CN100480856C - Water base developing organic silicon modified light-sensitive polyimide material and preparation method thereof - Google Patents
Water base developing organic silicon modified light-sensitive polyimide material and preparation method thereof Download PDFInfo
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Abstract
A method for preparing photosensitive polyimide material modified by water based developing organic silicon includes using aromatic diester - diacyl chlorine to carry out polymerization with monomers of 3.5 - diamino benzoic acid, 4.4 - diamino 3.3 dihydroxy diphenyl methance and 4.4 diamino 3.3 dihydroxy diphenyl sufoxide; then using 3 - amino propyl triethoxy silane to carry out modification for generating prepolymer of organic silicon modified polyimide, adding photosensitizer to obtain photosensitive material of modified polyimide.
Description
Technical field
The invention belongs to water base developing organic silicon modified light-sensitive polyimide material and preparation method thereof.
Background technology
Along with miniaturization, the lightweight of electronic device, the miniaturization of semiconductor device, slimming, granular also grow up rapidly, at electronic applications high performance, multifunction and low price are also pursued in the requirement of material like this.Polyimide is with resistant to elevated temperatures excellent specific property, and buffer coat (Buffer Coat) membrane material as LSI is widely used in the microelectronics industry.Photosensitive polyimide is because it not only has excellent thermotolerance, insulativity, mechanical property, and processing technology also can be simplified.The chip of LSI sticks with glue agent with on its lead frame of packing into after making monolithic, at this moment will stand 300 ℃, the condition of 30MPa.The buffer coat 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 physical shock shields to the LSI chip.This just requires buffer coat can bear this heat and physical shock, does not up to the present also use the report of polyimide other resin in addition.
Photoetching technique is the expulsive force of IC industrial development, and up to the present optical lithography in the production of LSI according in occupation of leading position.Traditional photoresist will form alkaline-resisting photoresist as mask on buffer coat, wash the technology more complicated after the etching again.After photo-sensistive polyimide resin is used, manufacturing procedure is simplified greatly, almost all use photo-sensistive polyimide as buffer coat at present.
Photo-sensistive polyimide is the same with photoresist to be divided into minus (cross-linking type) and the photosensitive eurymeric that is partly dissolved (change in polarity type) that photosensitive part stays.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 developer 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 developer solution also adopts and the general identical environment-friendly type tetramethylammonium hydroxide aqueous solution of photoresist, and the positive type photosensitive polyimide will become the main flow of buffer coat gradually from now on.
At exercise question is " a kind of preparation method of water base developing photosensitive polyimide material " (Zhang Chunhua, Chinese patent application number is 2004100113909) document in, although report has very high photosensitive property, good film forming and heat resistance, its cohesiveness is not very good.
Summary of the invention
In order to solve the technical matters that above-mentioned cohesiveness exists, the purpose of this invention is to provide water base developing organic silicon modified light-sensitive polyimide material and preparation method thereof.
A kind of water base developing organic silicon modified light-sensitive polyimide material of the present invention has following structural formula:
Ar wherein
1=aromatic series dianhydride residue, Ar
2=aromatic diamine A residue, Ar
3=(CH
2)
3Si (CH
3)
2OSi (CH
3)
2(CH
2)
3, Ar
4=aromatic diamine B residue, p are 1～5 integer, and n, m are the integer greater than 15;
Following structural formula is perhaps arranged:
Ar
1=aromatic series dianhydride residue, Ar
2=aromatic diamine A residue, Ar
4=aromatic diamine B residue, n, m are the integer greater than 15.
The polyimide photosensitive resin that the exposure principle will contain 2-diazo naphthoquinone derivant exactly exposes under 365nm (i line)～436nm (g line) ultraviolet light, 2-diazo naphthoquinone derivant is decomposed into the indenes acid derivative, this analog derivative can be dissolved in the alkaline aqueous solutions such as tetramethylphosphonihydroxide hydroxide amine, 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 present invention adopts the aromatic diesters diacid chloride with 3,5-diamines yl benzoic acid, 4,4 '-two amidos 3,3 '-dioxydiphenyl methane and 4,4 '-two amidos 3,3 '-dihydroxydiphenylsulisomer and organo-silicon compound 3-aminopropyltriethoxywerene werene or 1,3-two (3-aminopropyl)-1,1,3, the polymerization of 3-tetramethoxy-silicane generates organic-silicon-modified poly amic acid ester resin.Its limiting viscosity is in 0.35-0.45 scope, and adding 2-diazo naphthoquinone derivant is photosensitizer, makes it to become the photochromics with very high photosensitive property and advantages of good caking property energy and heat resistance.
The present invention adopts the following raw materials according component to prepare water base developing organic silicon modified light-sensitive polyimide material:
1. 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 ', 4,4 '-wherein a kind of of diphenyl ether tetracarboxylic dianhydride (ODPA) or pyromellitic acid dianhydride (PMDA) or two kinds;
2. aromatic diamine A is: 2,2-(3,3 '-dihydroxy 4,4 '-diamido) diphenyl propane (HDMMDA), 3,3 '-dihydroxy 4,4 '-benzidine (HOTOL), 3,3 '-dihydroxy 4,4 '-diamino-diphenyl sulfone (HDDS), 3,5-diamines yl benzoic acid (3,5-DABA), 2,4-diaminophenol or 2,2 '-(3,3 '-dihydroxy 4,4 '-diamido) diphenyl hexafluoorpropane (HD6FDA);
3. aromatic diamine B is: ether diamine (ODA), and 2,2-(4,4 '-diamido) diphenyl propane (DMMDA), 4,4 '-benzidine (OTOL), 4,4 '-diamino-diphenyl sulfone (4,4 '-DDS), 3,3 '-diamino-diphenyl sulfone (3,3 '-DDS), m-phenylene diamine, p-phenylenediamine (PPD) (p-DA) or 4,4 '-diaminodiphenyl-methane (MDA);
4. organo-silicon compound are: 3-aminopropyltriethoxywerene werene, and 1,3-two (3-aminopropyl)-1,1 ', 3,3 '-tetramethoxy-silicane;
5. esterifying agent is: wherein a kind of of methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol or butanols or two kinds;
6. chloride reagent is: thionyl chloride;
7. the developer solution of development usefulness is: tetramethylphosphonihydroxide hydroxide amine aqueous solution or aqueous sodium carbonate or sodium hydrate aqueous solution, and concentration expressed in percentage by weight is between 0.1-2.4%;
8. photosensitizer is following any one:
Wherein D is 1-naphthoquinones, 2-nitrine, 5-sulfonyl or 1-naphthoquinones, 2-nitrine, 4-sulfonyl;
9. solvent is: cyclohexanone, γ-butyrolactone, N-methyl pyrrolidone, N, N-dimethyl acetamide, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether ethyl acetate or ethylene glycol monoethyl ether ethyl acetate, these solvents can use separately, also can be that two or more mixes use.
Preparation method's of the present invention step and condition are as follows:
With mol ratio is aromatic series dianhydride and the esterifying agent of 1:1.9-2.0, reacts to generate the diester diacid in 8-10 hour; The chloride reagent that in this diester diacid, adds 2-2.5 moles, reacted 5-6 hours, at low temperature-10 ℃---25 ℃ add aromatic diamine A and aromatic diamine B, aromatic diamine A: the mol ratio of aromatic diamine B is 1:9～4:1, and the molal quantity of aromatic diamine A and aromatic diamine B and with the mole ratio of aromatic series dianhydride be 1:1, reacted 3～4 hours, add corresponding organo-silicon compound again, reacted 2～3 hours, and generated organic-silicon-modified poly amic acid ester resin solution; This resin solution is sunk in the ethanol again, filter, embathe 2-3 times with deionized water and absolute ethyl alcohol, air dry obtains organic-silicon-modified poly amic acid ester resin; Again this dry resin is dissolved in N-methyl pyrrolidone and γ-butyrolactone, ethylene glycol monobutyl ether, the volume ratio of ethylene glycol monobutyl ether ethyl acetate or ethylene glycol monoethyl ether ethyl acetate is in the mixed solvent of 2:1, be made into solid content and be 15～25% organic-silicon-modified poly amic acid ester resin solution, add 2-diazo naphthoquinone derivant then, the weight that adds 2-diazo naphthoquinone derivant is 10-30% of organic-silicon-modified poly amic acid ester weight resin, again this resin solution is coated on the polished silicon slice, dry 20-30min under 60-80 ℃, exposure under 365nm (i line)～436nm (g line) ultraviolet light, in concentration is that 0.1-2.4% tetramethylphosphonihydroxide hydroxide amine aqueous solution develops, use rinsed with deionized water, and then dry by the fire 30-60min after 250-360 ℃, obtain water base developing organic silicon modified light-sensitive polyimide material;
Measure the photoetching degree and the thermal stability of embodiment 1～17 organic silicon modified light-sensitive polyimide material.Here, by electron microscope observation photoetching degree.Thermal stability is to measure like this: the silicon temperature that will scribble organic silicon modified light-sensitive poly amic acid ester resin material is elevated to 300 ℃ from room temperature, reduces to room temperature thereafter again, then the deformation extent by the electron microscopy 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 organic silicon modified light-sensitive polyimide material on carrier (silicon chip).The polished silicon slice that will be coated with organic silicon modified light-sensitive polyimide material here at room temperature is dipped into concentration expressed in percentage by weight in 0.1-2.4% tetramethylammonium hydroxide aqueous solution, observes the dropping situations of film on silicon chip.Be " a kind of preparation method of water base developing photosensitive polyimide material " (Zhang Chunhua simultaneously with exercise question, Chinese patent application number is 2004100113909) document in light-sensitive polyimide material be coated on the polished silicon slice its adhesive property of test under identical condition.
Measurement result is: do not split away off from silicon chip in 60 seconds with organic silicon modified light-sensitive polyimide material, and needed just split away off from silicon chip in 300 seconds with organic silicon modified light-sensitive polyimide material.The adhesive property that the latter is described is higher than the former far away.
The invention has the advantages that photosensitive resin is easy to get, the water base developing organic silicon modified light-sensitive polyimide material of preparation has very high photosensitive property, well film forming and advantages of good caking property energy and heat resistance.Beneficial effect of the present invention can be proved from the measurement result of as above embodiment:
Embodiment is as follows:
Embodiment 1
Refining 6.44gBTDA (0.020 mole) is dissolved in 25mlN, in N-dimethyl acetamide, stirs adding 1.28g methyl alcohol (0.040 mole) down, at room temperature react 8hr; Add refining thionyl chloride 4.76g (0.040 mole) again, at room temperature react 5hr again; In 3-aminopropyltriethoxywerene werene (0.020 mole) of low temperature-10 ℃ adding 2.09g HDMMDA (0.0080 mole) and 0.40gODA (0.0020 mole) and 4.42g, react the organic-silicon-modified poly amic acid ester resin solution of acquisition after 5～6 hours.
Above-mentioned organic-silicon-modified poly amic acid ester resin is sunk in the ethanol, filter, embathe 2 times air dry with deionized water and absolute ethyl alcohol; Again will be the dry above-mentioned resin volume ratio that is dissolved in N-methyl pyrrolidone and γ-butyrolactone be in the mixed solvent of 2:1, it is 20% organic-silicon-modified poly amic acid ester resin solution that adding photosensitizer I derivant 1.5g is made into solid content.
Be applied to above-mentioned organic-silicon-modified poly amic acid ester resin solution on the silicon chip of polishing with spin-coating method, dry 20min under 80 ℃, 4min then exposes under 365nm (i line)～436nm (g line) ultraviolet light, develop at 1% tetramethylphosphonihydroxide hydroxide amine aqueous solution, use rinsed with deionized water, obtain the etching figure.After 250-360 ℃, dry by the fire 30-60min then, obtain water base developing organic silicon modified light-sensitive polyimide material.
Embodiment 2
To make with extra care 5.88gBPDA (0.02 mole) is dissolved in the 36ml dimethyl acetamide, stir and add 1.84g ethanol (0.04 mole) down, at room temperature react 10hr, add refining thionyl chloride 4.76g (0.040 mole) again, at room temperature react 6hr again, then in 3-aminopropyltriethoxywerene werene (0.020 mole) of low temperature-15 ℃ adding 1.22gHOTOL (0.005 mole) and 1.00gODA (0.005 mole) and 4.42g, reaction 5hr obtains organic-silicon-modified poly amic acid ester resin solution.
Above-mentioned organic-silicon-modified poly amic acid ester resin is sunk in the ethanol, filter, embathe 3 times air dry with deionized water and absolute ethyl alcohol.Again will be the dried resin volume ratio that is dissolved in N-methyl pyrrolidone and ethylene glycol monobutyl ether be in the mixed solvent of 2:1, it is 20% organic-silicon-modified poly amic acid ester resin solution that adding photosensitizer II derivant 1.8g is made into mass percent.
Above-mentioned organic-silicon-modified 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 light with spin-coating method.Develop at 2.4% tetramethylphosphonihydroxide hydroxide amine aqueous solution, use rinsed with deionized water, obtain the etching figure.After 250-360 ℃, dry by the fire 30-60min then, obtain water base developing organic silicon modified light-sensitive polyimide material.
Embodiment 3
Refining 3.6gPMDA (0.020 mole) is dissolved in 70mlN-methyl pyrrolidone, stir and add 2.40g propyl alcohol (0.040 mole) down, at room temperature react 8hr, add refining thionyl chloride 4.76g (0.040 mole) again, at room temperature react 6hr again, then at low temperature-20 ℃ adding 0.244gHOTOL (0.0010 mole) and 1.80gODA (0.0090 mole) and 2.48g 1,3-two (3-aminopropyl)-1,1,3,3-tetramethoxy-silicane (0.010 mole), reaction 5hr obtains organic-silicon-modified poly amic acid ester resin solution.
Above-mentioned organic-silicon-modified poly amic acid ester resin is sunk in the ethanol, filter, embathe 3 times air dry with deionized water and absolute ethyl alcohol.Again will be the dried resin volume ratio that is dissolved in N-methyl pyrrolidone and ethylene glycol monobutyl ether be in the mixed solvent of 2:1, it is 15% polyamic acid resin solution that adding photosensitizer III derivant 1.4g is made into solid content
Above-mentioned organic-silicon-modified 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 light with spin-coating method.Develop at 2% tetramethylphosphonihydroxide hydroxide amine aqueous solution, use rinsed with deionized water, obtain the etching figure.After 250-360 ℃, dry by the fire 30-60min then, obtain water base developing organic silicon modified light-sensitive polyimide material.
Embodiment 4
Refining 8.05gHQDPA (0.020 mole) is dissolved in 26mlN-methyl pyrrolidone, stir and add 2.40g isopropyl alcohol (0.040 mole) down, at room temperature react 8hr, add refining thionyl chloride 4.76g (0.040 mole) again, at room temperature react 6hr again, then at low temperature-25 ℃ adding 1.88gHD6FDA (0.005 mole) and 1.24g4,4 '-DDS (0.005 mole) and 2.48g 1,3-two (3-aminopropyl)-1,1,3,3-tetramethoxy-silicane (0.010 mole), reaction 5hr obtains organic-silicon-modified poly amic acid ester resin solution.
Above-mentioned organic-silicon-modified poly amic acid ester resin is sunk in the ethanol, filter, embathe 3 times air dry with deionized water and absolute ethyl alcohol.Again will be the dried resin volume ratio that is dissolved in N-methyl pyrrolidone and ethylene glycol monobutyl ether be in the mixed solvent of 2:1, it is 20% organic-silicon-modified poly amic acid ester resin solution that adding photosensitizer III derivant 1.4g is made into solid content.
Above-mentioned organic-silicon-modified 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% aqueous sodium carbonate, use rinsed with deionized water, obtain the etching figure.After 250-360 ℃, dry by the fire 30-60min then, obtain water base developing organic silicon modified light-sensitive polyimide material.
Embodiment 5
Refining 8.05gODPA (0.020 mole) is dissolved in 26mlN-methyl pyrrolidone, stir and add 2.96g butanols (0.040 mole) down, at room temperature react 10hr, add refining thionyl chloride 4.76g (0.040 mole) again, at room temperature react 6hr again, then at low temperature-25 ℃ adding 1.52g3,5-DABA (0.010 mole) and 2.48g1,3-two (3-aminopropyl)-1,1,3,3-tetramethoxy-silicane (0.010 mole), reaction 5hr obtains organic-silicon-modified poly amic acid ester resin solution.
Above-mentioned organic-silicon-modified poly amic acid ester resin is sunk in the ethanol, filter, embathe 3 times air dry with deionized water and absolute ethyl alcohol.Again will be the dried resin volume ratio that is dissolved in N-methyl pyrrolidone and ethylene glycol monobutyl ether be in the mixed solvent of 2:1, adding photosensitizer IV derivant 2.2g is made into 20% poly amic acid ester resin solution
Above-mentioned organic-silicon-modified 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 light with spin-coating method.Develop at 0.5% sodium hydrate aqueous solution, use rinsed with deionized water, obtain the etching figure.After 250-360 ℃, dry by the fire 30-60min then, obtain water base developing organic silicon modified light-sensitive polyimide material.
Embodiment 6
Refining 8.92g6FDA (0.020 mole) is dissolved in 25mlN-methyl pyrrolidone, stir and add 2.96g butanols (0.040 mole) down, at room temperature react 8hr, add refining thionyl chloride 4.76g (0.040 mole) again, at room temperature react 6hr again, then at low temperature-15 ℃ adding 0.76g3,5-DABA (0.005 mole) and 1.00gODA (0.005 mole) and 4.42g3-aminopropyltriethoxywerene werene (0.020 mole), reaction 5hr obtains the poly amic acid ester resin solution.All the other experiment conditions are with embodiment 5.
Embodiment 7
Refining 3.22gBTDA (0.020 mole) is dissolved in 20mlN-methyl pyrrolidone, stir and add 2.40g isopropyl alcohol (0.040 mole) down, at room temperature react 8hr, add refining thionyl chloride 4.76g (0.040 mole) again, at room temperature react 6hr again, then at low temperature-20 ℃ adding 1.88gHD6FDA (0.005 mole) and 1.24g4,4 '-DDS (0.005 mole) and 4.42g3-aminopropyltriethoxywerene werene (0.020 mole), reaction 5hr obtains the poly amic acid ester resin solution.All the other experiment conditions are with embodiment 4.
Embodiment 8
Refining 5.88gBPDA (0.020 mole) is dissolved in 30mlN-methyl pyrrolidone, stir and add 1.84g ethanol (0.04 mole) down, at room temperature react 10hr, add refining thionyl chloride 4.76g (0.040 mole) again, at room temperature react 6hr again, then in low temperature-25 ℃ adding 1.22gHOTOL (0.005 mole) and 1.00gODA (0.005 mole) and 4.42g3-aminopropyltriethoxywerene werene (0.020 mole), reaction 5hr obtains the poly amic acid ester resin solution.All the other experiment conditions are with embodiment 1.
Embodiment 9
Refining 4.36gPMDA (0.020 mole) is dissolved in 15mlN, in the N-dimethyl acetamide, stir and add 1.84g ethanol (0.04 mole) down, at room temperature react 10hr, add refining thionyl chloride 4.76g (0.040 mole) again, at room temperature react 6hr again, then add 1.95gHOTOL (0.008 mole) and 0.40gODA (0.002 mole) and 2.48g 1 low temperature-10 ℃～-15 ℃, two (3-aminopropyl)-1 of 3-, 1 ', 3,3 '-tetramethoxy-silicane (0.010 mole), reaction 5hr obtains the poly amic acid ester resin solution.
Except that " be made into solid content be 20% poly amic acid ester resin solution " among the embodiment 1 being changed into " be made into solid content be 15% poly amic acid ester resin solution ", all the other experiment conditions are with embodiment 1.
Embodiment 10
Refining 8.05gHQDPA (0.020 mole) is dissolved in 15mlN-methyl pyrrolidone, stir and add 2.96g butanols (0.040 mole) down, at room temperature react 8hr, add refining thionyl chloride 4.76g (0.040 mole) again, at room temperature react 6hr again, then at low temperature-20 ℃ adding 0.76g3,5-DABA (0.005 mole) and 1.00gODA (0.005 mole) and 2.48g1, two (the 3-aminopropyls)-1 of 3-, 1 ', 3,3 '-tetramethoxy-silicane (0.010 mole), reaction 5hr obtains the poly amic acid ester resin solution.All the other experiment conditions are with embodiment 5.
Embodiment 11
With the refining molten 25ml N of 8.80g6FDA (0.020 mole), in the N-dimethyl acetamide, stir and add 2.40g propyl alcohol (0.040 mole) down, at room temperature react 8hr, add refining thionyl chloride 4.76g (0.040 mole) again, at room temperature react 6hr again, then at low temperature-25 ℃ adding 2.44gHOTOL (0.01 mole) and 1.00gODA (0.005 mole) and 1.24g 1,3-two (3-aminopropyl)-1,1 ', 3,3 '-tetramethoxy-silicane (0.005 mole), reaction 5hr obtains the poly amic acid ester resin solution.All the other experiment conditions are with embodiment 3.
Embodiment 12
Refining 6.44gBTDA (0.020 mM) is dissolved in 25mlN-methyl pyrrolidone, stir and add 2.96g butanols (0.040 mole) down, at room temperature react 8hr, add refining thionyl chloride 4.76g (0.040 mole) again, at room temperature react 6hr again, then at low temperature-10 ℃ adding 0.30g3,5-DABA (0.002 mole) and 1.60gODA (0.008 mole) and 4.42g3-aminopropyltriethoxywerene werene (0.020 mole), reaction 5hr obtains the poly amic acid ester resin solution.All the other experiment conditions are with embodiment 5.
Embodiment 13
Refining 6.20gODPA (0.020 mole) and 1.1gPMDA (5 mM) are dissolved in the 20ml dimethyl acetamide, stir and add 2.96g butanols (0.040 mole) down, at room temperature react 8hr, add refining thionyl chloride 4.76g (0.040 mole) again, at room temperature react 6hr again, then at low temperature-15 ℃ adding 0.76g3,5-DABA (0.005 mole) and 2.00gODA (0.01 mole) and 1.24g1,3-two (3-aminopropyl)-1,1 ', 3,3 '-tetramethoxy-silicane (0.005 mole), reaction 5hr obtains the poly amic acid ester resin solution.Be changed to " adding photosensitizer V derivant " except that will " adding photosensitizer IV derivant ", all the other experiment conditions are with embodiment 5.
Embodiment 14
Refining 4.36gPMDA (0.020 mole) is dissolved in 15mlN-methyl pyrrolidone, remove will " 1.88gHD6FDA (0.005 mole) and 1.24g4; 4 '-DDS (0.005 mole) " be changed to " add 0.78g HDMMDA (0.003 mole) and 1.74g4; 4 '-DDS (0.007 mole) " outside, all the other experiment conditions are with embodiment 7.
Embodiment 15
Refining 6.44gBTDA (0.020 mole) is dissolved in 15ml N, in the N-dimethyl acetamide, be changed to outside " adding 3.67g HOTOL (0.015 mole) " except that will " adding 0.76g3,5-DABA (0.005 mole) and 2.00gODA (0.01 mole) ", all the other experiment conditions are with embodiment 13.
Embodiment 16
Refining 4.02gHQDPA (0.010 mole) and 2.94gBPDA (0.010 mole) are dissolved in 25mlN-methyl pyrrolidone, stir adding 2.96g butanols (0.040 mole) down, all the other experiment conditions are with embodiment 3.
Embodiment 17
Refining 4.02gHQDPA (0.010 mole) and 2.94gBPDA (0.010 mole) are dissolved in 20mlN-methyl 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 base developing organic silicon modified light-sensitive polyimide material, it is characterized in that: it has following structural:
Ar wherein
1=aromatic series dianhydride residue, Ar
2=aromatic diamine A residue, Ar
3=(CH
2)
3Si (CH
3)
2OSi (CH
3)
2(CH
2)
3, Ar
4=aromatic diamine B residue, p are 1～5 integer, and n, m are the integer greater than 15;
Following structure is perhaps arranged:
2. the preparation method of a kind of water base developing organic silicon modified light-sensitive polyimide material as claimed in claim 1, its step and condition are as follows: with mol ratio is aromatic series dianhydride and the esterifying agent of 1:1.9-2.0, reacts to generate the diester diacid in 8-10 hour; The chloride reagent that adds 2-2.5 moles in this diester diacid reacted 5-6 hours; At low temperature-10 ℃---25 ℃ add aromatic diamine A and aromatic diamine B, aromatic diamine A: the mol ratio of aromatic diamine B is 1:9～4:1, and the molal quantity of aromatic diamine A and aromatic diamine B and with the mole ratio of aromatic series dianhydride be 1:1, reacted 3～4 hours; Add corresponding organo-silicon compound again, reacted 2～3 hours, generate organic-silicon-modified poly amic acid ester resin solution; This resin solution is sunk in the ethanol again, filter, embathe 2-3 times with deionized water and absolute ethyl alcohol, air dry obtains organic-silicon-modified poly amic acid ester resin; Again this dry resin is dissolved in N-methyl pyrrolidone and γ-butyrolactone, ethylene glycol monobutyl ether, the volume ratio of ethylene glycol monobutyl ether ethyl acetate or ethylene glycol monoethyl ether ethyl acetate is in the mixed solvent of 2:1, be made into solid content and be 15～25% organic-silicon-modified poly amic acid ester resin solution, add 2-diazo naphthoquinone derivant then, the weight that adds 2-diazo naphthoquinone derivant is 10-30% of organic-silicon-modified poly amic acid ester weight resin, again this resin solution is coated on the polished silicon slice, dry 20-30min under 60-80 ℃, under 365nm i line～436nm g line ultraviolet light, expose, in concentration is that 0.1-2.4% tetramethylphosphonihydroxide hydroxide amine aqueous solution develops, use rinsed with deionized water, at 250-360 ℃ of baking 30-60min, obtain water base developing organic silicon modified light-sensitive polyimide material then; Described
The aromatic series dianhydride is: 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-BPDA, 3,3 ', 4,4 '-triphen diether tetracarboxylic dianhydride, 3,3 ', 4,4 '-wherein a kind of of diphenyl ether tetracarboxylic dianhydride or pyromellitic acid dianhydride or two kinds;
Aromatic diamine A is: 2,2-(3,3 '-dihydroxy 4,4 '-diamido) diphenyl propane, 3,3 '-dihydroxy 4,4 '-benzidine, 3,3 '-dihydroxy 4,4 '-diamino-diphenyl sulfone, 3,5-diamines yl benzoic acid, 2,4-diaminophenol or 2,2 '-(3,3 '-dihydroxy 4,4 '-diamido) the diphenyl hexafluoorpropane;
Aromatic diamine B is: ether diamine, and 2,2-(4,4 '-diamido) diphenyl propane, 4,4 '-benzidine, 4,4 '-diamino-diphenyl sulfone, 3,3 '-diamino-diphenyl sulfone, m-phenylene diamine, p-phenylenediamine (PPD) or 4,4 '-diaminodiphenyl-methane;
Organo-silicon compound are: 3-aminopropyltriethoxywerene werene, and 1,3-two (3-aminopropyl)-1,1 ', 3,3 '-tetramethoxy-silicane;
Esterifying agent is: wherein a kind of of methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol or butanols or two kinds;
Chloride reagent is: thionyl chloride;
Developer solution is: tetramethylphosphonihydroxide hydroxide amine aqueous solution or aqueous sodium carbonate or sodium hydrate aqueous solution, and concentration expressed in percentage by weight is between 0.1-2.4%;
Photosensitizer is following any one:
Wherein D is 1-naphthoquinones, 2-nitrine, 5-sulfonyl or 1-naphthoquinones, 2-nitrine, 4-sulfonyl;
Solvent is: cyclohexanone, γ-butyrolactone, N-methyl pyrrolidone, N,N-dimethylacetamide, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether ethyl acetate or ethylene glycol monoethyl ether ethyl acetate; These solvents can use separately, also can be that two or more forms the mixing use.
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| CN100480856C true CN100480856C (en) | 2009-04-22 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3919549A4 (en) * | 2019-01-29 | 2022-03-23 | Mitsubishi Chemical Corporation | Composition and metal-insulating coating material |
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| CN1206724A (en) * | 1997-07-24 | 1999-02-03 | 中国科学院长春应用化学研究所 | Process for preparing ester type photosensitive polyimide |
| JP2001228609A (en) * | 1999-11-30 | 2001-08-24 | Nissan Chem Ind Ltd | Positive photosensitive polyimide resin composition |
| CN1343755A (en) * | 2001-10-26 | 2002-04-10 | 中国科学院长春应用化学研究所 | Process for preparing liquid crystal orientated film from polyimide containing photosensitive terminating agent |
| JP2002275262A (en) * | 2001-03-22 | 2002-09-25 | Toshiba Chem Corp | Photosensitive resin composition and method for producing the same |
| CN1648154A (en) * | 2004-12-24 | 2005-08-03 | 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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2005
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1206724A (en) * | 1997-07-24 | 1999-02-03 | 中国科学院长春应用化学研究所 | Process for preparing ester type photosensitive polyimide |
| JP2001228609A (en) * | 1999-11-30 | 2001-08-24 | Nissan Chem Ind Ltd | 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 |
| CN1343755A (en) * | 2001-10-26 | 2002-04-10 | 中国科学院长春应用化学研究所 | Process for preparing liquid crystal orientated film from polyimide containing photosensitive terminating agent |
| CN1648154A (en) * | 2004-12-24 | 2005-08-03 | 中国科学院长春应用化学研究所 | Process for preparing water base developing photosensitive polyimide material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3919549A4 (en) * | 2019-01-29 | 2022-03-23 | Mitsubishi Chemical Corporation | Composition and metal-insulating coating material |
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