CN100492173C - Coating composition of positive type photosensitive polyimide - Google Patents
Coating composition of positive type photosensitive polyimide Download PDFInfo
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- CN100492173C CN100492173C CNB2004100425205A CN200410042520A CN100492173C CN 100492173 C CN100492173 C CN 100492173C CN B2004100425205 A CNB2004100425205 A CN B2004100425205A CN 200410042520 A CN200410042520 A CN 200410042520A CN 100492173 C CN100492173 C CN 100492173C
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- 239000004642 Polyimide Substances 0.000 title claims abstract description 54
- 229920001721 polyimide Polymers 0.000 title claims abstract description 54
- 239000008199 coating composition Substances 0.000 title claims abstract description 19
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 206010034960 Photophobia Diseases 0.000 claims abstract description 9
- 208000013469 light sensitivity Diseases 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 29
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- -1 phenolic group compound Chemical class 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 claims 2
- 229940116333 ethyl lactate Drugs 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 6
- 238000009413 insulation Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- TZRXHJWUDPFEEY-UHFFFAOYSA-N Pentaerythritol Tetranitrate Chemical compound [O-][N+](=O)OCC(CO[N+]([O-])=O)(CO[N+]([O-])=O)CO[N+]([O-])=O TZRXHJWUDPFEEY-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 230000035945 sensitivity Effects 0.000 abstract description 2
- 239000004615 ingredient Substances 0.000 abstract 3
- 206010034972 Photosensitivity reaction Diseases 0.000 abstract 1
- 239000012670 alkaline solution Substances 0.000 abstract 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 abstract 1
- 239000003208 petroleum Substances 0.000 abstract 1
- 230000036211 photosensitivity Effects 0.000 abstract 1
- 150000004053 quinones Chemical class 0.000 abstract 1
- 230000001235 sensitizing effect Effects 0.000 abstract 1
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 22
- 150000002148 esters Chemical class 0.000 description 16
- 229920005575 poly(amic acid) Polymers 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- 238000000576 coating method Methods 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- 239000011521 glass Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 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 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 238000004528 spin coating Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000009435 amidation Effects 0.000 description 4
- 238000007112 amidation reaction Methods 0.000 description 4
- RKFCDGOVCBYSEW-AUUKWEANSA-N tmeg Chemical compound COC=1C(OC)=CC(C(OC(C=2OC)=C34)=O)=C3C=1OC(=O)C4=CC=2O[C@@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O RKFCDGOVCBYSEW-AUUKWEANSA-N 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-methyl-pyrrolidinone Natural products CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- IBDMRHDXAQZJAP-UHFFFAOYSA-N dichlorophosphorylbenzene Chemical compound ClP(Cl)(=O)C1=CC=CC=C1 IBDMRHDXAQZJAP-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- LNSXAHXVHYLJEG-UHFFFAOYSA-N ethyl 2-hydroxypropanoate;2-hydroxy-2-methylbutanoic acid Chemical compound CCOC(=O)C(C)O.CCC(C)(O)C(O)=O LNSXAHXVHYLJEG-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- KUMMBDBTERQYCG-UHFFFAOYSA-N 2,6-bis(hydroxymethyl)-4-methylphenol Chemical compound CC1=CC(CO)=C(O)C(CO)=C1 KUMMBDBTERQYCG-UHFFFAOYSA-N 0.000 description 1
- ZGDMDBHLKNQPSD-UHFFFAOYSA-N 2-amino-5-(4-amino-3-hydroxyphenyl)phenol Chemical compound C1=C(O)C(N)=CC=C1C1=CC=C(N)C(O)=C1 ZGDMDBHLKNQPSD-UHFFFAOYSA-N 0.000 description 1
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 description 1
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 1
- 229940018563 3-aminophenol Drugs 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- WTQZSMDDRMKJRI-UHFFFAOYSA-N 4-diazoniophenolate Chemical compound [O-]C1=CC=C([N+]#N)C=C1 WTQZSMDDRMKJRI-UHFFFAOYSA-N 0.000 description 1
- ILSXRXCHOQJQEU-UHFFFAOYSA-N 6-amino-5-phenylcyclohexa-2,4-diene-1,1-diol Chemical compound NC1C(=CC=CC1(O)O)C1=CC=CC=C1 ILSXRXCHOQJQEU-UHFFFAOYSA-N 0.000 description 1
- WYLIRYQDDKDHLT-UHFFFAOYSA-N CC1=CC=CC=C1C.CC1=CC=CC=C1C Chemical compound CC1=CC=CC=C1C.CC1=CC=CC=C1C WYLIRYQDDKDHLT-UHFFFAOYSA-N 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 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 1
- 239000002253 acid Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- ARCGXLSVLAOJQL-UHFFFAOYSA-N anhydrous trimellitic acid Natural products OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- BXEMXLDMNMKWPV-UHFFFAOYSA-N pyridine Chemical compound C1=CC=NC=C1.C1=CC=NC=C1 BXEMXLDMNMKWPV-UHFFFAOYSA-N 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
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- Materials For Photolithography (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The present invention relates to a polyimide coating composition with positive type photosensitivity, which comprises an organic solvent, (a) polyimide dissolved in the organic solvent, a phenolic groThe invention relates to a positive light sensitivity medlin layer material component which comprises organic solvent and its soluble (a) medlin with a phenol or carboxyl on its main chain end, (b) coup or a carboxyl group on the terminal of the main chain of the polyimide, (b) a compound of the phenolic group, and (c) quinones nitrine sulphonate used as a sensitizer, wherein the dosage of per 100mponent with a phenol, and (c) chinone nitrogen petroleum sulfonate as sensitizing agent with the element of relatively one hundred units (a), 1-50 weight units element (b), and 1-50 weight units elem parts by weight of the ingredient (a)and the ingredient (b) is 1 to 50 parts by weight, and the dosage of the ingredient (c) is 1 to 50 parts by weight. The polyimide with the positive type photosensent (c). The said positive light sensitivity medlin can be used in alkaline solution and in display's insulation layer. itivity can be developed by an alkaline water solution. The present invention has the advantages of high sensitivity, favorable resolution, low rigidity baking temperature, high conservation rate of the film thickness, and gradually narrow figures of the cross section, can be used as an insulating layer on a display and can be used for satisfying the requirement of special standards.
Description
Technical field
The invention relates to a kind of polyimide coating composition of positive light sensitivity, it can be used for forming the insulation course of a display.
Background technology
Polyimide (polyimide; PI) owing to have excellent thermostability and favorable mechanical; electric and chemical property; be widely used in semiconductor and display industry; IC chip protection film for example; wafer-level package (chip scale package, CSP) and the insulation course on the display (insulator) etc.Owing to use photosensitive polyimide (PSPI) can simplify processing procedure, reduce cost and can improve the product fine rate, be a kind of trend so use PSPI.
The pertinent literature of the polyimide of positive light sensitivity is very many, but mostly be the precursor such as the poly amic acid ester (polyamic acid ester) of polyimide greatly, such as in the patents such as US 6329110, US 6291619, US 6232032 and US 5858584 announcement.The pattern of poly amic acid ester after development is standard rectangular, but the demand of insulation course is the figure that the cross section is gradually narrow (tapered-angle at the cross section) in the display, and poly amic acid ester also needs to carry out inferior amidation (imidized) with 350 ℃ of high temperature at last, conflicts mutually with the process requirement that is lower than 250 ℃.Therefore also inapplicable with the made PSPI of poly amic acid ester.There are the PSPI such as the patents such as US 6627377, US 5441845, US 5573886 of inferior amidation (imidized) to disclose in addition, though its firmly roasting temperature can be lower, but it generally all is the PI of solvable type, so its solvent resistance is all generally relatively poor, and need to develop, so its practicality is lower with the alkaline-based developer of high concentration.
People such as Masao Tomikawa are in Journal of Photopolymer Science andTechnology, 2002,15,205~208, US 6593043 and US 6524764 are disclosed in main chain, and to import terminal groups be that the poly amic acid ester of phenolic group and compound that adding has phenolic group (phenolic hydroxyl group) are used as crosslinking chemical (crosslinking agent), can make pattern have the cross section to be the effect of gradually narrow (tapered-angle at the cross section), but the main structure of its poly amic acid ester is still and need high temperature can guarantee that just its inferior amidation is complete when inferior amidation (imidized).Point out to cause contraction (shrinkage) in US6524764 embodiment 6~13 when poly amic acid ester is converted into polyimide, so its thickness conservation rate of the PSPI that poly amic acid ester is formed also lower (66%), its synthesis step is also complicated.
Summary of the invention
A fundamental purpose of the present invention is to propose a kind of polyimide coating composition of novel positive light sensitivity, synthesis step is simple, available alkaline aqueous solution develops at short notice and finishes, has high sensitivity, good resolution, low hard roasting temperature, high thickness conservation rate, and its pattern has the shape that the cross section is gradually narrow (tapered-angle at the cross section) after sclerosis.Coating composition of the present invention at room temperature has excellent storage.
The polyimide coating composition of positive light sensitivity of the present invention comprises an organic solvent and is dissolved in (a) polyimide in this organic solvent, its main chain end has a phenolic group (phenolic hydroxyl group) or carboxyl (carboxyl group), (b) has the compound of phenolic group (phenolic hydroxyl group), and (c) as the quinone nitrine sulfonate (quinonediazide sulfonate) of emulsion, wherein with respect to the composition (a) of each hundred weight portion, the consumption of composition (b) is 1~50 weight portion, 5~25 preferable weight portions, the consumption that reaches composition (c) is 1~50 weight portion, 5~25 preferable weight portions.
Preferable 5~25, this polyimide has the structure of following formula (1) or (2):
N is 10~600 integer in formula (1) and (2), Ar
1Be quadrivalent organic radical group, Ar
2Be two to quadrivalent organic radical group, Ar
3Be divalent aryl, R
1Be an OH base or COOH base.
Preferable, Ar
3For
Preferable, Ar
1For
Preferable, Ar wherein
2For
Wherein m is 1~20 integer, and X
1For
—O—,—S—,—C(CF
3)
2——C(CH
3)
2—
Wherein m is 1~20 integer, and Z is H or methyl.
Preferable, phenolic group (the phenolic hydroxyl group) compound that has of this composition (b) has following array structure:
R wherein
3To R
9For H ,-OH base, C
1~C
20Alkyl or C
4~C
20Cycloaliphatic radical, and z is 0~5 integer.Better, this composition (b) is:
Preferable, the emulsion of this composition (c) has following array structure:
Wherein D is a hydrogen,
And D is not hydrogen entirely.
Preferable, this composition (a), (b) and weight (c) and account for 5~50% of said composition total weight.
Preferable, this organic solvent is N-N-methyl-2-2-pyrrolidone N-, gamma-butyrolacton or ethyl lactate (ethyl lactate).
Embodiment
The synthesis step of polyimide is for to be dissolved in for example N-N-methyl-2-2-pyrrolidone N-(N-methyl-2-pyrrolidone of an appropriate organic solvent with an amount of diamine monomer and dicarboxylic anhydride monomer; NMP) in, and in 0~4 ℃ of following vigorous stirring 4 hours, adding end-capping reagent (endcapped agent) more for example one stirred 4 hours after having the elementary amine of phenolic group or carboxyl, add dimethylbenzene (xylene) and be heated to 180 ℃ and make its backflow, with its cooling, obtain polyimide (PI) solution that the main chain end has a phenolic group or carboxyl after about 3 hours.An amount of PI solution is got in being formulated as of photosensitive polyimide of the present invention (PSPI) solution, add phenolic group (phenolic hydroxyl group) crosslinking chemical and emulsion, wherein can add NMP, gamma-butyrolacton (γ-butyrolactone, GBL) or ethyl lactate (ethyl lactate) equal solvent with the PSPI solution dilution to desired concn, in order to using.
Use the micro-photographing process of PSPI solution of the present invention as follows: (i) PSPI soln using rotary coating or alternate manner to be coated on the suitable base material; (ii) roasting in advance; (iii) exposure; (iv) develop; And (v) roasting firmly, resulting pattern is a polyimide.In above-mentioned steps (i), on a suitable base material, and above-mentioned base material for example is a silicon substrate, glass or ito glass with this eurymeric PSPI solution coat.And the method for above-mentioned coating such as method of spin coating (spin coating), roller rubbing method (roller coating), half tone rubbing method (screen coating), a pouring curtain rubbing method (curtain coating), immersion plating (dipcoating) and spray coating method (spray coating), but be not limited to above-mentioned coating process.In preferred embodiment of the present invention, through be coated with formed film earlier 70~120 ℃ pre-down roasting (prebake) several minutes to steam the solvent that removes wherein.Then with above-mentioned through substrates coated under a light shield via the actinic ray exposure, above-mentioned actinic ray for example can be used as photoactinic light source etc. for x-ray, electron beam ray, ultraviolet light ray, visible light ray or other.
The exposure back is above-mentioned develops by an alkaline water developer subsequently through substrates coated, comes being exposed of this film of flush away partly to obtain a photoresistance figure.Above-mentioned alkaline water developer comprises an alkaline aqueous solution, for example being the aqueous solution of inorganic base (potassium hydroxide, NaOH), primary amine (ethamine), secondary amine (diethylamine), tertiary amine (triethylamine) or quarternary ammonium salt (Tetramethylammonium hydroxide (tetramethylammoniumhydroxide)), is preferable with the aqueous solution that contains Tetramethylammonium hydroxide wherein.Development can be finished by soaking, spray or cover liquid or using other known developing method.Above-mentioned photoresistance figure after developing subsequently via washed with de-ionized water after, and carry out hard roasting program (post-cure) down at 180~400 ℃ and remaining solvent caught up with dried, promptly obtain having the cross section and be gradually narrow polyimide figure.
The formula that is calculated as follows of thickness conservation rate (Film residual rate):
Thickness conservation rate (%)=[(thickness after hard the baking)/(thickness after pre-the baking)]
The present invention can further be understood by the following example, and these embodiment only are used for explanation, but not are used to limit the scope of the invention.
Medicine
Two (anhydrous-trimellitic acid) second diester (ethylene glycol bis (anhydro-trimellitate) is (TMEG)),
Two (3,4-two carboxy phenyls) ether dianhydride (bis (3,4-dicarboxyphenyl) ether dianhydride (ODPA)),
3,3-dihydroxy biphenylamine (3,3-dihydroxybenzidine (HAB)),
Hexafluoro-2,2-two (3-amino-4-hydroxyphenyl)
(Hexofluoro-2,2-bis(3-amino-4-hydroxyphenyl)(BisAPAF)),
3, the 5-diaminobenzoic acid (3,5-diaminobenzoic acid (3,5-DABA)),
4,4 '-oxygen diphenylamine (4,4 '-Oxydianiline (ODA)),
2,2-two (4-(4-amino-benzene oxygen) phenyl) propane
(2,2-bis(4-(4-aminophenoxyl)phenyl)propane(BAPP)),
2,2-two (4-(3-amino-benzene oxygen) phenyl) sulfone
(2,2-bis(4-(3-aminophenoxyl)phenyl)sulfone(m-BAPS))
2,3,4-trihydroxy-Benzophenone-1,2-two-fold quinoline quinone-5-sulfonate
(2,3,4-trihydroxy-benzophenone-1,2-diazonaphthoquinone-5-sulfonate (PIC-3) is buied by KOYO chemicals Inc.)
Description of drawings
Fig. 1 is the infrared spectrum of the polyimide that synthesized of the embodiment of the invention 1, and wherein analyzed polyimide has 180 ℃ of reactions 3 hours and two kinds of 190 ℃ of reactions 3 hours.
Fig. 2 a and 2b be respectively the polyimide coating composition that uses the prepared positive light sensitivity of the embodiment of the invention 1 figure on look and analyse and observe scanning electron microscope (SEM) photo.
Embodiment
Use is equipped with 1000 milliliters three neck round-bottomed flasks of a mechanical stirrer and nitrogen inlet, add the TMEG of the ODA of the BAPP of the Bis-APAF of 18.3 g (50 mMs), 12.3 g (30 mMs), 2.02 g (10 mMs), 20.5 g (50 mMs) and the ODPA of 15.5 g (50 mMs), and add the nmp solvent of 400 grams.With above-mentioned solution in 0 ℃ stir 4 hours after, add the end-capping reagent 3-amido benzene alcohol (3-aminophenol) of 2.18 grams (20 mM) again, and under room temperature, stirred again 4 hours, add again and be warming up to 180 ℃ behind the dimethylbenzene of 80 grams and stirred 3 hours.Can obtain sticky PI solution PI-1 after the cooling.Via infrared ray (IR) spectral analysis, the PI that present embodiment synthesized is at 1781cm
-1And 1377cm
-1The characteristic absorption that acid imide C=O and C-N are arranged, as shown in Figure 1.Get PI-1 solution 50 grams, evenly mixed behind adding 1.875 gram PIC-3, the 1.875 gram DML-PC, can get a light-sensitive polyimide coating composition PSPI-1.Utilize method of spin coating coating PSPI-1 coating composition then on ito glass, under 110 ℃, after 2 minutes the soft roasting program (prebake), just can obtain the film that a thickness is about 1.1 μ m via heating plate (Hot-Plate).(its measured wavelength is between 250~400nm), throws and gives about 100mJ/cm then above-mentioned ito glass through coating to be utilized the mercury-arc lamp of a filtered
2Energy, and exposed.Tetramethyl ammonium hydroxide (tetramethylammonium hydroxide with 2.38% (percentage by weight); TMAH) the aqueous solution developer is developed, and development time is 35 seconds.Under 230 ℃ of heated-air circulation ovens, the hard roasting program (post-cure) through 30 minutes just can obtain a stable on heating PI figure subsequently.Shown in Fig. 2 a and 2b, above-mentioned figure has live width and the spacing of one 10 μ m, and thickness is about 2.0 μ m.And this figure is compared with the thickness after its original soft baking in hard roasting back, has 91% thickness conservation rate (Film residual rate), (scanning electron microscope, SEM) to can be observed this polyimide pattern be to have the cross section (tapered-angle at the cross section) that is gradually narrow to the mirror photo by scanning electron microscopy.
Use is equipped with 1000 milliliters three neck round-bottomed flasks of a mechanical stirrer and nitrogen inlet, add 7.6 g (50 mMs) 3, the ODPA of the TMEG of the ODA of the m-BAPS of 5-DABA, 12.975 g (30 mMs), 1.54 g (7.5 mMs), 32.8 g (80 mMs) and 6.2 g (20 mMs), and add 400 nmp solvents that restrain.Above-mentioned solution, is added the end-capping reagent 3-amido benzene alcohol of 2.73 grams (25 mM) again, and stirred under room temperature 4 hours again after 4 hours in 0 ℃ of stirring, be warming up to 180 ℃ behind the dimethylbenzene of adding 80 grams and stirred 3 hours.Can obtain sticky PI solution PI-2 after the cooling.Get PI-2 solution 50 grams, evenly mixed behind adding 1.875 gram PIC-3, the 1.0 gram MTPC, can get a light-sensitive polyimide coating composition PSPI-2.Utilize method of spin coating coating PSPI-2 coating composition then on ito glass, and via heating plate under 110 ℃, after 2 minutes the soft roasting program, just can obtain the film that a thickness is about 1.1 μ m.(its measured wavelength is thrown between 250~400nm) and is given about 120mJ/cm then above-mentioned ito glass through coating to be utilized the mercury-arc lamp of a filtered
2Energy exposed.TMAH aqueous solution developer with 2.38% (percentage by weight) is developed, and development time is 35 seconds.Under 230 ℃ of heated-air circulation ovens, the hard roasting program through 30 minutes just can obtain a stable on heating PI figure subsequently.Above-mentioned PI figure has live width and the spacing of 15 μ m, and thickness is 0.95um.And this PI figure is compared with the thickness after its original soft baking in hard roasting back, has 86% thickness conservation rate, and also can be observed this polyimide pattern by SEM figure is to have the cross section that is gradually narrow.
Embodiment 3
Use is equipped with 1000 milliliters three neck round-bottomed flasks of a mechanical stirrer and nitrogen inlet, add the ODA of the m-BAPS of the HAB of 10.8 g (50 mMs), 12.975 g (30 mMs), 2.02 g (10 mMs) and the TMEG of 41.0 g (100 mMs), and add the nmp solvent of 400 grams.Above-mentioned solution, is added the end-capping reagent 3-amido benzene alcohol of 2.18 grams (20 mM) again, and stirred under room temperature 4 hours again after 4 hours in 0 ℃ of stirring, behind the dimethylbenzene of adding 80 grams, be warming up to 180 ℃ and stirred 3 hours.Can obtain sticky PI solution PI-3 after the cooling.Get PI-3 solution 50 grams, evenly mixed behind adding 1.875 gram PIC-3, the 2.25 gram BIPC-PC, can get a light-sensitive polyimide coating composition PSPI-3.Utilize method of spin coating coating PSPI-3 coating composition on ito glass, and via heating plate under 110 ℃, after 2 minutes the soft roasting program, just can obtain the film that a thickness is about 1.2 μ m.(its measured wavelength is thrown between 250~400nm) and is given about 120mJ/cm then above-mentioned ito glass through coating to be utilized the mercury-arc lamp of a filtered
2Energy exposed.TMAH aqueous solution developer with 2.38% (percentage by weight) is developed, and development time is 40 seconds.Under 230 ℃ of heated-air circulation ovens, the hard roasting program through 30 minutes just can obtain a stable on heating PI figure subsequently.Above-mentioned PI figure has live width and the spacing of 15 μ m, and thickness is 1.05 μ m.And the thickness of this PI figure after roasting firmly back and its original pre-baking is compared, have one and be the thickness conservation rate of original thickness 87.5% (Film residualrate), also can be observed its pattern by SEM figure and be (tapered-angle at the cross section).
Comparative example 1
Use is equipped with 1000 milliliters three neck round-bottomed flasks of a mechanical stirrer and nitrogen inlet, adds the Bis-APAF of 36.6 g (100 mMs), the ODPA of 31.0 g (100 mMs), and adds the nmp solvent of 400 grams.Above-mentioned solution is warming up to 180 ℃ in 0 ℃ of stirring adds 80 dimethylbenzene that restrain after 4 hours after stirred 3 hours.Can obtain sticky PI solution PI-C1 after the cooling.Get PI-C1 solution 50 grams, add 1.8 gram PIC-3 and mix evenly, can get a light-sensitive polyimide coating composition PSPI-C1.Utilize method of spin coating coating PSPI-C1 coating composition on ito glass, and via heating plate under 110 ℃, after 2 minutes the soft roasting program, just can obtain the film that a thickness is about 1.1 μ m.(its measured wavelength is thrown between 250~400nm) and is given about 120mJ/cm then above-mentioned ito glass through coating to be utilized the mercury-arc lamp of a filtered
2Energy exposed.TMAH aqueous solution developer with 2.38% (percentage by weight) is developed, and development time surpasses 3 minutes still can't obtain pattern.In this comparative example, the synthetic end-capping reagent that do not use of this PI.
Comparative example 2
Get PI-1 solution 50 grams of embodiment 1 preparation, evenly mixed behind the adding 1.875 gram PIC-3, can get a light-sensitive polyimide coating composition PSPI-C2.Repeat the micro-photographing process of embodiment 1, the thickness after wherein soft the baking is 1.0 μ m, and the development time that develops with the TMAH aqueous solution is 60 seconds, must have live width and the spacing of 20 μ m, and thickness is 0.8 μ m (a thickness conservation rate 80%).The cross section of being observed its PI pattern by SEM figure is a rectangle, there is no gradually narrow shape.In this comparative example, this light-sensitive polyimide coating composition PSPI-C2 does not use composition (b) to have the compound of phenolic group (phenolic hydroxyl group).
Comparative example 3
Synthesizing of HAB-ODPA-butanols (butanol)-poly amic acid ester (polyamic acid ester)
Use is equipped with 250 milliliters three neck round-bottomed flasks of a mechanical stirrer and nitrogen inlet, adds the normal butyl alcohol (n-butanol) of the ODPA of 15.50 g (50 mMs), 7.40 g (100 mMs) and 115 g nmp solvent.Heating said mixture to 80 ℃ also stirred 4 hours under this temperature, carry out esterification, above-mentioned solution is cooled to below 4 ℃, adds the pyridine (pyridine) of 16.63 g (200 mMs) and the phenyl-phosphonic acid dichloride of 19.50 g (100 mMs) again
(phenylphosphonic dichloride), after stirring 2 hours under the room temperature, carry out the priming reaction of COOH base again.After above-mentioned solution is cooled to 0~4 ℃, add the HAB of 10.8 g (50 mMs) again, and in 0~4 ℃ stir 1 hour down after, under room temperature, stir 8 hours (carrying out the polyreaction of poly amic acid ester) again.Utilize 1000 milliliters methyl alcohol that formed solution is precipitated, and filtration collecting polymkeric substance wherein, and collected polymkeric substance is utilized washed with de-ionized water three times.The vacuum environment that at last resulting poly amic acid ester is placed in 80 ℃ made it dry in following 24 hours.Get 5 g poly amic acid ester, 1.25 g PIC-3 and 18.75 g nmp solvent and be made into photosensitive polyamic acid ester paint composition PSPI-C3.Repeat embodiment 1 micro-photographing process, wherein soft thickness after roasting is 1.0 μ m, and the development time that develops with the TMAH aqueous solution is 60 seconds, obtains having the figure of live width and the spacing of 20 μ m, and thickness is 0.9um.And this figure is compared with its original soft roasting thickness in 350 ℃ of hard roasting backs, has 70% thickness conservation rate (Film residual rate), and its pattern is a rectangle.
Comparative example 3 is general photosensitive polyamic acid ester paint composition, emphasizes just that at this its need are baked firmly via 350 ℃ and the thickness conservation rate is lower.
Claims (7)
1. the polyimide coating composition of a positive light sensitivity, comprise an organic solvent and be dissolved in (a) polyimide in this organic solvent, its main chain end has a phenolic group or carboxyl, (b) has the compound of phenolic group, and (c) as the quinone diazosulfonate of emulsion, wherein with respect to the composition (a) of each hundred weight portion, the consumption of composition (b) is 1~50 weight portion, and the consumption of composition (c) is 1~50 weight portion;
Wherein this polyimide has the structure of following formula (1) or (2):
N is 10~600 integer in formula (1) and (2); R1 is an OH base or COOH base;
Ar
1For
Ar
2For
Wherein m is 1~20 integer, and X
1For
—O—,—S—,—C(CF
3)
2—,—C(CH
3)
2—
Wherein m is 1~20 integer, and Z is H or methyl;
Ar
3For
2. composition as claimed in claim 1, wherein with respect to the composition (a) of each hundred weight portion, the consumption of composition (b) is 5~25 weight portions.
6. composition as claimed in claim 1, composition (a) wherein, (b) and weight (c) and account for 5~50% of said composition total weight.
7. composition as claimed in claim 1, organic solvent wherein are N-N-methyl-2-2-pyrrolidone N-, gamma-butyrolacton or ethyl lactate.
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TWI618979B (en) * | 2017-06-30 | 2018-03-21 | 律勝科技股份有限公司 | Thermally conductive polyimide substrate |
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Effective date of registration: 20170607 Address after: Hsinchu County, Taiwan, China Co-patentee after: Chang Chun Petrochemical Co.,Ltd. Patentee after: Industrial Technology Research Institute Address before: Taiwan County, Hsinchu, China Town, the eastern part of Zhongxing Road, No. four, No. 195 Patentee before: Industrial Technology Research Institute |
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