CN1793201A - Water radical developing copolymerized type photosensitive polyimide material and preparation process thereof - Google Patents
Water radical developing copolymerized type photosensitive polyimide material and preparation process thereof Download PDFInfo
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Abstract
本发明属于一种水基显影共聚型光敏聚酰亚胺材料及其制备方法。采用芳香二酯二酰氯同3，3’，4，4’－二苯酮四酸二酐(BTDA)、3，3’，4，4’－联苯四酸二酐(BPDA)等芳香族二酐及间苯二胺，醚二胺(ODA)等芳香族二胺单体聚合，特性粘度在0.45－0.55范围内，加入2－重氮萘醌衍生物为光敏剂，使之成为具有很高的感光性能，很好的成膜性和很好的粘结性能以及耐热性能的光敏材料。The invention belongs to a water-based developing copolymerized photosensitive polyimide material and a preparation method thereof. Using aromatic diester diacid chloride with 3,3',4,4'-benzophenone tetra-acid dianhydride (BTDA), 3,3',4,4'-biphenyl tetra-acid dianhydride (BPDA) and other aromatic Dianhydride and m-phenylenediamine, ether diamine (ODA) and other aromatic diamine monomers are polymerized, and the intrinsic viscosity is in the range of 0.45-0.55. Adding 2-diazonaphthoquinone derivatives as photosensitizers makes it a very It is a photosensitive material with high photosensitive performance, good film-forming performance, good bonding performance and heat resistance.
Description
Technical field
The invention belongs to water radical developing copolymerized type photosensitive polyimide material and preparation method thereof.
Background technology
Polyimide is the high performance material that a class has good thermostability, chemical stability, electrical insulating property and physical strength.Widespread use in microelectronics industry can be as buffer coating (Buffer Coat) mould material of LSI.The chip of LSI will will stand the condition of High Temperature High Pressure (300 ℃, 30MPa) on its lead frame of packing into after making monolithic.The buffer coating film not only plays the Alpha-ray effect of shielding, and the packaging process of installing at resin embedding and lead frame can also be heated and mechanical shock shields to the LSI chip.Up to the present also do not use the report of polyimide other resin in addition.
In unicircuit fine process process, photoetching process is a critical process, and photoresist material is again a basic functional materials the most key in the photoetching process, and it is directly restricting the development of microelectronics.Photoetching technique is the impellent of IC industrial development, and up to the present optical lithography in the production of LSI according in occupation of dominant position.Light-sensitive polyimide is meant high-energy radiation (as UV-light, X ray, electron beam or ionic fluid) responsive, the mask figure directly can be transferred to polyimide or polyimide prepolymer (precursor) on the mould material with photoetching technique.Exactly because the ability of this direct formation figure of photosensitive polyimide makes that complicated fine process is simplified.
The same negative photoresist and the positive photoresist of being divided into of light-sensitive polyimide glue with common photoresist material.Negative photoresist is meant glued membrane behind mask exposure, and its exposure region generation photo-crosslinking causes solubility property to descend or do not dissolve, and after the development, the glued membrane of non-exposed area is dissolved, and exposure region stays and is called litho pattern, i.e. optical patterning.Positive photoresist is then opposite.The production of minus light-sensitive polyimide mainly concentrates on Japan-US a few company, as toray, Dupont etc.The positive type photosensitive polyimide was reported first at the end of the eighties, and the design of positive type photosensitive polyimide is more much more difficult than minus.Along with the raising of integrated level and the speed of LSI, the interval of electrode narrows down, and this just requires photo-sensistive polyimide that higher resolution is arranged.The developing solution of the light-sensitive polyimide of minus is an organic solvent, has some problem aspect environment.The eurymeric of exploitation is improved largely than minus resolution now, and developing solution also adopts and the general identical environment-friendly type tetramethylammonium hydroxide aqueous solution of photoresist material, and the positive type photosensitive polyimide will become the main flow of buffer coating gradually from now on.
At exercise question is that although reported that the copoly type of very high photosensitive property resol is arranged, its thermotolerance is very poor in the document of " positive photoresist that comprises new Photoactive compounds " (patent No. such as D.L. Dole writing brush nurse is CN1249824A).
In the patent No. is US6600006B2) document in, although reported polyamic acid---the poly amic acid ester resin, usefulness be the method for physical blending, molecular weight is wayward.
Summary of the invention
A kind of water radical developing copolymerized type photosensitive polyimide material of the present invention, it has following structural:
Ar1 wherein, Ar3=aromatic series dianhydride residue, Ar2=aromatic diamine residue, R are esterifying agent, n, m are integer and the n greater than 15: m=1: 1～9.
The exposure principle is exactly that the light-sensitive polyimide material that will contain 2-diazo naphthoquinone derivative exposes under 365nm (i line)～436nm (g line) UV-light, 2-diazo naphthoquinone derivative is decomposed into the indenes acid derivative, this analog derivative can be dissolved in the tetramethylphosphonihydroxide hydroxide amine alkaline aqueous solution, like this, exposed portion can be dissolved in the above-mentioned weak base, unexposed part is not dissolved in above-mentioned weak base, forms positive glue pattern.
The purpose of this invention is to provide a kind of water radical developing copolymerized type photosensitive polyimide material and preparation method thereof.Adopt the aromatic diesters diacid chloride with 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA), 3,3 ', 4,4 '-BPDA aromatic series dianhydride monomer and mphenylenediamines such as (BPDA), ether diamine aromatic diamine monomer polymerizations such as (ODA), limiting viscosity is in the 0.45-0.55 scope, adding 2-diazo naphthoquinone derivative is photosensitizers, makes it to become to have very high photosensitive property, well the photochromics of film-forming properties and advantages of good caking property energy and resistance toheat.
The present invention adopts following component to synthesize the water-based developing copolymerized type photosensitive polyimide material:
(1) aromatic series dianhydride: 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA), 3,3 ', 4,4 '-BPDA (BPDA), 3,3 ', 4,4 '-triphen diether tetracarboxylic dianhydride (HQDPA), 3,3 ', 4, wherein a kind of of 4 '-phenyl ether tetracarboxylic dianhydride (ODPA) or pyromellitic acid dianhydride (PMDA) or two kinds;
(2) aromatic diamine: ether diamine (ODA), 2,2-(4,4 '-diamino) diphenyl propane (DMMDA), 4,4 '-benzidine (OTOL), 4,4 '-diaminodiphenylsulfone(DDS) (4,4 '-DDS), 3,3 '-diaminodiphenylsulfone(DDS) (3,3 '-DDS), mphenylenediamine, Ursol D (p-DA) or 4,4 '-diaminodiphenyl-methane (MDA);
(3) esterifying agent R: wherein a kind of of methyl alcohol, ethanol, propyl alcohol, Virahol or butanols or two kinds;
(4) developing solution is: the tetramethylphosphonihydroxide hydroxide amine aqueous solution, and concentration expressed in percentage by weight is between 0.1-2.4%;
(5) photosensitizers is following any one:
Wherein D is 1-naphthoquinones 2-nitrine 5-alkylsulfonyl or 1-naphthoquinones 2-nitrine 4-alkylsulfonyl.
(6) solvent: pimelinketone, gamma-butyrolactone, N-Methyl pyrrolidone, N,N-dimethylacetamide, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether vinyl acetic monomer or ethylene glycol monoethyl ether vinyl acetic monomer.These solvents can use separately, also can be that two or more forms the mixing use.
Preparation method's of the present invention step and condition are as follows:
Taking by weighing starting material according to said proportioning, is 1 with mol ratio: the aromatic series dianhydride of 1.9-2.0 and esterifying agent reaction generated the diester diacid in 8-10 hour, then, added 2 moles chloride reagent in this diester diacid, reacted 5-6 hour, obtained the diester diacid chloride; At low temperature-10 ℃--25 ℃ add aromatic diamine and aromatic series dianhydride, the total amount of the aromatic series dianhydride of the add-on of aromatic diamine and aforesaid aromatic series dianhydride add-on and this adding is for waiting mole, reacted 5～6 hours, and obtained copoly type polyamic acid-poly amic acid ester resin solution; Then this resin is sunk in the ethanol, filter, embathe 2-3 time with deionized water and dehydrated alcohol, seasoning obtains copoly type polyamic acid-poly amic acid ester resin; This resin of exsiccant is dissolved in N-Methyl pyrrolidone and gamma-butyrolactone again, ethylene glycol monobutyl ether, the volume ratio of ethylene glycol monobutyl ether vinyl acetic monomer or ethylene glycol monoethyl ether vinyl acetic monomer is in 2: 1 the mixed solvent, be made into solid content and be polyamic acid-poly amic acid ester resin solution of 15～25%, add 2-diazo naphthoquinone derivative then, the weight of the 2-diazo naphthoquinone derivative that adds is the 10-30% of polyamic acid-poly amic acid ester tree weight, again this resin solution is coated on the polished silicon slice, dry 20-30min under 60-80 ℃, under 365nm (i line)～436nm (g line) UV-light, expose, in concentration is the tetramethylphosphonihydroxide hydroxide amine aqueous solution development of 0.1-2.4%, use rinsed with deionized water, and then dry by the fire 30-60min after 250-360 ℃, obtain a kind of water radical developing copolymerized type photosensitive polyimide material.
Measure the photoetching degree and the thermostability of embodiment 1～17 light-sensitive polyimide material.Here, by electron microscope observation photoetching degree.Thermostability is to measure like this: the silicon temperature that will scribble light-sensitive polyimide material is elevated to 300 ℃ from room temperature, reduces to room temperature thereafter again, then the deformation extent by the submicroscopy film pattern.
Measurement result is: in embodiment 1～17, be used in the 4min that exposes under 365nm (i line)～436nm (g line) ultraviolet source and can obtain good litho pattern.
Measure the adhesive property of embodiment 1～17 light-sensitive polyimide material on silicon chip.The silicon chip that will scribble light-sensitive polyimide material here is dipped among the embodiment 1～17 in the pairing developing solution, soaks 360S and observes the dropping situations of film on silicon chip.
Measurement result is: the light-sensitive polyimide material in embodiment 1～17 is in pairing developing solution, and behind the immersion 360S, light-sensitive polyimide material does not all come off on silicon chip.
The invention has the advantages that photosensitive resin is easy to get, the polyimide resin glue of preparation has photosensitive property well, well film-forming properties and advantages of good caking property energy and resistance toheat.The measurement result of embodiment 1～17 can prove.
Embodiment is as follows:
Embodiment 1
Purified 6.44gBTDA (0.020 mole) is dissolved in 25mlN, in the N-N,N-DIMETHYLACETAMIDE, stir and add 1.28g methyl alcohol (0.040 mole) down, at room temperature react 8hr, add purified thionyl chloride 4.76g (0.040 mole) again, at room temperature react 5hr again, at low temperature-10 ℃ adding 9.05gDMMDA (0.040 mole) and 5.88gBPDA (0.02 mole), reacted 5～6 hours, and obtained copoly type polyamic acid-poly amic acid ester resin solution.
Above-mentioned resin solution is sunk in the ethanol, filter, embathe 2 times with deionized water and dehydrated alcohol, seasoning obtains polyamic acid-poly amic acid ester resin.Again will be the dried resin volume ratio that is dissolved in N-Methyl pyrrolidone and gamma-butyrolactone be in 2: 1 the mixed solvent, it is polyamic acid-poly amic acid ester resin solution of 20% that adding photosensitizers I derivative 1.5g is made into solid content.
Above-mentioned resin solution is applied to spin-coating method on the silicon chip of polishing, dry 20min under 80 ℃, the 4min that then exposes under 365nm (i line)～436nm (g line) UV-light develops at 1% tetramethylphosphonihydroxide hydroxide amine aqueous solution, uses rinsed with deionized water.After 250-360 ℃, dry by the fire 30-60min then, obtain water radical developing copolymerized type photosensitive polyimide material.
Embodiment 2
To make with extra care 5.88gBPDA (0.02 mole) and be dissolved in 36mlN, in the N-N,N-DIMETHYLACETAMIDE, stir and add 1.84g ethanol (0.04 mole) down, at room temperature react 10hr, add purified thionyl chloride 4.76g (0.040 mole) again, at room temperature react 6hr again, then at low temperature-15 ℃ adding 4.24gOTOL (0.02 mole) and 4.00gODA (0.02 mole) and 3.6gPMDA (0.020 mole), reaction 5hr obtains polyamic acid-poly amic acid ester resin solution.
Above-mentioned polyamic acid-poly amic acid ester resin is sunk in the ethanol, filter, embathe 3 times seasoning with deionized water and dehydrated alcohol.Again will be the dried resin volume ratio that is dissolved in N-Methyl pyrrolidone and ethylene glycol monobutyl ether be that adding photosensitizers II derivative 1.8g is made into the polyamic acid-poly amic acid ester resin solution of solid content 25% in 2: 1 the mixed solvent.
Above-mentioned polyamic acid-poly amic acid ester resin solution is applied to spin-coating method on the silicon chip of polishing, dry 20min under 80 ℃, 4min then exposes under 365nm (i line)～436nm (g line) UV-light.Develop at 2.4% tetramethylphosphonihydroxide hydroxide amine aqueous solution, use rinsed with deionized water.After 250-360 ℃, dry by the fire 30-60min then, obtain water radical developing copolymerized type photosensitive polyimide material.
Embodiment 3
Purified 3.6gPMDA (0.020 mole) is dissolved in the 70mlN-methyl-2-pyrrolidone, stir and add 2.40g propyl alcohol (0.040 mole) down, at room temperature react 8hr, add purified thionyl chloride 4.76g (0.040 mole) again, at room temperature react 6hr again, then at low temperature-20 ℃ adding 4.24gOTOL (0.02 mole) and 4.00gODA (0.02 mole) and 6.44gBTDA (0.020 mole), reaction 5hr obtains polyamic acid-poly amic acid ester resin solution.
Above-mentioned polyamic acid-poly amic acid ester resin is sunk in the ethanol, filter, embathe 3 times seasoning with deionized water and dehydrated alcohol.Again will be the dried resin volume ratio that is dissolved in N-Methyl pyrrolidone and ethylene glycol monobutyl ether be in 2: 1 the mixed solvent, it is polyamic acid-poly amic acid ester resin solution of 15% that adding photosensitizers III derivative 1.4g is made into solid content.
Above-mentioned polyamic acid-poly amic acid ester resin solution is applied to spin-coating method on the silicon chip of polishing, dry 20min under 80 ℃, 4min then exposes under 365nm (i line)～436nm (g line) UV-light.Develop at 2% tetramethylphosphonihydroxide hydroxide amine aqueous solution, use rinsed with deionized water.After 250-360 ℃, dry by the fire 30-60min then, obtain water radical developing copolymerized type photosensitive polyimide material.
Embodiment 4
Purified 8.05gHQDPA (0.020 mole) is dissolved in the 26mlN-methyl-2-pyrrolidone, stir and add 2.40g Virahol (0.040 mole) down, at room temperature react 8hr, add purified thionyl chloride 4.76g (0.040 mole) again, at room temperature react 6hr again, then at low temperature-25 ℃ adding 9.96g4,4 '-DDS (0.04 mole) and 3.6gPMDA (0.020 mole) react 5hr and obtain polyamic acid-poly amic acid ester resin solution.
Above-mentioned polyamic acid-poly amic acid ester resin is sunk in the ethanol, filter, embathe 3 times seasoning with deionized water and dehydrated alcohol.Again will be the dried resin volume ratio that is dissolved in N-Methyl pyrrolidone and ethylene glycol monobutyl ether be in 2: 1 the mixed solvent, it is polyamic acid-poly amic acid ester resin solution of 20% that adding photosensitizers III derivative 1.4g is made into solid content.
Above-mentioned polyamic acid-poly amic acid ester resin solution is applied on the silicon chip of polishing dry 20min under 80 ℃, then exposure 4min under 365nm (i line)～436nm (g line) ultraviolet source with spin-coating method.Develop at 2% tetramethylphosphonihydroxide hydroxide amine aqueous solution, use rinsed with deionized water.After 250-360 ℃, dry by the fire 30-60min then, obtain water radical developing copolymerized type photosensitive polyimide material.
Embodiment 5
Purified 8.05gODPA (0.020 mole) is dissolved in the 26mlN-methyl-2-pyrrolidone, stir and add 2.96g butanols (0.040 mole) down, at room temperature react 10hr, add purified thionyl chloride 4.76g (0.040 mole) again, at room temperature react 6hr again, then at low temperature-25 ℃ adding 8.00gODA (0.04 mole) and 6.44gBTDA (0.020 mole), reaction 5hr obtains polyamic acid-poly amic acid ester resin solution.
Above-mentioned polyamic acid-poly amic acid ester resin is sunk in the ethanol, filter, embathe 3 times seasoning with deionized water and dehydrated alcohol.Again will be the dried resin volume ratio that is dissolved in N-Methyl pyrrolidone and ethylene glycol monobutyl ether be in 2: 1 the mixed solvent, it is polyamic acid-poly amic acid ester resin solution of 20% that adding photosensitizers IV derivative 2.2g is made into solid content.
Above-mentioned polyamic acid-poly amic acid ester resin solution is applied to spin-coating method on the silicon chip of polishing, dry 20min under 80 ℃, 4min then exposes under 365nm (i line)～436nm (g line) UV-light.Develop at 2% tetramethylphosphonihydroxide hydroxide amine aqueous solution, use rinsed with deionized water.After 250-360 ℃, dry by the fire 30-60min then, obtain water radical developing copolymerized type photosensitive polyimide material.
Embodiment 6
Purified 8.05gHQDPA (0.020 mole) is dissolved in the 25mlN-methyl-2-pyrrolidone, stir and add 2.96g butanols (0.040 mole) down, at room temperature react 8hr, add purified thionyl chloride 4.76g (0.040 mole) again, at room temperature react 6hr again, then at low temperature-15 ℃ adding 8.00gODA (0.04 mole) and 3.22gBTDA (0.020 mole), reaction 5hr obtains polyamic acid-poly amic acid ester resin.All the other experiment conditions are with embodiment 5.
Embodiment 7
Purified 3.22gBTDA (0.020 mole) is dissolved in the 20mlN-methyl-2-pyrrolidone, stir and add 2.40g Virahol (0.040 mole) down, at room temperature react 8hr, add purified thionyl chloride 4.76g (0.040 mole) again, at room temperature react 6hr again, then at low temperature-20 ℃ adding 4.96g4,4 '-DDS (0.02 mole) and 4.00gODA (0.02 mole) and 3.22gBTDA (0.020 mole) react 5hr and obtain polyamic acid-poly amic acid ester resin.All the other experiment conditions are with embodiment 4.
Embodiment 8
Purified 5.88gBPDA (0.020 mole) is dissolved in the 30mlN-methyl-2-pyrrolidone, stir and add 1.84g ethanol (0.04 mole) down, at room temperature react 10hr, add purified thionyl chloride 4.76g (0.040 mole) again, at room temperature react 6hr again, then at low temperature-25 ℃ adding 4.24gOTOL (0.02 mole) and 4.00gODA (0.02 mole) and 8.05gHQDPA (0.020 mole), reaction 5hr obtains polyamic acid-poly amic acid ester resin solution.All the other experiment conditions are with embodiment 1.
Embodiment 9
Purified 4.36gPMDA (0.020 mole) is dissolved in the 15ml N,N-DIMETHYLACETAMIDE, stir and add 1.84g ethanol (0.04 mole) down, at room temperature react 10hr, add purified thionyl chloride 4.76g (0.040 mole) again, at room temperature react 6hr again, then at low temperature-10 ℃ ℃ adding 3.40gOTOL (0.016 mole) and 5.96g3,3 '-DDS (0.024 mole) and 8.05gHQDPA (0.020 mole) react 5hr and obtain polyamic acid-poly amic acid ester resin solution.
Except that " be made into solid content be 20% polyamic acid-poly amic acid ester resin solution " among the embodiment 1 being changed into " be made into solid content be 15% polyamic acid-poly amic acid ester resin solution ", all the other experiment conditions are with embodiment 1.
Embodiment 10
Purified 8.05gHQDPA (0.020 mole) is dissolved in the 15mlN-methyl-2-pyrrolidone, stir and add 2.96g butanols (0.040 mole) down, at room temperature react 8hr, add purified thionyl chloride 4.76g (0.040 mole) again, at room temperature react 6hr again, then at low temperature-20 ℃ adding 8.00gODA (0.04 mole) and 4.36gPMDA (0.020 mole), reaction 5hr obtains polyamic acid-poly amic acid ester resin solution.All the other experiment conditions are with embodiment 5.
Embodiment 11
In the molten 25ml N,N-DIMETHYLACETAMIDE of purified 4.36gPMDA (0.020 mole), stir and add 2.40g propyl alcohol (0.040 mole) down, at room temperature react 8hr, add purified thionyl chloride 4.76g (0.040 mole) again, at room temperature react 6hr again, then at low temperature-25 ℃ adding 2.12gOTOL (0.01 mole) and 6.00gODA (0.03 mole) and 6.20gODPA (0.020 mole), reaction 5hr obtains polyamic acid-poly amic acid ester resin solution.All the other experiment conditions are with embodiment 3.
Embodiment 12
Purified 6.44gBTDA (0.020 mmole) is dissolved in the 25mlN-methyl-2-pyrrolidone, stir and add 2.96g butanols (0.040 mole) down, at room temperature react 8hr, add purified thionyl chloride 4.76g (0.040 mole) again, at room temperature react 6hr again, then at low temperature-10 ℃ adding 2.12gOTOL (0.01 mole) and 6.00gODA (0.03 mole) and 6.20gODPA (0.020 mole), reaction 5hr obtains polyamic acid-poly amic acid ester resin solution.All the other experiment conditions are with embodiment 5.
Embodiment 13
Purified 6.20gODPA (0.020 mole) and 1.1gPMDA (5 mmole) are dissolved in 20mlN, in the N-N,N-DIMETHYLACETAMIDE, stir and add 2.96g butanols (0.040 mole) down, at room temperature react 8hr, add purified thionyl chloride 4.76g (0.040 mole) again, at room temperature react 6hr again, then at low temperature-15 ℃ adding 8.00gODA (0.04 mole) and 5.88gBPDA (0.02 mole), reaction 5hr obtains polyamic acid-poly amic acid ester resin solution.Be changed to " adding photosensitizers V derivative " except that will " adding photosensitizers IV derivative ", all the other experiment conditions are with embodiment 5.
Embodiment 14
Purified 4.36gPMDA (0.020 mole) is dissolved in the 15mlN-methyl-2-pyrrolidone, be changed to outside " adding 8.49gOTOL (0.040 mole) " except that will " adding 4.96g4; 4 '-DDS (0.02 mole) and 4.00gODA (0.02 mole) ", all the other experiment conditions are with embodiment 7.
Embodiment 15
Purified 6.44gBTDA (0.020 mole) is dissolved in the 15ml N,N-DIMETHYLACETAMIDE, be changed to " adding 2.12TOL (0.01 mole) and 6.00gODA (0.03 mole) " except that will " adding 8.00gODA (0.04 mole) ", all the other experiment conditions are with embodiment 13.
Embodiment 16
Purified 4.02gHQDPA (0.010 mole) and 2.94gBPDA (0.010 mole) are dissolved in the 25mlN-methyl-2-pyrrolidone, stir adding 2.96g butanols (0.040 mole) down, all the other experiment conditions are with embodiment 3.
Embodiment 17
Purified 4.02gHQDPA (0.010 mole) and 2.94gBPDA (0.010 mole) are dissolved in the 20mlN-methyl-2-pyrrolidone, stir and add 1.48g butanols (0.020 mole) and 0.64g methyl alcohol (0.020 mole) down, at room temperature react 9hr, all the other experiment conditions are with embodiment 1.
Claims (2)
1. water radical developing copolymerized type photosensitive polyimide material is characterized in that having following structural formula:
Ar1 wherein, Ar3=aromatic series dianhydride residue, Ar2=aromatic diamine residue, R are esterifying agent, n, m are the integer greater than 15.
2. the preparation method of a kind of water radical developing copolymerized type photosensitive polyimide material as claimed in claim 1 is characterized in that step and condition are as follows:
Taking by weighing starting material according to said proportioning, is 1 with mol ratio: the aromatic series dianhydride of 1.9-2.0 and esterifying agent reaction generated the diester diacid in 8-10 hour; Then, in this diester diacid, add 2 moles chloride reagent, reacted 5-6 hour, obtain the diester diacid chloride; At low temperature-10 ℃--25 ℃ add aromatic diamine and aromatic series dianhydride, the total amount of the aromatic series dianhydride of the add-on of aromatic diamine and aforesaid aromatic series dianhydride add-on and this adding is for waiting mole, reacted 5～6 hours, and obtained copoly type polyamic acid-poly amic acid ester resin solution; Then this resin is sunk in the ethanol, filter, embathe 2-3 time with deionized water and dehydrated alcohol, seasoning obtains copoly type polyamic acid-poly amic acid ester resin; This resin of exsiccant is dissolved in N-Methyl pyrrolidone and gamma-butyrolactone again, ethylene glycol monobutyl ether, the volume ratio of ethylene glycol monobutyl ether vinyl acetic monomer or ethylene glycol monoethyl ether vinyl acetic monomer is in 2: 1 the mixed solvent, be made into solid content and be polyamic acid-poly amic acid ester resin solution of 15～25%, add 2-diazo naphthoquinone derivative then, the weight of the 2-diazo naphthoquinone derivative that adds is the 10-30% of polyamic acid-poly amic acid ester tree weight, again this resin solution is coated on the polished silicon slice, dry 20-30min under 60-80 ℃, under 365nm (i line)～436nm (g line) UV-light, expose, in concentration is the tetramethylphosphonihydroxide hydroxide amine aqueous solution development of 0.1-2.4%, use rinsed with deionized water, after 250-360 ℃, dry by the fire 30-60min then, obtain a kind of water radical developing copolymerized type photosensitive polyimide material; Wherein said
The aromatic series dianhydride is: 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA), 3,3 ', 4,4 '-BPDA (BPDA), 3,3 ', 4,4 '-triphen diether tetracarboxylic dianhydride (HQDPA), 3,3 ', 4, wherein a kind of of 4 '-phenyl ether tetracarboxylic dianhydride (ODPA) or pyromellitic acid dianhydride (PMDA) or two kinds;
Aromatic diamine is: ether diamine (ODA), and 2,2-(4,4 '-diamino) diphenyl propane (DMMDA), 4,4 '-benzidine (OTOL), 4,4 '-diaminodiphenylsulfone(DDS) (4,4 '-DDS), 3,3 '-diaminodiphenylsulfone(DDS) (3,3 '-DDS), mphenylenediamine, Ursol D (p-DA) or 4,4 '-diaminodiphenyl-methane (MDA);
Esterifying agent R is: wherein a kind of of methyl alcohol, ethanol, propyl alcohol, Virahol or butanols or two kinds;
Developing solution is: the tetramethylphosphonihydroxide hydroxide amine aqueous solution, and concentration expressed in percentage by weight is between 0.1-2.4%;
Photosensitizers is following any one:
Wherein D is 1-naphthoquinones 2-nitrine 5-alkylsulfonyl or 1-naphthoquinones 2-nitrine 4-alkylsulfonyl;
Solvent is: pimelinketone, gamma-butyrolactone, N-Methyl pyrrolidone, N,N-dimethylacetamide, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether vinyl acetic monomer or ethylene glycol monoethyl ether vinyl acetic monomer; These solvents can use separately, also can be that two or more forms the mixing use.
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| CN112521296A (en) * | 2021-02-05 | 2021-03-19 | 武汉柔显科技股份有限公司 | Diamine compound, heat-resistant resin or heat-resistant resin precursor using same, photosensitive resin composition, cured film, and display device |
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| CN1072238C (en) * | 1997-07-24 | 2001-10-03 | 中国科学院长春应用化学研究所 | Process for preparing ester type photosensitive polyimide |
| JP4450136B2 (en) * | 1999-11-30 | 2010-04-14 | 日産化学工業株式会社 | Positive photosensitive polyimide resin composition |
| JP2002275262A (en) * | 2001-03-22 | 2002-09-25 | Toshiba Chem Corp | Photosensitive resin composition and method for producing the same |
| CN1175082C (en) * | 2001-10-26 | 2004-11-10 | 中国科学院长春应用化学研究所 | Method for preparing liquid crystal alignment film from polyimide containing photosensitive end-capping agent |
| CN1272365C (en) * | 2004-12-24 | 2006-08-30 | 中国科学院长春应用化学研究所 | Process for preparing water base developing photosensitive polyimide material |
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