のままである。このような、光照射によるアルカリ現像液への溶解性変化を利用して、感光性樹脂組成物によるパターン樹脂膜を製造することができる。また、そのパターンを硬化させることでパターン硬化膜を得ることができる。
光酸発生剤の量は、ポリシロキサン化合物を100質量部としたときに、例えば0.01~10質量部、好ましくは0.05~5質量部である。適度な量の光酸発生剤を用いることで、十分な感度や解像力と、組成物の貯蔵安定性の両立を図ることができる。
増感剤を用いる場合、その配合量は、ポリシロキサン化合物100質量部に対して、通常、0.001~10質量部である。
感光性樹脂組成物を基材上に塗布して感光性樹脂膜を形成する膜形成工程と、
感光性樹脂膜を露光する露光工程と、
露光後の感光性樹脂膜を現像して、パターン樹脂膜を形成する現像工程と、
パターン樹脂膜を加熱することによってパターン樹脂膜をパターン硬化膜にする硬化工程と、
を含む一連の工程により製造することができる。
感光性樹脂組成物を塗布する基材としては、形成される硬化膜の用途に応じて、例えば、シリコンウェハ、金属、ガラス、セラミック、プラスチック製の基材から選択される。
塗布方法としては、スピンコート、ディップコート、スプレーコート、バーコート、アプリケーター、インクジェットまたはロールコーター等、公知の塗布方法を特に制限無く適用できる。
例えば、膜形成工程で得られた感光性樹脂膜に対し、目的のパターンを形成するためのフォトマスクを介して光を照射する。
次に、露光工程で得られた、露光後の感光性樹脂膜を現像することで、パターン形状を有する膜(以下、「パターン樹脂膜」とも記載する)を作成する。アルカリ性の水溶液を現像液として用いることで、露光後の感光性樹脂膜における露光部が溶解し、パターン樹脂膜が形成される。
より具体的には、水酸化カリウム、水酸化ナトリウム、アンモニア、エチルアミン、ジエチルアミン、トリエチルアミン、トリエタノールアミン、テトラメチルアンモニウムヒドロキシド(略称:TMAH)などのアルカリ水溶液が挙げられる。中でも、TMAH水溶液を用いることが好ましく、特に、0.1質量%以上5質量%以下、より好ましくは2質量%以上3質量%以下のTMAH水溶液を用いることが好ましい。
現像工程で得られたパターン樹脂膜を加熱処理することで、最終的なパターン硬化膜が得られる。加熱処理により、ポリシロキサン化合物において未反応性基として残存するアルコキシ基やシラノール基を縮合させることができる。また、感光性樹脂組成物中にエポキシ基、オキセタン基、メタクリロイル基、アクリロイル基等が含まれる場合は、それらを十分に硬化させることができる。
加熱温度としては、80~400℃が好ましく、100~350℃がより好ましい。加熱時間は、通常1~90分、好ましくは5~60分である。加熱温度および時間を適切に調整することで、樹脂膜中に含まれる成分の分解を抑えつつ、樹脂膜を十分に硬化させることができる。そして、薬液耐性が良好で、透明性が高く、クラック発生が抑えられた硬化膜を得やすい。
上記<ケイ素化合物および反応性材料>の項で、本実施形態の反応性材料は、さらに下記一般式(y)で表されるケイ素化合物(Y)を含むことができること等を述べた。
これに関して、本発明の実施形態の一部は、以下のような「組成物」として捉えることもできる。
この組成物中に含まれるケイ素化合物(X)の質量をMX、ケイ素化合物(Y)の質量をMYとしたとき、{MY/(MX+MY)}×100で表されるケイ素化合物(Y)の比率(質量%)は、好ましくは1×10-4~12%、より好ましくは5×10-4~10%、さらにより好ましくは0.001~8%、特に好ましくは0.01~5%である組成物。」
MOMCl:クロロメチルメチルエーテル
Boc2O:二炭酸ジ-tert-ブチル
TBAI:テトラブチルアンモニウムヨージド
TMAH:テトラメチルアンモニウムヒドロキシド
Ph-Si:フェニルトリエトキシシラン
KBM-303:信越化学工業株式会社製、2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン
KBM-5103:信越化学工業株式会社製、3-アクリロキシプロピルトリメトキシシラン
エチルポリシリケート:多摩化学工業株式会社製、シリケート40
共鳴周波数400MHzの核磁気共鳴装置(日本電子株式会社製、機器名JNM-ECA-400)を使用し、1H-NMRおよび19F-NMRを測定した。
ガスクロマトグラフとしては、株式会社島津製作所、機器名Shimadzu GC-2010を用い、キャピラリーカラムとしては、アジレント社、形式DB5(長さ30mm×内径0.25mm×膜厚0.25μm)を用いた。
東ソー株式会社製の高速GPC装置、機器名HLC-8320GPCを用い、ポリスチレン換算での重量平均分子量を測定した。
(合成例1-1:HFA-Si-MOMを含む反応性材料の製造)
氷浴につけた三口フラスコ中のTHF(150g)およびNaH(16.2g、0.41mol)の混合液に、HFA-Si(150g、0.37mol)を滴下し、その後、MOMCl(32.6g、0.38mol)を滴下した。その後、室温で20時間攪拌した。
上記の攪拌終了後、エバポレーターで反応液を濃縮した。濃縮された反応液に、トルエン300gと水150gとを投入して攪拌した。攪拌後にしばらく静置して二層分離後、下層の水層を除去した。得られた上層の有機層に対して、さらに水150gを投入して、同様の操作を繰り返した。最終的に得られた上層の有機層をエバポレーターで濃縮して、180gの粗体を得た。
得られた粗体を単蒸留(減圧度2.5kPa、バス温200~220℃、トップ温170℃)して、HFA-Si-MOMを含む反応性材料(液状)を145g得た。
上記において、HFA-Si-MOMの収率は84.3%、GC純度は97%であった。また、得られた反応性材料中には微量のHFA-Siが含まれており、{HFA-Siの量/(HFA-Si-MOMの量 + HFA-Siの量)}×100で計算されるHFA-Siの比率は、0.1質量%であった。
1H-NMR(溶媒CDCl3、TMS):δ7.92(s,1H)、7.79-7.76(m,1H)、7.68-7.67(m,1H)、7.49-7.45(m,1H)、4.83(s,2H)、3.86(q,6H)、3.55(s,3H)、1.23(t,9H)
19F-NMR(溶媒CDCl3、C6F6):δ-71.4(s,6F)
氷浴につけた三口フラスコ中に、THF(10g)、NaH(1.2g、0.03mol)、HFA-Si(10g、0.025mol)を加え、30分攪拌した。その後、フラスコ中にBoc2O(5.2g、0.027mol)およびTBAI(0.3g、0.001mol)を加え、室温で18時間攪拌した。
得られた反応生成物に、ジイソプロピルエーテル(20g)と水(10g)を加え、攪拌し、その後しばらく静置した。静置して二層分離した後の下層の水層を除去した。得られた上層の有機層を硫酸マグネシウムで乾燥し、その後、エバポレーターで濃縮して、HFA-Si-BOC 10g(収率83%、GC純度95%)を得た。
1H-NMR(溶媒CDCl3、TMS):δ7.78-7.75(m,2H)、7.52-7.43(m、2H)、3.84(q,6H)、1.46(s,9H)、1.22(t,9H)
19F-NMR(溶媒CDCl3、C6F6):δ-70.2(s,6F)
国際公開第2019/167770号の段落0124、実施例5に記載の手順に準じて、HFA-Siを合成した。
評価用サンプルとして、合成例1-1で製造された反応性材料(ケイ素化合物(Y)に該当するHFA-Siを0.1質量%含有)を準備した(これを「サンプル1」とする)。また、サンプル1に、さらにその反応性材料にさらにHFA-Siを加えたサンプル2~5を準備した。
各サンプルにおける、{MY/(MX+MY)}×100で表されるケイ素化合物(Y)の比率は、後掲の表に示す。
後掲の表2には、以下の評価基準に基づく評価結果を記載した。
変化なし:Mw値の変化量が±20以内
変化あり:Mw値の増加量が200以上
変化なし:GC純度の変化量が±1.5%以内
変化あり:GC純度の減少量が10%以上
(「GC純度」とは、ガスクロマトグラフ測定で得られるチャートの面積から求めた、サンプル中のHFA-Si-MOMの純度を表す。)
(合成例2-1:塩基条件でのポリシロキサン化合物の合成)
反応容器中に、合成例1-1で得られたHFA-Si-MOMを含む反応性材料(1.0g、2.2mmol)、EtOH(0.5g)、水(0.13g、7.0mmol)、25質量%TMAH水溶液(TMAHとして0.002g、0.02mmol)を入れ、攪拌しながら60℃で4時間反応を実施した。
その後、反応液にトルエン(5g)を加え、105℃で20時間、ディーン・スターク装置を付け還流させ、水とEtOHを留去した。さらに水洗を3回行い(各回水を2g使用)、そして有機層をエバポレーターで濃縮した(条件:30hPa、60℃、30min)。
以上により、目的物であるポリシロキサン化合物を0.8g得た。GPC測定による重量平均分子量Mwは2100であった。
反応容器中にHFA-Si(1g、2.5mmol)、EtOH(1g)水(0.14g、7.8mmol)、25質量%TMAH水溶液(TMAHとして0.002g、0.02mmol)を加え、攪拌しながら60℃で4時間反応させた。
その後、反応液にトルエン(5g)を加え、105℃で20時間、ディーン・スターク装置を付け還流させ、水とEtOHを留去した。さらに水洗を3回行い(各回水を2g使用)、そして有機層をエバポレーターで濃縮した(条件:30hPa、60℃、30min)。
以上により、ポリシロキサン化合物を0.8g得た。GPC測定による重量平均分子量Mwは1000であった。
反応容器中に、HFA-Si(1g、2.5mmol)、NaOH(0.4g、3.0mmol)、水(0.14g、7.8mmol)、EtOH(1g)を入れ、攪拌しながら60℃で4時間反応させた。これによりポリシロキサン化合物を得た。GPC測定による重量平均分子量Mwは1300であった。
また、前述の、反応性材料の保存安定性の評価結果(保存安定性は良好であった)とあわせ、本実施形態の反応性材料は、保存安定性が良好でありつつ、反応性も良好であることが示された。
反応容器中に、合成例1-1で得られたHFA-Si-MOMを含む反応性材料(1.0g、2.2mmol)、アセトン(2g)、水(4.13g、7.0mmol)、酢酸(0.02g、0.1mmol)を加え、60℃で20時間反応させた。その後、エバポレーターを用いて、反応液からアセトンと水、を留去して、ポリマーを0.8g得た(収率100%)。GPC測定による重量平均分子量Mwは1600であった。また、19F-NMRでの分析によると、メトキシメチル基は脱離していなかった。
以上より、本実施形態の反応性材料は、酸性条件下においても、ポリシロキサン化合物の原料などとして好ましく使用可能なことが示された。
合成例2-1において、重合触媒としてTMAHではなくKOHを用いた以外は、同様にしてポリシロキサン化合物を得た(合成例2-1')。
また、合成例2-2において、重合触媒として酢酸ではなく塩酸を用いた以外は、同様にしてポリシロキサン化合物を得た(合成例2-3)。
さらに、合成例2-1において、原料の種類および仕込み比を後掲の表のように変更した以外は、同様にしてポリシロキサン化合物を得た(合成例2-4~2-9)。
溶液組成物P-1、P-1'、P-2~P-9を、それぞれ、株式会社SUMCO製の直径4インチ、厚み525μmのシリコンウェハ上に、回転数500rpmでスピンコートした。その後、シリコンウェハをホットプレート上で100℃、3分間乾燥させた。さらにその後、230℃で1時間焼成させた。このようにして膜厚1~2μmのポリシロキサンの硬化膜を得た。
触指によりタック性の有無を確認したところ、いずれの膜でもタック性は認められなかった。つまり、本実施形態の反応性材料を、酸性触媒下または塩基性触媒下で重縮合することで得られたポリシロキサン化合物は、膜形成などへの適用において、大きな問題がないことを確認した。
溶液組成物P-1、P-1'、P-2~P-9を用いて、4インチシリコンウエハーの代わりに4インチガラス基板を用いたこと以外は上記と同様にして、膜厚1~2μmのポリシロキサンの硬化膜を得た。そして、硬化膜の透過スペクトルを測定した。
溶液組成物P-1、P-1'、P-2~P-9から得られた硬化膜の、膜厚2μm換算での波長400nmの光の透過率は、全て90%超であった。また、P-1、P-1'、P-2~P-4、およびP-9から得られた硬化膜の、膜厚2μm換算での波長350nmの光の透過率は、全て90%超であった。
このような、波長350~400nmの良好な光透過性より、本実施形態の反応性材料を、酸性触媒下または塩基性触媒下で重縮合することで得られたポリシロキサン化合物は、例えばi線露光に適用される感光性樹脂組成物、有機ELや液晶ディスプレイ、CMOSイメージセンサーなどのコーティング材料などに好ましく適用可能であるといえる。
溶液組成物P-1、P-1'、P-2~P-4それぞれ3gに対して、光酸発生剤であるCPI-100TF(サンアプロ社製)0.04gを添加し、攪拌して、均一な感光性樹脂組成物(5種)を作成した。
各感光性樹脂組成物を、株式会社SUMCO製の直径4インチ、厚み525μmのシリコンウェハ上に、回転数500rpmでスピンコートで塗布した。その後、シリコンウェハをホットプレート上で100℃、3分間加熱処理し、膜厚1~2μmの感光性樹脂膜を得た。
以上により、ポジ型パターンが形成されたパターン硬化膜を得た。5種の感光性樹脂組成物全てにおいて、10~20μmのラインアンドスペースパターンを解像することができた。すなわち、本反応性材料を重縮合することで得られるポリシロキサン化合物は、感光性樹脂組成物に好ましく適用可能といえる。
また、本実施形態のケイ素化合物または反応性材料を重縮合して得られるポリシロキサン化合物を含む樹脂組成物に感光剤を添加することで、アルカリ現像によるパターニング可能な感光性樹脂組成物とすることが可能ある。
さらに、本実施形態の樹脂組成物または感光性樹脂組成物から得られる硬化膜は、透明性に優れる。このことから、本実施形態の樹脂組成物または感光性樹脂組成物は、半導体用保護膜、有機ELや液晶ディスプレイ用保護膜、イメージセンサー用のコーティング材、平坦化材料、マイクロレンズ材料、タッチパネル用の絶縁性保護膜材料、液晶ディスプレイTFT平坦化材料、光導波路のコアやクラッドの形成材料、電子線用レジスト、多層レジスト用の中間膜、下層膜、反射防止膜等に好適に用いられる。これらの用途の内、ディスプレイやイメージセンサーなどの光学系部材に用いられる場合は、ポリテトラフルオロエチレン、シリカ、酸化チタン、酸化ジルコニウム、フッ化マグネシウムなどの微粒子を、屈折率調整の目的で任意の割合で混合して用いることができる。
Claims (15)
- 下記一般式(x)で表されるケイ素化合物。
R1は、複数ある場合はそれぞれ独立に、炭素数1~10の直鎖状、炭素数3~10の分岐状もしくは炭素数3~10の環状のアルキル基、炭素数2~10の直鎖状、炭素数3~10の分岐状もしくは炭素数3~10の環状のアルケニル基であり、アルキル基またはアルケニル基中の水素原子の全てまたは一部がフッ素原子により置換されていてもよく、
R2は、複数ある場合はそれぞれ独立に、炭素数1~4の直鎖状または炭素数3~4の分岐状のアルキル基であり、アルキル基中の水素原子の全てまたは一部がフッ素原子により置換されていてもよく、
RAは、酸不安定性基であり、
aは1~3の整数、bは0~2の整数、cは1~3の整数であり、a+b+c=4であり、
nは1~5の整数である。 - 請求項1に記載のケイ素化合物であって、
前記RAは、アルキル基、アルコキシカルボニル基、アセタール基、シリル基およびアシル基からなる群より選ばれる少なくともいずれかであるケイ素化合物。 - 下記一般式(x)で表されるケイ素化合物(X)を含む反応性材料。
R1は、複数ある場合はそれぞれ独立に、炭素数1~10の直鎖状、炭素数3~10の分岐状もしくは炭素数3~10の環状のアルキル基、炭素数2~10の直鎖状、炭素数3~10の分岐状もしくは炭素数3~10の環状のアルケニル基であり、アルキル基またはアルケニル基中の水素原子の全てまたは一部がフッ素原子により置換されていてもよく、
R2は、複数ある場合はそれぞれ独立に、炭素数1~4の直鎖状または炭素数3~4の分岐状のアルキル基であり、アルキル基中の水素原子の全てまたは一部がフッ素原子により置換されていてもよく、
RAは、酸不安定性基であり、
aは1~3の整数、bは0~2の整数、cは1~3の整数であり、a+b+c=4であり、
nは1~5の整数である。 - 請求項3に記載の反応性材料であって、
前記RAは、アルキル基、アルコキシカルボニル基、アセタール基、シリル基およびアシル基からなる群より選ばれる少なくともいずれかである反応性材料。 - 酸性触媒下または塩基性触媒下で、請求項1もしくは2に記載のケイ素化合物、または、請求項3~5のいずれか1項に記載の反応性材料を重縮合することで得られるポリシロキサン化合物。
- 請求項6に記載のポリシロキサン化合物であって、
重量平均分子量が1,000~100,000であるポリシロキサン化合物。 - 請求項6または7に記載のポリシロキサン化合物と、溶剤とを含む樹脂組成物。
- 請求項8に記載の樹脂組成物であって、
前記溶剤が、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテル、シクロヘキサノン、乳酸エチル、γ―ブチロラクトン、ジアセトンアルコール、ジグライム、メチルイソブチルケトン、酢酸3-メトキシブチル、2-ヘプタノン、N、N-ジメチルホルムアミド、N、N-ジメチルアセトアミド、N-メチルピロリドン、グリコール類、グリコールエーテル類およびグリコールエーテルエステル類からなる群から選ばれる少なくとも1種を含む樹脂組成物。 - 請求項8または9に記載の樹脂組成物と、光酸発生剤とを含む感光性樹脂組成物。
- 請求項8または9に記載の樹脂組成物の硬化膜。
- 請求項8または9に記載の樹脂組成物を基材上に塗布した後、100~350℃の温度で加熱する加熱工程を含む硬化膜の製造方法。
- 請求項10に記載の感光性樹脂組成物のパターン硬化膜。
- 請求項10に記載の感光性樹脂組成物を基材上に塗布して感光性樹脂膜を形成する膜形成工程と、
前記感光性樹脂膜を露光する露光工程と、
露光後の前記感光性樹脂膜を現像して、パターン樹脂膜を形成する現像工程と、
前記パターン樹脂膜を加熱することによって前記パターン樹脂膜をパターン硬化膜にする硬化工程と、
を含むパターン硬化膜の製造方法。 - 請求項14に記載のパターン硬化膜の製造方法であって、
前記露光工程の露光に用いられる光の波長が100~600nmであるパターン硬化膜の製造方法。
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