WO2024082896A1 - 碱溶性树脂、感光性树脂组合物和感光性固化膜 - Google Patents
碱溶性树脂、感光性树脂组合物和感光性固化膜 Download PDFInfo
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- WO2024082896A1 WO2024082896A1 PCT/CN2023/119327 CN2023119327W WO2024082896A1 WO 2024082896 A1 WO2024082896 A1 WO 2024082896A1 CN 2023119327 W CN2023119327 W CN 2023119327W WO 2024082896 A1 WO2024082896 A1 WO 2024082896A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- alkali
- photosensitive
- soluble resin
- cured film
- resin composition
- Prior art date
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- 239000011347 resin Substances 0.000 title claims abstract description 45
- 229920005989 resin Polymers 0.000 title claims abstract description 45
- 239000011342 resin composition Substances 0.000 title claims abstract description 28
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 15
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000004427 diamine group Chemical group 0.000 claims abstract description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 10
- 125000006159 dianhydride group Chemical group 0.000 claims abstract description 8
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 6
- 125000000962 organic group Chemical group 0.000 claims abstract description 5
- 239000010408 film Substances 0.000 claims description 29
- 239000002904 solvent Substances 0.000 claims description 16
- 239000003431 cross linking reagent Substances 0.000 claims description 14
- 239000010410 layer Substances 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000003504 photosensitizing agent Substances 0.000 claims description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 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
- 238000002834 transmittance Methods 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 239000004065 semiconductor Substances 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 239000011229 interlayer Substances 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 230000009477 glass transition Effects 0.000 claims description 3
- 239000010409 thin film Substances 0.000 claims description 3
- 230000004580 weight loss Effects 0.000 claims description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 2
- IYUOYLLVOZNGKW-UHFFFAOYSA-N 2-azidonaphthalene-1,4-dione Chemical group C1=CC=C2C(=O)C(N=[N+]=[N-])=CC(=O)C2=C1 IYUOYLLVOZNGKW-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 238000012546 transfer Methods 0.000 claims description 2
- -1 siloxane structure Chemical group 0.000 abstract description 20
- 238000001723 curing Methods 0.000 abstract description 12
- 239000000758 substrate Substances 0.000 abstract description 9
- 238000013035 low temperature curing Methods 0.000 abstract description 6
- 125000003118 aryl group Chemical group 0.000 abstract description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011737 fluorine Substances 0.000 abstract description 4
- 125000001424 substituent group Chemical group 0.000 abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- 230000015572 biosynthetic process Effects 0.000 description 20
- 238000003786 synthesis reaction Methods 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 150000004985 diamines Chemical class 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000009413 insulation Methods 0.000 description 6
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229920001721 polyimide Polymers 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- 239000004642 Polyimide Substances 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- YQNRVGJCPCNMKT-LFVJCYFKSA-N 2-[(e)-[[2-(4-benzylpiperazin-1-ium-1-yl)acetyl]hydrazinylidene]methyl]-6-prop-2-enylphenolate Chemical compound [O-]C1=C(CC=C)C=CC=C1\C=N\NC(=O)C[NH+]1CCN(CC=2C=CC=CC=2)CC1 YQNRVGJCPCNMKT-LFVJCYFKSA-N 0.000 description 3
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 3
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- 101000838335 Homo sapiens Dual specificity protein phosphatase 2 Proteins 0.000 description 3
- 101001080401 Homo sapiens Proteasome assembly chaperone 1 Proteins 0.000 description 3
- 101001104570 Homo sapiens Proteasome assembly chaperone 2 Proteins 0.000 description 3
- 229960005552 PAC-1 Drugs 0.000 description 3
- 102100027583 Proteasome assembly chaperone 1 Human genes 0.000 description 3
- 102100041008 Proteasome assembly chaperone 2 Human genes 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
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- 239000007787 solid Substances 0.000 description 3
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- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- XROLBZOMVNMIFN-UHFFFAOYSA-N 1-(1-benzofuran-4-yl)propan-2-amine Chemical compound CC(N)CC1=CC=CC2=C1C=CO2 XROLBZOMVNMIFN-UHFFFAOYSA-N 0.000 description 2
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 2
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- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical group FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 description 2
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- 239000003513 alkali Substances 0.000 description 1
- ZIXLDMFVRPABBX-UHFFFAOYSA-N alpha-methylcyclopentanone Natural products CC1CCCC1=O ZIXLDMFVRPABBX-UHFFFAOYSA-N 0.000 description 1
- LBDSXVIYZYSRII-IGMARMGPSA-N alpha-particle Chemical compound [4He+2] LBDSXVIYZYSRII-IGMARMGPSA-N 0.000 description 1
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 1
- 239000001191 butyl (2R)-2-hydroxypropanoate Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- DMEXFOUCEOWRGD-UHFFFAOYSA-N chloro-[chloro(dimethyl)silyl]oxy-dimethylsilane Chemical compound C[Si](C)(Cl)O[Si](C)(C)Cl DMEXFOUCEOWRGD-UHFFFAOYSA-N 0.000 description 1
- DDYAZDRFUVZBMM-UHFFFAOYSA-N chloro-[chloro-di(propan-2-yl)silyl]oxy-di(propan-2-yl)silane Chemical compound CC(C)[Si](Cl)(C(C)C)O[Si](Cl)(C(C)C)C(C)C DDYAZDRFUVZBMM-UHFFFAOYSA-N 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- RZIPTXDCNDIINL-UHFFFAOYSA-N cyclohexane-1,1,2,2-tetracarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCCC1(C(O)=O)C(O)=O RZIPTXDCNDIINL-UHFFFAOYSA-N 0.000 description 1
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009459 flexible packaging Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical group NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229940057867 methyl lactate Drugs 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- ILVGAIQLOCKNQA-UHFFFAOYSA-N propyl 2-hydroxypropanoate Chemical compound CCCOC(=O)C(C)O ILVGAIQLOCKNQA-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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
- G03F7/075—Silicon-containing compounds
- G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Definitions
- the invention relates to the technical field of polymer materials, and in particular to an alkali-soluble resin, a photosensitive resin composition and a photosensitive cured film.
- Polyimide due to its unique aromatic ring conjugation and imide ring structure, has good heat resistance, high insulation, chemical resistance and good mechanical properties, and is widely used in surface passivation layers, stress buffer layers and interlayer insulation layers of semiconductor devices; it also has important application value in signal line distribution, ⁇ -particle shielding layers, micro-solder ball processes, stress buffer layers of plastic-sealed circuits, flexible packaging substrates, etc. in semiconductor advanced packaging (BGA, CSP, SiP, WLP, etc.); at the same time, in display devices such as organic EL display devices or liquid crystal display devices, photosensitive polyimide resins are widely used in the flat layer and pixel definition layer of the display device to improve interlayer insulation and reduce display color difference.
- the present invention provides an alkali-soluble resin, a photosensitive resin composition and a photosensitive cured film, which are used to solve the defects of the prior art such as poor adhesion to a substrate, high dielectric constant, poor transparency and high curing temperature, and achieve good adhesion to a substrate, dielectric constant, transparency, heat resistance and low-temperature curing characteristics.
- the present invention provides an alkali-soluble resin having a structure shown in general formula (1):
- Ar 1 represents a dianhydride residue
- R 1 represents an organic group having 1 to 10 H or C atoms
- m is an integer of 10 to 10000
- r is an integer of 0 to 2;
- Ar 2 represents a diamine residue, wherein the diamine residue comprises at least two structural units, one of which is as shown in the general formula (2);
- R 2 represents one of H, F, and a fluorinated alkane having 1 to 3 carbon atoms
- R 3 represents a single bond or an alkylene having 1 to 10 carbon atoms
- R 4 , R 5 , R 6 and R 7 each independently represent one of an alkyl having 1 to 6 carbon atoms, a phenyl group, a fluorinated or CF 3 -substituted phenyl group
- n is an integer of 0 to 10;
- Ar 1 and Ar 2 contain at least one phenolic hydroxyl group.
- the present invention introduces a structural unit represented by the general formula (2) into the alkali-soluble resin structure, including a siloxane structure, an aromatic structure and, in some selected cases, a fluorine-containing substituent structure, so that when applied to a photosensitive resin composition, good adhesion to a substrate and good transparency can be achieved, while ensuring good heat resistance and low-temperature curing characteristics after curing.
- a structural unit represented by the general formula (2) into the alkali-soluble resin structure, including a siloxane structure, an aromatic structure and, in some selected cases, a fluorine-containing substituent structure, so that when applied to a photosensitive resin composition, good adhesion to a substrate and good transparency can be achieved, while ensuring good heat resistance and low-temperature curing characteristics after curing.
- the alkali-soluble resin is polyamic acid soluble in alkaline aqueous solution; when R1 represents an organic group with 1 to 10 C atoms, the alkali-soluble resin is polyamide ester soluble in alkaline aqueous solution, and preferably, the organic group is an alkyl group.
- the dianhydride residue refers to a residue obtained by removing two anhydride groups from a dianhydride.
- the dianhydride includes but is not limited to the following dianhydrides, such as pyromellitic dianhydride (PMDA), 3,3,3',4'-biphenyltetracarboxylic dianhydride (s-BPDA), 2,3,3',4'-biphenyltetracarboxylic dianhydride ( ⁇ -BPDA), 4,4'-oxydiphthalic anhydride (ODPA), 4,4'-(hexafluoroisopropylene) diphthalic anhydride (6FDA), 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA), p-phenylene-triphenylene dianhydride (TAHQ), 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride (BSDA), cyclobutane
- the diamine residue refers to a residue obtained by removing two amino groups from a diamine.
- the diamine includes but is not limited to a diamine represented by two amino groups connected by the general formula (2) and other hydroxyl-containing diamines and hydroxyl-free diamines, such as 2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis[3-(4-aminobenzamide)-4-hydroxyphenyl]propane, 2,2-bis[3-(4-aminobenzamide)-4-hydroxyphenyl]sulfone, 2,2-bis[3-(4-aminobenzamide)-4-hydroxyphenyl]ether, 2,2-bis[3-(4-aminobenzamide)-4-hydroxyphenyl]hexafluoropropane, N-(2-hydroxyphenyl)propane, and N-(2-hydroxyphenyl)propane.
- Ar 1 and Ar 2 contain at least one phenolic hydroxyl group, including the following three situations: (1) the dianhydride residue represented by Ar 1 contains at least one phenolic hydroxyl group, and the diamine residue represented by Ar 2 does not contain a phenolic hydroxyl group; (2) the diamine residue represented by Ar 2 contains at least one phenolic hydroxyl group, and the dianhydride residue represented by Ar 1 does not contain a phenolic hydroxyl group; (3) both the dianhydride residue represented by Ar 1 and the diamine residue represented by Ar 2 contain a phenolic hydroxyl group.
- at least one of the raw material monomers of the dianhydride and diamine used is a phenolic hydroxyl group-containing structure.
- the diamine represented by two amino groups connected at both ends of the general formula (2) does not contain a phenolic hydroxyl group.
- the raw material dianhydride used does not contain a phenolic hydroxyl group
- the other diamine used must contain a phenolic hydroxyl group.
- the present invention has found through research that when the general formula (1) contains a phenolic hydroxyl group, the alkali solubility of the obtained alkali-soluble resin is better.
- the preparation method of the alkali-soluble resin of the present invention comprises the following steps:
- silane diamine, other diamines, dianhydride and other materials are successively dissolved in an organic solvent, and a polymerization reaction is performed to obtain a polyimide precursor solution with a solid content of 10 to 50%;
- the structural unit represented by the general formula (2) accounts for 0.5% to 20% of the total weight of the diamine residues.
- the present invention has found that the higher the specific gravity of the structural unit represented by the general formula (2), the better. When the specific gravity exceeds 20%, the thermal performance is greatly damaged, while when the specific gravity is too low, the improvement effect is not significant.
- the structural unit represented by the general formula (2) is selected from one or more of the following:
- the present invention provides a photosensitive resin composition, comprising (a) an alkali-soluble resin, (b) a photosensitizer, (c) a cross-linking agent and (d) a solvent, wherein the (a) alkali-soluble resin comprises any one of the above-mentioned alkali-soluble resins.
- the amount of photosensitizer (b) is 0.05 to 50 parts
- the amount of crosslinking agent (c) is 1 to 50 parts
- the amount of solvent (d) is appropriately selected according to the solid content of 5 to 40%.
- the (b) photosensitizer is a naphthoquinone azide photosensitizer.
- the naphthoquinone azido type photosensitizer is an esterification product of a phenolic hydroxyl compound and naphthoquinone azido sulfonyl chloride.
- the phenolic hydroxyl compound is selected from one or more of Bis-Z, BisP-EZ, BisOPP-Z, BisP-CP, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, Tris-PHBA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, and BisP-PZ (trade names, manufactured by Honshu Chemical Industry Co., Ltd.).
- the crosslinking agent (c) has no special requirements, and can be a heat-crosslinking compound that can undergo a crosslinking reaction with the alkali-soluble resin.
- the crosslinking agent (c) can be selected from one or more of epoxy compounds, alkoxymethylol compounds, and alkoxymethylol triazine ring compounds; the functionality of the crosslinking agent (c) is greater than or equal to 2.
- the epoxy compound is selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, and propylene glycol diglycidyl ether.
- the alkoxymethylol compound is selected from polyalkoxymethylolated phenolic hydroxyl compounds, wherein the phenolic hydroxyl compound is selected from one or more of Bis-Z, BisP-EZ, BisOPP-Z, BisP-CP, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, Tris-PHBA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, and BisP-PZ (trade names, manufactured by Honshu Chemical Industry Co., Ltd.).
- the alkoxy hydroxymethyl triazine ring compound is selected from one or more compounds represented by general formula (3);
- R 8 and R 9 each independently represent H, CH 2 OCH 3 or CH 2 OCH 2 CH 3 , and not all of them are H.
- the (d) solvent is one or more of ketone solvents, ester solvents, ether solvents, aromatic hydrocarbon solvents and other solvents.
- the ketone solvent is one of acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone.
- the ester solvent is one or more of ethyl acetate, butyl acetate, n-propyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, propylene glycol methyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate and gamma-butyrolactone.
- the ether solvent is one or more of propylene glycol methyl ether, propylene glycol monoethyl ether and ethylene glycol monomethyl ether.
- the aromatic hydrocarbon solvent may be one or more of toluene and xylene.
- the other solvents are one or more of N-methylpyrrolidone, tetrahydrofuran, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide.
- the present invention provides a photosensitive cured film formed by curing any one of the above-mentioned photosensitive resin compositions.
- the curing of the above-mentioned photosensitive resin composition to form a cured film generally includes some pre-treatments, such as coating, hot plate drying, exposure, and development before curing. Among them, each step adopts conventional operation means in the art. For example, a rotational viscometer is used for coating, hot plate drying is used for drying, and curing is performed by heat curing under nitrogen.
- the adhesion of the photosensitive cured film is tested by the Baige method, and the transfer area is ⁇ 10%; the transmittance at 400nm is greater than 85%; the dielectric constant Dk is ⁇ 3.0, the glass transition temperature Tg is less than 300°C, and the thermal weight loss temperature T5% is greater than 350°C.
- the above performance test results indicate that the photosensitive cured film obtained by the present invention has good adhesion, excellent light transmittance, low dielectric properties and good heat resistance.
- the photosensitive cured film is suitable for use as a surface protective film and an interlayer insulating film of a semiconductor element, an insulating layer of an organic electroluminescent element, and an insulating layer of a thin film transistor.
- the present invention provides an alkali-soluble resin, a photosensitive resin composition and a photosensitive cured film.
- a structural unit represented by the general formula (2) into the alkali-soluble resin structure, wherein the structural unit comprises a siloxane structure, an aromatic structure and/or a fluorine-containing substituent structure, the photosensitive resin composition can achieve good adhesion to a substrate and good transparency when used to form a cured film, while ensuring good heat resistance and low-temperature curing characteristics after curing.
- the raw materials mentioned above can be obtained from public commercial channels.
- TrisP-HAP 1,1,1-tris(4-hydroxyphenyl)ethane
- MAP and SM-B in Synthesis Example 1 were replaced by 2-trifluoromethyl-5-aminophenol, 2-trifluoromethyl-4-aminophenol, 2-trifluoromethyl-4-aminophenylbutanol, dimethyldichlorosilane, 1,1,3,3-tetramethyl-1,3-dichloro-disiloxane, 1,1,3,5,7,7-hexamethyl-3,5-(2-trifluoromethyl)phenyl-1,7-dichloro-tetrasiloxane and other raw materials, and silanediamines 2-2, 2-3, 2-4, 2-5 and 2-6 were prepared respectively by a similar synthesis method.
- the reaction vessel was vented with nitrogen in advance. After 30 minutes, 260 g of dioxane (water was removed with molecular sieves 24 hours in advance), 10.60 g (0.025 mol) of TrisP-PA (trade name, made by Honshu Chemical) and 20.1 g (0.075 mol) of naphthoquinone azidosulfonyl chloride were added respectively, and a mixed solution of triethylamine (6.3 g)-dioxane (20 g) was slowly added dropwise. The temperature was controlled at 30 °C. After the addition is completed, keep warm at 30°C for 2h; filter, wash with deionized water 3 times, and rinse with dilute hydrochloric acid and deionized water 3 times respectively, and dry in vacuum at 60°C for 24h.
- TrisP-PA trade name, made by Honshu Chemical
- the photosensitizer PAC-2 was prepared by a similar synthesis method to that in Synthesis Example 2, except that TrisP-PA (trade name, manufactured by Honshu Chemical) was replaced by Trisp-HAP (trade name, manufactured by Honshu Chemical).
- the dried white product was further reacted with methanol at room temperature for 24 hours, and the methanol was removed by distillation under reduced pressure to obtain the cross-linking agent C-1.
- Crosslinking agent C-2 was prepared by a similar synthesis method to that in Synthesis Example 4 except that Trisp-HAP (trade name, manufactured by Honshu Chemical) was replaced with melamine.
- the reaction vessel was vented with nitrogen in advance. After 30 minutes, 156.6 g of N-methylpyrrolidone (NMP, water was removed by molecular sieve 24 hours in advance) was added, and then 4.61 g (0.01 mol) of compound 2-1 and 29.30 g (0.08 mol) of compound 6FAP were added respectively, and stirred at 25°C until completely dissolved; then 31.02 g (0.1 mmol) of compound ODPA was added, and the reaction was stirred at room temperature for 12 hours, and 2.18 g (0.02 mol) of MAP was added, and the reaction was kept warm for 12 hours; 36.80 g of DMFDEA was added, the temperature was raised to 40°C, and the temperature was kept warm for 4 hours;
- NMP N-methylpyrrolidone
- the diamine and dianhydride were replaced with the ratios shown in Table 1 below, and resin polymerization was performed, followed by precipitation and purification; and the corresponding alkali-soluble resins A-2 to A-8 were obtained.
- alkali-soluble resins A-2 to A-4 were used to replace alkali-soluble resin A-1, respectively, and the photosensitive resin compositions were prepared in the same manner as in Example 1.
- alkali-soluble resins A-5 and A-6 are used to replace alkali-soluble resin A-1, photosensitive agent PAC-1 is replaced by PAC-2, and crosslinking agent C-1 is replaced by C-2.
- Photosensitive resin compositions are prepared in the same manner as in Example 1.
- Comparative Example 1 Alkali-soluble resin A-7 was used to replace alkali-soluble resin A-1, and a photosensitive resin composition was prepared in the same manner as in Example 1.
- Comparative Example 2 Alkali-soluble resin A-8 was used to replace alkali-soluble resin A-1, and a photosensitive resin composition was prepared in the same manner as in Example 1.
- Preparation of photosensitive curing film wet film coating was performed using a rotational viscometer (Mikasa: MS-B150+DA-60S), pre-dried on a hot plate at 120°C for 3 minutes, and then transferred to a nitrogen drying oven for further curing after exposure and development, cured at 150/200/250°C for 30min/30min/60min respectively, and then cooled to room temperature and taken out.
- a rotational viscometer Melt film coating was performed using a rotational viscometer (Mikasa: MS-B150+DA-60S), pre-dried on a hot plate at 120°C for 3 minutes, and then transferred to a nitrogen drying oven for further curing after exposure and development, cured at 150/200/250°C for 30min/30min/60min respectively, and then cooled to room temperature and taken out.
- Adhesion was evaluated by a 100-grid test. A grid was made on the surface of the cured film at 1 mm intervals in 10 rows and 10 columns. The film was transferred using an adhesive tape. The adhesion between the cured film and the substrate was evaluated based on the size of the transferred area. ⁇ 10% was recorded as A; >10% and ⁇ 20% was recorded as B; >20% was recorded as C.
- thermomechanical analyzer TAI-Tietrachlorostyrene, Model Q400. Atmosphere: nitrogen atmosphere; Temperature: heating rate: 10°C/min.
- the thermal decomposition temperature was measured using a thermogravimetric analyzer (model TGA-55), with a heating rate of 10°C/min and a sample size of 3 to 5 mg; Temperature range: RT ⁇ 500°C.
- the test was carried out using a Keysight N5224B vector network analyzer (cavity resonator method) with a test frequency of 10 GHz and a sample size of 6*6 cm.
- the alkali-soluble resin provided by the present invention can achieve good adhesion to the substrate and good transparency when applied to the photosensitive resin composition by introducing a siloxane structure, an aromatic structure and/or a fluorine-containing and its substituent structure into the alkali-soluble resin structure; at the same time, it ensures good heat resistance and low-temperature curing characteristics after curing.
- the photosensitive resin composition after being coated with a rotational viscometer, dried on a hot plate, exposed, developed and thermally cured under nitrogen, exhibits good adhesion, excellent light transmittance, low dielectric properties and good heat resistance; the adhesion test is A; the light transmittance at 400nm is greater than 85%; Dk ⁇ 3.0, Tg ⁇ 300°C, T5%>350°C. It is suitable for surface protection films and interlayer insulation films of semiconductor elements, insulation layers of organic electroluminescent elements and insulation layers of thin film transistors (TFTs).
- TFTs thin film transistors
- the addition ratio of the siloxane diamine monomer that is, the ratio of the general formula (2) to Ar 2 .
- the ratio is too low, the adhesion improvement effect is minimal; when the ratio is too high, the thermal performance is greatly damaged; when F/CF 3 and other structures are appropriately introduced, the dielectric properties and transmittance can be effectively improved; and the influence of the exposure process on the sensitivity can be reduced.
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Abstract
一种碱溶性树脂、感光性树脂组合物和感光性固化膜,碱溶性树脂具有通式(1)所示结构,其中,Ar 1表示二酐残基;R 1表示H或C原子个数为1~10的有机基团;m为10~10000的整数,r为0~2的整数;Ar 2表示二胺残基,二胺残基包括至少两种结构单元,其中一种结构单元如通式(2)所示;且Ar 1和Ar 2中至少含一个酚羟基。通过向碱溶性树脂结构中引入通式(2)所示的结构单元,其中包括硅氧烷结构、芳香结构和/或含氟取代基结构,可实现应用于感光树脂组合物形成固化膜时,与基底之间良好的粘接性,以及良好的透明性,同时保证了固化后良好的耐热性以及低温固化特性。
Description
交叉引用
本申请要求2022年10月20日提交的专利名称为“碱溶性树脂、感光性树脂组合物和感光性固化膜”的第202211283494.X号中国专利申请的优先权,其全部公开内容通过引用整体并入本文。
本发明涉及高分子材料技术领域,尤其涉及一种碱溶性树脂、感光性树脂组合物和感光性固化膜。
聚酰亚胺因其特有的芳环共轭以及酰亚胺环结构,体现出了良好的耐热性、高绝缘性、耐化学品性以及良好的机械性能,广泛应用于半导体器件的表面钝化层、应力缓冲层以及层间绝缘层;在半导体先进封装(BGA、CSP、SiP、WLP等)的信号线分配、α-粒子屏蔽层、微焊球工艺、塑封电路的应力缓冲层、柔性封装基板等方面同样具有重要的应用价值;同时在有机EL显示装置或液晶显示装置等显示装置中,光敏聚酰亚胺树脂广泛应用于显示装置的平坦层和像素定义层,以提高层间绝缘性和减少显示色差。
随着微电子产品的小型化、精密化和多功能化发展,对材料本身性能如介电性能、光学性能、热性能以及低温固化特性等提出了更高的要求;但聚酰亚胺因其共轭结构及酰亚胺结构的存在,导致其本身吸水率较高、介电性能较差;同时存在与基板粘附性差、透明性差以及固化温度高等缺点,极大地限制了光敏聚酰亚胺材料在半导体领域和显示领域的发展。
发明内容
本发明提供一种碱溶性树脂、感光性树脂组合物和感光性固化膜,用以解决现有技术中与基板粘附性差、介电常数高、透明性差以及固化温度高等缺陷,实现与基底之间良好的粘接性、介电常数、透明性、耐热性以及低温固化特性。
第一方面,本发明提供一种碱溶性树脂,具有通式(1)所示结构:
其中,Ar1表示二酐残基;R1表示H或C原子个数为1~10的有机基团;m为10~10000的整数,r为0~2的整数;
Ar2表示二胺残基,所述二胺残基包括至少两种结构单元,其中一种结构单元如通式(2)所示;
其中,R2表示H、F、C原子个数为1~3的氟代烷烃中的一种;R3表示单键或C原子个数为1~10的亚烷基;R4、R5、R6和R7分别独立地表示C原子个数为1~6的烷基、苯基、氟代或CF3-取代的苯基中的一种;n为0~10的整数;
且Ar1和Ar2中至少含一个酚羟基。
本发明通过向碱溶性树脂结构中引入通式(2)所示的结构单元,其中包括硅氧烷结构、芳香结构以及某些选择下包括含氟取代基结构,可实现应用于感光树脂组合物时,与基底之间良好的粘接性,以及良好的透明性,同时保证了固化后良好的耐热性以及低温固化特性。
需要说明的是,当R1表示H时,所述碱溶性树脂为碱性水溶液可溶的聚酰胺酸;当R1表示C原子个数为1~10的有机基团时,所述碱溶性树脂为碱性水溶液可溶的聚酰胺酯,优选地,所述有机基团为烷基。
所述二酐残基指从二酐中除去2个酸酐基团而得的残基。所述二酐,包含但不仅限于以下二酐,如均苯四甲酸二酐(PMDA)、3,3,3',4'-联苯四羧酸二酐(s-BPDA)、2,3,3',4'-联苯四羧酸二酐(α-BPDA)、4,4’-氧双邻苯二甲酸酐(ODPA)、4,4'-(六氟异丙烯)二酞酸酐(6FDA)、3,3',4,4'-二苯甲酮四甲酸二酐(BTDA)、对-亚苯基-双苯偏三酸酯二酐(TAHQ)、3,3',4,4'-二苯甲砜四甲酸二酐(BSDA)、环丁烷四羧酸二酐(CBDA)、环己烷四羧酸二酐(HPMDA)、N,N'-[2,2,2-三氟-1-(三氟甲基)亚乙基]双(6-羟基-3,1-亚苯基)]双(1,3-二氧基-1,3-二氢异苯并呋喃-5-甲酰胺)(6FAP-ATA)和N-[5-[3-[(1,3-二氧基-2-苯并呋喃-5-羰基)氨基]-4-羟基苯基]磺酰基-2-羟基苯基]-1,3-二氧基-2-苯并呋喃-5-甲酰胺(6FAP-ASA)中的一种或多种。
所述二胺残基指从二胺中除去两个氨基而得的残基。所述二胺,包含但不仅限于通式(2)连接两个氨基表示的二胺以及其他含羟基二胺和不含羟基二胺,含羟基二胺如2’-双(3-氨基-4-羟基苯基)六氟丙烷、2,2-双[3-(4-氨基苯甲酰胺基)-4-羟基苯基]丙烷、2,2-双[3-(4-氨基苯甲酰胺基)-4-羟基苯基]砜基、2,2-双[3-(4-氨基苯甲酰胺基)-4-羟基苯基]醚基、2,2-双[3-(4-氨基苯甲酰胺基)-4-羟基苯基]六氟丙烷、N-(2-羟基-5-氨基)苯基-3-氨基苯甲酰胺、N-(5-氨基-2-羟基苯基)-4-[2-[4-[(4-氨基苯基)氨甲酰]苯基]-丙烷-2-基]苯甲酰胺、N-(5-氨基-2-羟基苯基)-4-[2-[4-[(4-氨基苯基)氨甲酰]苯基]-砜基-2-基]苯甲酰胺、N-(5-氨基-2-羟基苯基)-4-[2-[4-[(4-氨基苯基)氨甲酰]苯基]-醚基-2-基]苯甲酰胺和N-(5-氨基-2-羟基苯基)-4-[2-[4-[(4-氨基苯基)氨甲酰]苯基]-六氟丙烷-2-基]苯甲酰胺中的一种或多种;不含羟基二胺如1,4-对苯二胺(PDA)、间苯二胺(m-PDA)、邻苯二胺(o-PDA)、4,4'-二胺基二苯醚(ODA)、4,4’-二氨基-对三联苯(DATP)、4,4’-二氨基二苯甲烷(MDA)、和2,2'-二甲基-4,4'-二氨基联苯(m-TB)、对氨基苯甲酸对氨基苯酯(APAB)、1,4-双(4’-氨基苯氧基)苯(1,4,4-APB)、1,3,4-APB:1,3-双(4’-氨基苯氧基)苯(1,3,4-APB)、1,3-双(3’-氨基苯氧基)苯(1,3,3-APB)、2,2-双(4-(4-氨基苯氧基)苯基)丙烷(BAPP)、2,2’-双(三氟甲基)-4,4’-二氨基二苯醚(6FODA)、2,2’-双(三氟甲基)-4,4’-二氨基联苯(TFMB)、2,2-双[4-(4-氨基苯氧基)苯基]六氟丙烷(HFBAPP)中的一种或多种。
Ar1和Ar2中至少含一个酚羟基,包括以下三种情况:(1)Ar1表示的二酐残基中含有至少一个酚羟基,Ar2表示的二胺残基中不含酚羟基;(2)Ar2表示的二胺残基中含有至少一个酚羟基,Ar1表示的二酐残基中不含酚羟基;(3)Ar1表示的二酐残基和Ar2表示的二胺残基中均含有酚羟基。质言之,采用的原料二酐和二胺中,至少有一种原料单体为含酚羟基结构。其中,通式(2)两端连接两个氨基表示的二胺不含酚羟基,则当采用的原料二酐不含酚羟基时,采用的其他二胺必然含有酚羟基。
本发明经过研究发现,当通式(1)中含有酚羟基时,所得碱溶性树脂的碱溶性较好。
本发明所述碱溶性树脂的制备方法包括如下步骤:
(1)根据自设计结构和工艺制取所需硅烷二胺(通式(2)两端连接两个氨基表示的二胺),经提纯等后处理后备用;
(2)惰性气体保护下,将硅烷二胺、其他二胺与二酐等物料先后溶于有机溶剂中,聚合反应得到固体含量为10~50%的聚酰亚胺前驱体溶液;
(3)利用沉淀剂进行树脂沉淀,经过滤、洗涤和干燥后得到目标碱溶性树脂。
根据本发明提供的碱溶性树脂,所述通式(2)所示结构单元占所述二胺残基总比重的0.5%~20%。
本发明研究发现,通式(2)所示结构单元并非比重越高越好,当超过20%,则对热性能破坏较大,过低则改善作用不显著。
根据本发明提供的碱溶性树脂,所述通式(2)所示结构单元选自以下的一种或多种:
第二方面,本发明提供一种感光性树脂组合物,包括(a)碱溶性树脂、(b)感光剂、(c)交联剂和(d)溶剂,所述(a)碱溶性树脂包括上述任一种碱溶性树脂。
其中,相对100份碱溶性树脂(a),感光剂(b)用量为0.05~50份,交联剂(c)用量为1~50份,溶剂(d)用量根据固含5~40%进行适当选择。
根据本发明提供的感光性树脂组合物,所述(b)感光剂为叠氮萘醌型感光剂。
所述叠氮萘醌型感光剂为含酚羟基化合物与叠氮萘醌磺酰氯的酯化结合产物。其中,所述含酚羟基化合物选自Bis-Z、BisP-EZ、BisOPP-Z、BisP-CP、BisP-EZ、TekP-4HBPA、TrisP-HAP、TrisP-PA、Tris-PHBA、TrisP-SA、TrisOCR-PA、BisOCHP-Z、BisP-MZ、BisP-PZ(商品名,本州化学工业(株)制)中的一种或多种。
根据本发明提供的感光性树脂组合物,所述(c)交联剂无特殊要求,为可与所述碱溶性树脂进行交联反应的热交联性化合物即可。具体地,所述(c)交联剂可选自环氧基类化合物、烷氧基羟甲基化合物、烷氧基羟甲基三嗪环化合物中的一种或多种;所述(c)交联剂的官能度大于等于2。
其中,所述环氧基类化合物选自双酚A型环氧树脂、双酚F型环氧树脂、丙二醇二缩水甘油醚中的一种或多种。
所述烷氧基羟甲基化合物选自多烷氧基羟甲基化酚羟基化合物,其中酚羟基化合物选自Bis-Z、BisP-EZ、BisOPP-Z、BisP-CP、BisP-EZ、TekP-4HBPA、TrisP-HAP、TrisP-PA、Tris-PHBA、TrisP-SA、TrisOCR-PA、BisOCHP-Z、BisP-MZ、BisP-PZ(商品名,本州化学工业(株)制)中的一种或多种。
所述烷氧基羟甲基三嗪环化合物选自通式(3)所示化合物中的一种或多种;
其中,R8和R9分别独立地表示H、CH2OCH3或CH2OCH2CH3,且不全部为H。
根据本发明提供的感光性树脂组合物,所述(d)溶剂为酮类溶剂、酯类溶剂、醚类溶剂、芳香烃类溶剂和其他溶剂中的一种或多种。
示例性但非限制性地,所述酮类溶剂为丙酮、甲基乙基酮、甲基丙基酮、甲基异丁基酮、环戊酮、环己酮中的一种。
所述酯类溶剂为乙酸乙酯、乙酸丁酯、乙酸正丙酯、乳酸甲酯、乳酸乙酯、乳酸丙酯、乳酸丁酯、丙二醇甲醚醋酸酯、乙二醇单甲醚醋酸酯、乙二醇单乙醚醋酸酯和γ-丁内酯中的一种或多种。
所述醚类溶剂为丙二醇甲醚、丙二醇单乙醚、乙二醇单甲醚中的一种或多种。
所述芳香烃类溶剂可以是甲苯、二甲苯中的一种或多种。
所述其他溶剂为N-甲基吡咯烷酮、四氢呋喃、二氧杂环己烷、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲基亚砜中的一种或多种。
第三方面,本发明提供一种感光性固化膜,由上述任一种感光性树脂组合物固化形成。
本领域技术人员可以理解的是,上述感光性树脂组合物固化形成固化膜,通常还包括一些前置处理,常规的如经过涂布、热板烘干、曝光、显影后再进行固化。其中,各步骤采取本领域常规操作手段。例如采用旋转黏度计进行涂布,烘干采取热板烘干,固化为在氮气下进行热固化。
根据本发明提供的感光性固化膜,所述感光性固化膜采用百格法测试粘附性,转印面积≤10%;400nm下透光率>85%;介电常数Dk≤3.0,玻璃化转变温度Tg<300℃,热失重温度T5%>350℃。
上述性能测试结果说明本发明得到的感光性固化膜具有良好的粘附性、优异的透光性、低介电性能和良好的耐热性。
根据本发明提供的感光性固化膜,所述感光性固化膜适用于半导体元件的表面保护膜和层间绝缘膜、有机场致发光元件的绝缘层和薄膜晶体管的绝缘层。
本发明提供一种碱溶性树脂、感光性树脂组合物和感光性固化膜,通过向碱溶性树脂结构中引入通式(2)所示的结构单元,其中包括硅氧烷结构、芳香结构和/或包括含氟取代基结构,可实现应用于感光树脂组合物形成固化膜时,与基底之间良好的粘接性,以及良好的透明性,同时保证了固化后良好的耐热性以及低温固化特性。
为使本发明的目的、技术方案和优点更加清楚,下面将对本发明中的技术方案进行清楚、完整地描述,显然,所描述的实施例是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
若无特别说明,所述原材料均能从公开商业途径获得。
以下实施例中涉及化合物的缩写:
ODA:4,4'-二氨基二苯醚
ODPA:4,4’-氧双邻苯二甲酸酐
6FAP:2,2’-双(3-氨基-4-羟基苯基)六氟丙烷
DMFDEA:N,N’-二甲基甲酰胺二乙基缩醛
MAP:间氨基苯酚
Cbz-Cl:苯甲醚甲酰氯
SM-B:1,1,3,3-四异丙基-1,3-二氯-二硅氧醚
TrisP-HAP:1,1,1-三(4-羟基苯基)乙烷
合成例1硅烷二胺(2-1)的合成
3L玻璃反应瓶中,加入600mL四氢呋喃(THF),600ml水,300g间氨基苯酚,开启搅拌,降温至10℃,滴加539.3g Cbz-Cl,保温搅拌6h,1000ml水加入至反应液中,分液,乙酸乙酯(EA)萃取,饱和氯化钠溶液(Sat.NaCl)洗涤,加入无水硫酸钠干燥,抽滤,得到棕色固体,加入乙酸乙酯(EA)和正庚烷重结晶得到黄色中间体IM-A。
加入273.93g IM-A,166.17g三乙胺,1500ml甲苯,开启搅拌,加入148g SM-B,加热至60℃,保温搅拌8h,降温至10℃,搅拌过夜。抽滤,甲苯淋洗,减压浓缩得到棕黄色油状液体,柱层析分离提纯,得到黄色粘稠状油状物IM-B;
5L玻璃反应瓶中,加入312gIM-B,加入1000mlTHF,1500ml无水乙醇,开启搅拌,搅拌均匀,加入40g Pd/C(5%),加热升温至65℃,加入216g甲酸铵,控温70℃,保温搅拌2h,降温至10℃,1500ml水加入至反应液中,EA萃取,Sat.NaCl洗,无水硫酸钠干燥,抽滤,减压浓缩得棕黄色粘稠状油状物,柱层析分离提纯(洗脱剂EA:正庚烷=1:15)减压浓缩得到黄色粘稠状油状物(2-1);
通过2-三氟甲基-5-氨基苯酚、2-三氟甲基-4-氨基苯酚、2-三氟甲基-4-氨基苯基丁醇、二甲基二氯硅烷、1,1,3,3-四甲基-1,3-二氯-二硅氧醚、1,1,3,5,7,7-六甲基-3,5-(2-三氟甲基)苯基-1,7-二氯-四硅氧烷等原料分别替换合成例1中的MAP和SM-B,并采用类似合成方法分别制备了硅烷二胺2-2、2-3、2-4、2-5和2-6。
合成例2感光剂(PAC-1)的合成
提前使用氮气对反应容器进行排气,30min后,加入260g二氧六环(提前24h用分子筛除水),再分别加入10.60g(0.025mol)TrisP-PA(商品名,本州化学制)和20.1g(0.075mol)叠氮萘醌磺酰氯,缓慢滴加三乙胺(6.3g)-二氧六环(20g)混合溶液,温度控制在30℃以
内;滴加完成后30℃保温2h;过滤,去离子水洗涤3遍,并分别用稀盐酸和去离子水冲洗3遍,60℃真空干燥24h。
合成例3感光剂(PAC-2)的合成
将TrisP-PA(商品名,本州化学制)替换为Trisp-HAP(商品名,本州化学制),采用合成例2类似的合成方法制得感光剂PAC-2。
合成例4交联剂(C-1)的合成
提前使用氮气对反应容器进行排气,30min后,加入200g水,再分别加入20g(0.5mol)NaOH和25.8g(0.1mol)1,1,1-三(4-羟基苯基)乙烷,充分溶解后,缓慢滴加18eq当量的甲醛溶液,温度控制在20℃以内;滴加完成后20℃保温24h;加入硫酸和水中和得白色产物,去离子水洗涤3遍,50℃真空干燥72h;
将干燥后白色产物与甲醇进一步室温24h反应,减压蒸馏除去甲醇得交联剂C-1。
合成例5交联剂(C-2)的合成
将Trisp-HAP(商品名,本州化学制)替换为三聚氰胺,采用合成例4类似的合成方法制得交联剂C-2。
合成例6碱溶性树脂A-1的合成
提前使用氮气对反应容器进行排气,30min后,加入156.6gN-甲基吡咯烷酮(NMP,提前24h用分子筛除水),再分别加入4.61g(0.01mol)化合物2-1和29.30g(0.08mol)化合物6FAP,25℃下搅拌至完全溶解;再加入31.02g(0.1mmol)化合物ODPA,室温搅拌反应12h,加入MAP2.18g(0.02mol),保温反应12h;加入DMFDEA36.80g,升温至40℃,保温4h;
反应结束后,投入3L去离子水中,沉淀、过滤、洗涤三次;80℃真空干燥72h,得碱溶性树脂A-1。
合成例7~13碱溶性树脂A-2~A-8的合成
将二胺和二酐替换为下表1中所示的比例分别进行树脂聚合,沉淀提纯;分别制得相应的碱溶性树脂A-2~A-8。
表1
实施例1
分别将10g合成例6制得的碱溶性树脂A-1、3g合成例2制得的PAC-1和1g合成例4制得的交联剂C-1溶于γ-丁内酯30g中,充分混合均匀后制得感光性树脂组合物。
实施例2~4
实施例2~4分别取碱溶性树脂A-2~A-4替换碱溶性树脂A-1,按实施例1同样的方法配置得到感光性树脂组合物。
实施例5~6
实施例5~6分别取碱溶性树脂A-5~A-6替换碱溶性树脂A-1,感光剂PAC-1替换为PAC-2,交联剂C-1替换为C-2,按实施例1同样的方法配置得到感光性树脂组合物。
对比例1
对比例1取碱溶性树脂A-7替换碱溶性树脂A-1,按实施例1同样的方法配置得到感光性树脂组合物。
对比例2
对比例2取碱溶性树脂A-8替换碱溶性树脂A-1,按实施例1同样的方法配置得到感光性树脂组合物。
对各实施例和对比例中得到的感光性树脂组合物,按以下制作方法制得感光固化膜,并按以下所述的方法测量所得感光固化膜特性,其结果汇总于表2中。
感光固化膜的制作:利用旋转粘度计(Mikasa:MS-B150+DA-60S)进行湿膜涂布,热板120℃3min预烘干,再经曝光、显影后转移至氮气烘干进行进一步固化,150/200/250℃分别固化30min/30min/60min,降至室温取出。
(1)粘附性评价
采用百格测试方式进行粘附性评价,利用划格器按1mm间隔在固化膜表面进行10行10列划格,利用胶带进行转印,根据转印面积大小来评价固化膜与基板之间粘附性优良;其中≤10%记为A;>10%且≤20%记为B;>20%记为C。
(2)透光率(T%)
采用Agilent紫外可见分光光度计Cary4000,采用透射模式进行测试而得。
(3)玻璃化转变温度(Tg)
利用热机械分析仪(TAInstrument公司,型号Q400)测得的。气氛:氮气气氛下;温度:加热速率10℃/min。
(4)热失重温度(T5%)
采用热重分析仪(型号TGA-55)进行热分解温度测定,升温速率10℃/min,试样3~5mg;
温度区间R.T.~500℃。
(5)介电常数(Dk)&介电损耗(Df)
利用Keysight N5224B矢量网络分析仪(空腔共振器法)进行测试,测试频率10GHz,试样大小分别为6*6cm。
表2
由表2中的数据可以看出,本发明提供的碱溶性树脂,通过向碱溶性树脂结构中引入硅氧烷结构、芳香结构和/或含氟及其取代基结构,可实现应用于感光树脂组合物时,与基底之间良好的粘接性,以及良好的透明性;同时保证了固化后良好的耐热性以及低温固化特性。
所述感光性树脂组合物,经旋转黏度计涂布、热板烘干、曝光、显影和氮气下热固化后,感光性固化膜体现出了良好的粘附性、优异的透光性、低介电性能和良好的耐热性;粘附性测试为A;400nm下透光率>85%;Dk≤3.0,Tg<300℃,T5%>350℃。适用于半导体元件的表面保护膜和层间绝缘膜、有机场致发光元件的绝缘层和薄膜晶体管(TFT)的绝缘层。
但需控制硅氧烷二胺单体的添加比例,即通式(2)占Ar2的比例,比例过低时,对粘附性改善效果甚微;比例过高时,对热性能破坏较大;在适当引入F/CF3等结构时,可有效改善介电性能和透光率;减少曝光过程对感度的影响。
最后应说明的是:以上实施例仅用以说明本发明的技术方案,而非对其限制;尽管参照
前述实施例对本发明进行了详细的说明,本领域的普通技术人员应当理解:其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换;而这些修改或者替换,并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。
Claims (10)
- 一种碱溶性树脂,其特征在于,具有通式(1)所示结构:
其中,Ar1表示二酐残基;R1表示H或C原子个数为1~10的有机基团;m为10~10000的整数,r为0~2的整数;Ar2表示二胺残基,所述二胺残基包括至少两种结构单元,其中一种结构单元如通式(2)所示;
R2表示H、F、C原子个数为1~3的氟代烷烃中的一种;R3表示单键或C原子个数为1~10的亚烷基;R4、R5、R6和R7分别独立地表示C原子个数为1~6的烷基、苯基、氟代或CF3-取代的苯基中的一种;n为0~10的整数;且Ar1和Ar2中至少含一个酚羟基。 - 根据权利要求1所述的碱溶性树脂,其特征在于,所述通式(2)所示结构单元占所述二胺残基总比重的0.5%~20%。
- 根据权利要求2所述的碱溶性树脂,其特征在于,所述通式(2)所示结构单元选自以下的一种或多种:
- 一种感光性树脂组合物,其特征在于,包括(a)碱溶性树脂、(b)感光剂、(c)交联剂和(d)溶剂,所述(a)碱溶性树脂包括权利要求1-3任一项所述的碱溶性树脂。
- 根据权利要求4所述的感光性树脂组合物,其特征在于,所述(b)感光剂为叠氮萘醌型感光剂。
- 根据权利要求4所述的感光性树脂组合物,其特征在于,所述(c)交联剂选自环氧基类化合物、烷氧基羟甲基化合物、烷氧基羟甲基三嗪环化合物中的一种或多种;所述(c)交联剂的官能度大于等于2。
- 根据权利要求4所述的感光性树脂组合物,其特征在于,所述(d)溶剂为酮类溶剂、酯类溶剂、醚类溶剂、芳香烃类溶剂和其他溶剂中的一种或多种;所述其他溶剂为N-甲基吡咯烷酮、四氢呋喃、二氧杂环己烷、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲基亚砜中的一种或多种。
- 一种感光性固化膜,其特征在于,由权利要求4-7任一项所述的感光性树脂组合物固化形成。
- 根据权利要求8所述的感光性固化膜,其特征在于,所述感光性固化膜采用百格法测试粘附性,转印面积≤10%;400nm下透光率>85%;介电常数Dk≤3.0,玻璃化转变温度Tg<300℃,热失重温度T5%>350℃。
- 根据权利要求8所述的感光性固化膜,其特征在于,所述感光性固化膜适用于半导体元件的表面保护膜和层间绝缘膜、有机场致发光元件的绝缘层和薄膜晶体管的绝缘层。
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