CN1970603A - Intrinsical fluorinated photosensitive polyimide resin and its preparation method - Google Patents
Intrinsical fluorinated photosensitive polyimide resin and its preparation method Download PDFInfo
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Abstract
The invention discloses an intrinsic-typed photoactive polyimide resin and making method, which is polycondensated by 3,3',4,4' -benzophenone pyromellitic dianhydride 40 with polyalkyl substituted aromatic methane diamine 20-42 as fluorine aromatic lateral group, wherein the carbon atom number of A, B, C and D in the formula I is 1-10; E, F, G is H atom or trifluoromethyl. The invention possesses superior solubility, which can be reserved for half year under indoor temperature and 18 months under 4 deg.c.
Description
Technical field
The present invention relates to a kind of Intrinsical fluorinated photosensitive polyimide resin and preparation method thereof.
Background technology
High temperature resistant, low temperature resistant, corrosion-resistant, high insulation that polyimide material has, low-k and advantages such as low-dielectric loss, mechanical property excellence have been widely used as the passivation tunic of semi-conductor chip and interlayer dielectric, insulation diaphragm and the flexible PCB etc. that the insulating layer film in the microelectronics Packaging, dielectric tunic, stress buffer are protected tunic, multilevel metal interconnection structure.In these are used, often need between the circuit of the circuit of polyimide rete one side and opposite side or equipment, to form conductive channel, thereby need on the polyimide rete, make passage or through hole by the ultraviolet photolithographic method.
The polyimide resin that is applicable to the photoetching drawing comprises photo-sensistive polyimide resin and non-photosensitivity polyimide resin two big class (Rao R.Tummala, E.J.Rymaszewski, A.G.Klopfenstein, Ed.Microelectronics Packaging Handbook, Chapman ﹠amp; Hall, 1997,509-613).The non-photosensitivity polyimide resin is owing to realizing the photoetching drawing by common photoresist material, so processing step is more loaded down with trivial details; In addition, because the photoresist material that uses needs to remove, usually can influence the performance of final polyimide tunic.Photo-sensistive polyimide resin comprises interpolation photosensitizer additive type resin and two types of (K.Hasegawa of eigenmode resin; Progress inPolymer Science, 26 (2001), p259-335).Add photosensitizer additive type resin and in the non-photosensitivity resin, introduce a large amount of photosensitizer additives, these photosensitizer additives need heating that its decomposition is all removed after finishing figure, often cause the degradation etc. of volumetric shrinkage, collapse-deformation and the polyimide rete of litho pattern.The eigenmode resin can be when in polymkeric substance, not adding photosensitizer additive by main polymer chain in mutual photo-crosslinking between the functional group obtain the developing rate contrast, realize the transfer of lithographic images, thereby have many advantages, comprise that solidification value is low, the power consumption of unit weight resin solidification less, picture quality height, less subside and distortion, surface and internal void are few, film mechanical strength and insulating property are good etc.
The photo-crosslinking effect of eigenmode polyimide photosensitive resin is mainly finished by benzophenone group in the main polymer chain structure and the photo-crosslinking that contiguous fatty alkyl is rolled into a ball.Under ultraviolet lighting, benzophenone based can be captured the proton of contiguous alkyl, the free radical coupling reaction takes place generate cross-linked structure, makes exposure area and unexposed area produce bigger dissolution rate difference.After utilizing dissolution with solvents to remove the uncrosslinked resin of unexposed area, obtain the specific solid figure structure that forms by cross-linked resin.
Eigenmode polyimide photosensitive resin is when ultraviolet photolithographic charts, needs adopt organic solvent as developing solution unexposed area to be dissolved and get rid of, the organic solvent that is adopted is strong polar aprotic solvent, comprise: N-N-methyl-2-2-pyrrolidone N-, N, dinethylformamide (DMF), N,N-dimethylacetamide etc. (DMAc).In addition, eigenmode polyimide photosensitive resin must have higher solubleness and lower viscosity in organic solvent, and this resin solution should have good coating film forming properties on surfaces such as silicon single crystal, silicon-dioxide, glass, pottery, metals.But, the solubleness of disclosed eigenmode polyimide photosensitive resin in high boiling point, strong polar organic solvent is lower, and the viscosity of solution is higher, so need higher solidification value all except that desolvate (more than＞200 ℃), this has all proposed to bear the harsh requirement of hot environment simultaneously not only to the substrate of carrying polyimide tunic (silica-based, aluminium base etc.) to mounted components and parts, annex etc.In addition, higher solidification value also has certain destruction to the solid figure that the back of developing forms, and directly influences the yield rate of product.Along with the develop rapidly of microelectronics manufacturing and encapsulation technology, the integrated level and the packaging density of electron device are more and more higher, and the mutual signal that is caused by the raising of wiring density postpones, and signal cross-talk and waste of energy more and more cause people's attention.Therefore, require employed polyimide tunic should have low specific inductivity and low moisture absorption etc., to improve the reliability and stability of device.Though eigenmode polyimide photosensitive resin has excellent performance, the existence of the problems referred to above has limited this class material and has used widely in microelectronics manufacturing and packaging process.
The Josef Pfeifer of Ciba-Geigy company (US 4629777) discloses the eigenmode polyimide photosensitive resin that a class has higher photosensitivity.The alkyl of the polyalkyl-substituted aromatic diamine that this resin is used comprises CH
3, CH
2CH
3, CH (CH
3)
2, OCH
3, OCH
2CH
3Deng; Two fragrant phenyl ring of aromatic diamines are asked by following radicals and are connected :-CH
2-,-O-,-S-,-CO-,-SO
2-,-SO-,-COO-,-CONCH
3-,-NCH
3-,-CONH-,-NH-,-Si (CH
3)
2-,-CH
2CH
2-,-C
6H
4-,-C (CH
3)-,-C (CF
3)-.On the basis of (UP4629777), Ciba-Geigy company on the backbone structure of polyimide by increase the dyeing group increase resin in the absorption of ultraviolet region improving its photosensitive property, but the degree that has improved solubility of this quasi-polyimide is limited.
Ciba-Geigy company (US 4657832) is afterwards by introducing the bridged ring substituting group to improve its solubility property on the benzene ring structure of aromatic diamines; US 4698295 discloses a class eigenmode photosensitive polyimide resin, and this resin uses the organic tetracarboxylic dianhydride that contains a plurality of carbonyls to replace the ketone acid anhydride of single carbonyl to improve its photosensitive property; The poplar scholar bravely waits (CN1448421A) to disclose a kind of eigenmode photosensitive polyimide resin, has obviously improved the solubility property of resin in organic solvent, but in the intrinsic light sensitivity, still there are above-mentioned problem in water-intake rate and dielectric properties aspect.
Summary of the invention
The purpose of this invention is to provide a kind of Intrinsical fluorinated photosensitive polyimide resin and preparation method thereof.
Intrinsical fluorinated photosensitive polyimide resin provided by the present invention is mainly formed by polycondensation by following parts by weight of component:
3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride 40,
The methane diamines 20-42 of polyalkyl-substituted aromatic family of the fluorinated aromatic pendant of formula I structure;
Among the formula I, A, B, C, D are that carbonatoms is the alkyl of 1-10; E, F, G are H atom or trifluoromethyl.
Here, A, B, C, D are preferably methyl, ethyl or sec.-propyl.
When carrying out polycondensation and prepare polyimide resin, can also add the component of following weight part:
Aromatic diamine 0-20,
Molecular weight regulator 0-50.
This Intrinsical fluorinated photosensitive polyimide resin can adopt following two kinds of methods to be prepared:
Method one comprises the steps:
1) polyalkyl-substituted aromatic family methane diamines and the 0-20 weight part aromatic diamine with the fluorinated aromatic pendant of 20-42 weight part formula I structure is dissolved in the 300-800 weight part organic solvent, under nitrogen protection, add 40 weight 3 again, 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride and 0-50 weight part molecular weight regulator, in nitrogen atmosphere stirring at room 12-24 hour then, obtain polyamic acid solution;
2) add 28-100 weight part diacetyl oxide-pyridine mixtures in above-mentioned solution, diacetyl oxide in this mixture/pyridine volume ratio is 5/4, at 25 ℃ of-60 ℃ of following stirring reaction 4-12 hours, obtains described eigenmode photosensitive polyimide resin.
Method two; be polyalkyl-substituted aromatic family methane diamines, 0-20 weight part aromatic diamine, 0-50 weight part molecular weight regulator and 40 weight parts 3 with the fluorinated aromatic pendant of 20-42 weight part formula I structure; 3 '; 4; 4 '-benzophenone tetracarboxylic dianhydride is dissolved in the 400-850 weight part meta-cresol; under nitrogen protection, drip 1-5 weight part isoquinoline 99.9 and 50-200 parts by weight of toluene; reaction mixture is heated to 160-180 ℃ of reaction 3-9 hour, obtains described eigenmode photosensitive polyimide resin.
In the above reaction process, aromatic diamine can be selected for use and be Ursol D, ask phenylenediamine, 2, the 5-diaminotoluene, 2, the 6-diaminotoluene, 4,4 '-diaminodiphenyl oxide, 3,4 '-diaminodiphenyl oxide, 3,3 '-diaminodiphenyl oxide, 2,4 '-diaminodiphenyl oxide, 4,4 '-diaminodiphenylsulfone(DDS), 4,4 '-diaminodiphenylmethane, 3,3 '-dimethyl-4,4 '-diaminodiphenylmethane, 3,3 ', 5,5 '-tetramethyl--4,4 '-diaminodiphenylmethane, 3,3 ', 5,5 '-tetraethyl--4,4 '-diaminodiphenylmethane, 4,4 '-two (4-amino-benzene oxygen) propane, 4,4 '-two (4-amino-benzene oxygen) benzene, 4,4 '-two (4-amino-benzene oxygen) sulfobenzides and the mixture that mixes by arbitrary proportion thereof;
Molecular weight regulator is meant adjustable polyimide polymer molecular chain length and the organic carbon hydrogen compound or the silicoorganic compound that increase its adhesiveproperties, and commonly used have a Tetra hydro Phthalic anhydride, the phenylacetylene phthalic anhydride, phenylacetylene aniline, norbornene dicarboxylic anhydride, aniline, γ-An Bingjisanyiyangjiguiwan, γ-An Bingjisanjiayangjiguiwan, two-(γ-aminopropyl) tetramethyl-silica alkane, two-(γ-ammonia butyl) tetramethyl-silica alkane, two-(γ-aminopropyl) tetramethyl-polysiloxane, two-(γ-aminopropyl) tetraphenyl silica alkane, two-(γ-aminopropyl) tetraphenyl polysiloxane, two-(γ-ammonia butyl) tetraphenyl silica alkane, two-(γ-ammonia butyl) tetraphenyl polysiloxane and the mixture that mixes by arbitrary proportion thereof.
Reaction selected organic solvent usually can be N-Methyl pyrrolidone, N, N-N,N-DIMETHYLACETAMIDE, N, dinethylformamide, dimethyl sulfoxide (DMSO), gamma-butyrolactone, chloroform, 1,2-ethylene dichloride, tetrahydrofuran (THF), acetone and the mixing solutions that mixes by arbitrary proportion thereof.
Through above-mentioned reaction process, adopt methanol extraction, washing, after super-dry, promptly can obtain available fluorinated photosensitive polyimide resin solid.The solid polyimide resin is dissolved in the organic solvent, obtains Intrinsical fluorinated polyimide photosensitive resin solution, can also in this solution, add some photosensitizer additives to improve the lightsensitivity of resin.This solution can adopt methods such as spin-coating method, pickling process, spraying method or silk screen printing to be coated on the substrate, after exposure, developing, obtains required image; Further heat treated obtains having high-resolution photoetching pattern or through hole, and key step is: (1) coating: polyimide resin is coated on the substrate surface; (2) prebake: the partial solvent in the above-mentioned resin is evaporated the coating that has certain degree of hardness with formation; (3) exposure: photomask is covered on the resin, adopt the exposure of ultraviolet exposure equipment; (4) develop: adopt developing solution dissolution and remove the resin of unexposed portion, finish cleaning with washing fluid then, obtain required image; (5) completely solidified: the resin of above-mentioned formation image is added the heat extraction residual solvent, obtain the polyimide tunic after the thermofixation.
Here, photosensitizer additive is commonly used comprises benzophenone, 4, two (dimethylamino) benzophenone of 4-, benzoin ether, anthraquinone or thioxanthone derivates, 2,6-two (4,4-diethylin benzyl) pimelinketone, 1-phenyl-5 mercapto-tetrazole, 1-phenyl-2-propanedione-2-(ethoxy carbonyl) oxime and the mixture that mixes by arbitrary proportion thereof.
A plurality of fluoro-containing groups have been introduced in the backbone structure of the Intrinsical fluorinated polyimide photosensitive resin of the present invention, reduce the molecular chain of main polymer chain and pile up efficient, hinder the formation of intermolecular charge transfer complex compound, obviously reduced in the main chain fragrant chain link in the absorbancy of carbonyl with the sensitive band of the photo-crosslinking of contiguous alkyl.This polyimide photosensitive resin has excellent solubility property, can be dissolved in strong polarity, high boiling solvent, also can be dissolved in general polarity, low boiling point solvent, has efficient, characteristics such as technology is simple, etching condition tolerance simultaneously; In addition, the stability in storage of this photosensitive resin is good, and the shelf lives at room temperature surpasses half a year, and is following to 18 months at 4 ℃.Many advantages such as that the polyimide tunic that forms after being heating and curing has is high temperature resistant, low temperature, corrosion-resistant, high insulation, low-k, the excellent water-intake rate of mechanical property are low; simultaneously still have good organic solvent dissolution performance, can be widely used in the interlayer dielectric, insulation diaphragm of passivation tunic in the semiconductor manufacturing industry and the insulating layer film in the microelectronics Packaging industry, dielectric tunic, stress buffer protection tunic, multi-layer metal wiring interconnect architecture etc.
Embodiment
In the present invention, the polyalkyl-substituted aromatic family methane diamines (formula I) of used fluorinated aromatic pendant can be by alkyl substituted benzene amine synthetic under lewis acidic catalysis of formula II structure fluorobenzene ethanone derivatives and formula III structure, wherein, A, B are that carbonatoms is the alkyl of 1-10; E, F, G are H atom or trifluoromethyl.
Here, Chang Yong Lewis acid has hydrochloric acid, methylsulfonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid etc.
In the reaction process, the mol ratio of fluorobenzene ethanone derivatives and alkyl substituted benzene amine is 1: 1.1-10.The temperature of reaction is controlled at 150-210 ℃.
The reaction equation of this preparation process is as follows, the visible embodiment of concrete preparation process, and various raw materials used in following examples all can be commercially available.
Embodiment 1,1, two (4 '-amino-3 ', 5 '-two (methyl) phenyl)-1-(3 ', 5 '-two (trifluoromethyl) phenyl)-2,2 of 1-, 2-Halothane synthetic
2,6-xylidine 65 grams, 2,6-dimethylaniline dihydrochloride 35 grams and 3 ', 5 '-two (trifluoromethyl)-2,2,2 trifluoroacetophenones, 35 grams mix in reaction flask.Mixture heating up to 130 ℃ 1 hour is dissolved fully until raw material.Reactant was heated to 180 ℃ of reflux 10 hours then.Reaction system is cooled to room temperature, and 100 grams, 20% sodium hydroxide solution is splashed in the reaction soln.Then, filter insolubles, dry then, obtain clean product, reaction yield 49% with ethyl alcohol recrystallization with water washing with this solution of wet distillation 4 hours.
Product fusing point: 151 ℃;
Infrared (KBr, cm
-1): 3494 (N-H absorption peaks), 3403 (the amino absorption peaks of N-H), 2973 (CH alkyl absorption peaks), 2861,1624,1496,1365,1279,1232,1145 (C-F absorption peaks);
Nucleus magnetic resonance-hydrogen spectrum (300 megahertzes, DMSO-d
6, δ): 2.0 (S; 12H), 4.8 (S; 4H), 6.5 (S; 4H), 7.6 (S; 2H), 8.2 (S; 1H);
Nucleus magnetic resonance-carbon spectrum (300 megahertzes, CDCl3-d
6, δ): 17.9,64.5,121.3,123.2,128.0,129.5,130.1,130.9,142.3,144.3;
Mass spectrum: 534 (molecular ion peak, intensity 22%);
Ultimate analysis: calculated value C, 58.43%, H, 4.34%, N, 5.24%, measured value: C, 58.37%, H, 4.34%, N, 5.27%.
Embodiment 2,1, two (4 '-amino-3 ', 5 '-two (methyl) phenyl)-1-(4 '-trifluoromethyl)-2,2 of 1-, 2-Halothane synthetic
2,6-xylidine 100 grams, 2,6-dimethylaniline dihydrochloride 40 grams and 4 '-trifluoromethyl-2,2,2 trifluoroacetophenones, 50 grams mix in reaction flask.Mixture heating up to 120 ℃ 1.5 hours is dissolved fully until raw material.Reactant was heated to 170 ℃ of reflux 8 hours then.Reaction system is cooled to room temperature, and 100 grams, 20% potassium hydroxide solution is splashed in the reaction soln.Then, filter insolubles, dry then, obtain clean product with ethyl alcohol recrystallization with water washing with this solution of wet distillation 4 hours.
Product fusing point: 162 ℃;
Nucleus magnetic resonance-hydrogen spectrum (300 megahertzes, DMSO-d
6, δ): 2.3 (S; 12H), 4.8 (S; 4H), 6.5 (S; 4H), 7.0 (D; 2H), 7.4 (D; 2H);
Nucleus magnetic resonance-carbon spectrum (300 megahertzes, CDCl3-d
6, δ): 16.7,64.5,124.2,125.7,127.9,128.5,128.6,129.4,129.5,133.4,142.4,146.9;
Ultimate analysis: calculated value C, 64.37%, H, 5.19%, N, 6.01%, measured value: C, 64.01%, H, 5.26%, N, 6.25%.
Embodiment 3,1, two (4 '-amino-3 ', 5 '-two (methyl) phenyl)-1-(3 '-trifluoromethyl)-2,2 of 1-, 2-Halothane synthetic
2,6-xylidine 80 grams, 2,6-dimethylaniline dihydrochloride 25 grams and 3 '-trifluoromethyl-2,2,2 trifluoroacetophenones, 45 grams mix in reaction flask.Mixture heating up to 120 ℃ 2 hours is dissolved fully until raw material.Reactant was heated to 170 ℃ of reflux 12 hours then.Reaction system is cooled to room temperature, and 100 grams, 20% ammonia soln is splashed in the reaction soln.Then with this solution of wet distillation 4 hours, filtering insolubles with water washing, after the oven dry, is eluant with petroleum ether-ethyl acetate (volume ratio 1: 1) mixed solution, separates obtaining clean product with silica gel column chromatography.
Product fusing point: 149 ℃;
Nucleus magnetic resonance-hydrogen spectrum (300 megahertzes, DMSO-d
6, δ): 2.4 (S; 12H), 4.0 (S; 4H), 6.6 (S; 4H), 7.12, (D; 1H), 7.14 (T; 1H), 7.27 (D; 1H), 7.37 (D; 1H);
Nucleus magnetic resonance-carbon spectrum (300 megahertzes, CDCl3-d
6, δ): 16.9,62.1,122.7,124.5,126.2,127.9,129.4,129.5,129.6,131.5,131.6,133.4,142.4,143.9;
Ultimate analysis: calculated value C, 64.37%, H, 5.19%, N, 6.01%, measured value: C, 64.12%, H, 5.30%, N, 6.22%.
Embodiment 4,1, two (4 '-amino-3 ', 5 '-two (ethyl) phenyl)-1-(4 '-trifluoromethyl)-2,2 of 1-, 2-Halothane synthetic
2,6-Diethyl Aniline 140 grams, 2,6-diethylbenzene amine hydrochlorate 30 grams and 4 '-trifluoromethyl-2,2,2 trifluoroacetophenones, 75 grams mix in reaction flask.Mixture heating up to 100 ℃ is dissolved fully until raw material.Reactant is heated to 170 ℃ then, reacts 12 hours.Reaction system is cooled to room temperature, and 100 grams, 20% sodium hydroxide solution is splashed in the reaction soln.Then with this solution of wet distillation 4 hours, filter insolubles with water washing, oven dry with ethyl alcohol recrystallization, obtains clean product then.
Product fusing point: 166 ℃;
Nucleus magnetic resonance-hydrogen spectrum (300 megahertzes, DMSO-d
6, δ): 1.4, (T; 12H), 2.4 (T; 8H), 4.0 (S; 4H), 6.5 (S; 4H), 7.1 (D; 1H), 7.4 (D; 1H);
Ultimate analysis: calculated value C, 65.58%, H, 5.71%, N, 5.66%, measured value: C, 65.29%, H, 5.68%, N, 5.77%.
Embodiment 5,1, two (4 '-amino-3 ', 5 '-two (sec.-propyl) phenyl)-1-(4 '-trifluoromethyl)-2,2 of 1-, 2-Halothane synthetic
2,6-diisopropyl aniline 110 grams, 2,6-diisopropyl benzene amine hydrochlorate 15 grams and 4 '-trifluoromethyl-2,2,2 trifluoroacetophenones, 60 grams mix in reaction flask.Mixture heating up to 120 ℃ is dissolved fully until raw material.Reactant is heated to 190 ℃ then, reacts 12 hours.Reaction system is cooled to room temperature, and 85 grams, 20% sodium hydroxide solution is splashed in the reaction soln.Then with this solution of wet distillation 5 hours, filter insolubles with water washing, oven dry with ethyl alcohol recrystallization, obtains clean product then.
Product fusing point: 167 ℃;
Nucleus magnetic resonance-hydrogen spectrum (300 megahertzes, DMSO-d
6, δ): 1.3, (D; 24H), 3.1 (H; 4H), 4.0 (S; 4H), 6.5 (S; 4H), 7.1 (D; 1H), 7.4 (D; 1H);
Ultimate analysis: calculated value C, 68.49%; H, 6.97%; N, 4.84%, measured value: C, 68.29%, H, 6.88%, N, 4.95%.
Embodiment 6,1, two (4 '-amino-3 ', 5 '-two (methyl) phenyl)-1-(3 ', 5 ,-two (trifluoromethyl) phenyl)-2,2 of 1-, 2-Halothane synthetic
2,6-xylidine 65 grams, trifluoromethanesulfonic acid 10 grams and 3 ', 5 '-two (trifluoromethyl)-2,2,2 trifluoroacetophenones, 35 grams mix in reaction flask.Mixture heating up to 130 ℃ is dissolved fully until raw material.Reactant was heated to 180 ℃ of reflux 10 hours then.Reaction system is cooled to room temperature, and 100 grams, 20% sodium hydroxide solution is splashed in the reaction soln.Then, filter insolubles, dry then, obtain clean product, reaction yield 55% with ethyl alcohol recrystallization with water washing with this solution of wet distillation 4 hours.
Product fusing point: 151 ℃;
Infrared (KBr, cm
-1): 3494 (N-H absorption peaks), 3403 (the amino absorption peaks of N-H), 2973 (CH alkyl absorption peaks), 2861,1624,1496,1365,1279,1232,1145 (C-F absorption peaks);
Nucleus magnetic resonance-hydrogen spectrum (300 megahertzes, DMSO-d
6, δ): 2.0 (S; 12H), 4.8 (S; 4H), 6.5 (S; 4H), 7.6 (S; 2H), 8.2 (S; 1H);
Nucleus magnetic resonance-carbon spectrum (300 megahertzes, CDCl3-d
6, δ): 17.9,64.5,121.3,123.2,128.0,129.5,130.1,130.9,142.3,144.3;
Mass spectrum: 534 (molecular ion peak, intensity 22%);
Ultimate analysis: calculated value C, 58.43%, H, 4.34%, N, 5.24%, measured value: C, 58.37%, H, 4.34%, N, 5.27%
Embodiment 7,
With 40 grams 1, two (the 4-amino-3 of 1-, 5-two (methyl) phenyl)-1-(3 ', 5 '-two (trifluoromethyl) phenyl)-2,2,2-Halothane (FMA) is dissolved in the 670 gram N-Methyl pyrrolidone (NMP), add 40 grams 3 again, 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA) and other 50 gram NMP.Mixture in stirring at room 24 hours, obtains polyamic acid (PAA) solution of solids content 10% under nitrogen protection.With 100 the gram diacetyl oxide-pyridine mixtures (5/4, v/v) join in the PAA solution; The reactant mechanical stirring heated 4 hours down for 60 ℃, poured in the excessive methanol solution, separated out the white solid polymkeric substance.The white solid polymkeric substance in 80 ℃ of following vacuum-dryings, is obtained the Intrinsical fluorinated photosensitive polyimide solid resin.
Limiting viscosity (25 ℃, NMP): 0.74dl/g;
FT-IR(film，cm
-1)：2933，1784，1731，1492，1369，1280，1232，904，844。
Ultimate analysis: calculated value C, 62.93%; H, 3.07%; N, 3.41%; Measured value: C, 62.48%; H, 3.18%; N, 3.74%.
1HNMR(CDCl
3，δppm)：8.32(s，2H)，8.30-8.32(d，2H)，8.16-8.18(d，2H)，7.93(s，1H)，7.71(s，2H)，6.93-6.98(d，4H)，2.17(s，12H)。
10 gram polyimide solid resins are dissolved among the 30 gram NMP, it are dissolved fully obtain transparent homogeneous resin solution.Adopt spin-coating method to be coated in the surface of monocrystalline silicon piece this solution, toasted 15 minutes down at 90 ℃ and 120 ℃ respectively; Place optical mask plate on resin coating film, utilize the exposure of uv-exposure machine, exposure energy is 200 milli Jiao/square centimeters; (2/1, v/v) development in 200 ℃ of curing, obtains final lithographic images then with the DMF/ tetrahydrofuran (THF).The light sensitivity 100 milli Jiao/square centimeters of this image, volumetric shrinkage＜15% does not occur subsiding, degradation phenomena such as distortion.The polyimide layer water-intake rate is 0.32%, and specific inductivity is 2.98.
Embodiment 8,
With 40 grams 1, two (4-amino-3,5-two (methyl) the phenyl)-1-(3 ' of 1-; 5 '-bis trifluoromethyl phenyl)-2; 2,2-Halothane (FMA) and 40 gram BTDA are dissolved in the 750 gram meta-cresols fully, drip the mixture of 2 gram isoquinoline 99.9 and 50 gram toluene under nitrogen protection.After dropwising, reaction mixture is heated to 180 ℃, constant temperature stirred 3 hours.After reactant is cooled to room temperature, pour in the excessive methanol, separate out white solid precipitates, white depositions obtains Intrinsical fluorinated photosensitive polyimide resin with methanol wash, 80 ℃ of following vacuum-dryings.
10 gram polyimide solid resins are dissolved in 30 gram NMP/1, the 2-ethylene dichloride (1/1, v/v) in, add 0.025 gram benzophenone (photosensitizer additive), it is dissolved fully obtains transparent homogeneous resin solution.Adopt spin-coating method to be coated in silicon polished surface this solution, toasted 12 minutes down at 80 ℃ and 100 ℃ respectively.Place optical mask plate on resin molding, utilize the exposure of uv-exposure machine, exposure energy is 150 milli Jiao/square centimeters; (2/1, v/v) development in 200 ℃ of curing, obtains final litho pattern then with the DMF/ tetrahydrofuran (THF).The volumetric shrinkage of this figure＜12% does not occur subsiding, degradation phenomena such as distortion.
Embodiment 9,
With 40 grams 1, two (4 '-amino-3 ', 5 '-two (ethyl) phenyl)-1-(4 '-trifluoromethyl)-2,2 of 1-, the 2-Halothane is dissolved in the 370 gram N,N-dimethylacetamide, adds 40 gram BTDA and other 50 gram N,N-dimethylacetamide again.Mixture in stirring at room 20 hours, obtains polyamic acid (PAA) solution of solids content 20% under nitrogen protection.With 100 the gram diacetyl oxide-pyridine mixtures (5/4, v/v) join in the PAA solution; Reactant mechanical stirring 12hr pours in the excessive methanol solution, separates out the white solid polymkeric substance.The white solid polymkeric substance in 80 ℃ of following vacuum-dryings, is obtained the Intrinsical fluorinated photosensitive polyimide solid resin.
10 gram polyimide solid resins are dissolved in the 30 gram gamma-butyrolactones, it are dissolved fully obtain transparent homogeneous resin solution.Adopt spin-coating method to be coated in the surface of clean silicon chip this solution, toasted 5 minutes down at 90 ℃ and 110 ℃ respectively; Place optical mask plate on resin coating film, utilize the exposure of uv-exposure machine, exposure energy is 200 milli Jiao/square centimeters; Use CHCl
3/ tetrahydrofuran (THF) (2/1, v/v) develop, in 180 ℃ of curing, obtain final litho pattern then.Subsiding does not appear in the volumetric shrinkage of this figure＜14%, degradation phenomenas such as distortion.
Embodiment 10,
With 40 grams 1, two (4 '-amino-3 ', 5 '-two (methyl) phenyl)-1-(4 '-trifluoromethyl)-2,2 of 1-, 2-Halothane and 40 gram BTDA are dissolved in the 750 gram meta-cresols fully, drip 2 gram isoquinoline 99.9 and 50 gram toluene mixture under nitrogen protection.After dropwising, reaction mixture is heated to 180 ℃, constant temperature stirred 8 hours.After reactant is cooled to room temperature, pour in the excessive methanol, separate out white solid precipitates, the white depositions methanol wash, 80 ℃ of following vacuum-dryings obtain Intrinsical fluorinated photosensitive polyimide resin.
10 gram polyimide solid resins are dissolved in 30 gram gamma-butyrolactone/1, the 2-ethylene dichloride (1/1, v/v) in, it is dissolved fully obtains transparent homogeneous resin solution.Adopt spin-coating method to be coated in the surface of clean glass this solution, toasted 15 minutes down at 80 ℃ and 120 ℃ respectively; Place optical mask plate on resin coating film, utilize the exposure of uv-exposure machine, exposure energy is 200 milli Jiao/square centimeters; (2/1, v/v) development in 200 ℃ of curing, obtains final litho pattern then with the DMF/ tetrahydrofuran (THF).Subsiding does not appear in the volumetric shrinkage of this figure＜12%, degradation phenomenas such as distortion.
Embodiment 11,
With 32 grams 1,1-two (4 '-amino-3 ', 5 '-two (sec.-propyl) phenyl)-1-(4 '-trifluoromethyl)-2,2,2-Halothane and 10 grams 3,4 '-diaminodiphenyl oxide (3,4 '-ODA) is dissolved in 750 gram N, in the dinethylformamide, add 40 gram BTDA and other 50 gram N again, dinethylformamide.Mixture in stirring at room 20 hours, obtains polyamic acid (PAA) solution of solids content 25% under nitrogen protection.With 100 the gram diacetyl oxide-pyridine mixtures (5/4, v/v) join in the PAA solution; Reactant heated 4 hours down for 60 ℃, poured in the excessive methanol solution, separated out the white solid polymkeric substance.The white solid polymkeric substance in 80 ℃ of following vacuum-dryings, is obtained the Intrinsical fluorinated photosensitive polyimide solid resin.
10 gram polyimide solid resins are dissolved in the 30 gram Y-butyrolactone, it are dissolved fully obtain transparent homogeneous resin solution.Adopt spin-coating method to be coated in the surface of monocrystalline silicon piece this solution, toasted 5-10 minute down at 90 ℃ and 115 ℃ respectively; Place optical mask plate on resin coating film, utilize the exposure of uv-exposure machine, exposure energy is 220 milli Jiao/square centimeters; Use CHCl
3/ tetrahydrofuran (THF) (2/1, v/v) develop, in 180 ℃ of curing, obtain final litho pattern then.The volumetric shrinkage of this figure＜13% does not occur subsiding, degradation phenomena such as distortion.
Embodiment 12
With 40 grams 1, two (4 '-amino-3 ', 5 '-two (methyl) phenyl)-1-(3 '-trifluoromethyl)-2,2 of 1-, 2-Halothane and 40 gram BTDA are dissolved in the 750 gram meta-cresols fully, drip the toluene mixture of 2 gram isoquinoline 99.9 and 50 grams under nitrogen protection.After dropwising, reaction mixture is heated to 180 ℃, constant temperature stirred 3 hours.After reactant is cooled to room temperature, pour in the excessive methanol, separate out white solid precipitates.The white depositions methanol wash, 80 ℃ of following vacuum-dryings obtain Intrinsical fluorinated photosensitive polyimide resin.
10 gram polyimide solid resins are dissolved in 30 gram gamma-butyrolactone/1, in the 2-ethylene dichloride (1/1 v/v), it are dissolved fully obtain transparent homogeneous resin solution.Adopt spin-coating method to be coated in the surface of silicon chip this solution, toasted 10 minutes down at 90 ℃ and 130 ℃ respectively.Place optical mask plate on resin coating film, utilize the exposure of uv-exposure machine, exposure energy is 240 milli Jiao/square centimeters.(2/1, v/v) development in 200 ℃ of curing, obtains final litho pattern then with the DMF/ tetrahydrofuran (THF).Subsiding does not appear in the volumetric shrinkage of this figure＜12%, degradation phenomenas such as distortion,
Embodiment 13
With 40 grams 1, two (4 '-amino-3 ', 5 '-two (methyl) phenyl)-1-(3 ', 5 '-bis trifluoromethyl phenyl)-2,2 of 1-, 2-Halothane and molecular weight regulator γ-An Bingjisanyiyangjiguiwan 2 grams are dissolved in the 670 gram gamma-butyrolactones.In mixing solutions, add 40 gram BTDA and other 50 gram gamma-butyrolactones again.Mixture in stirring at room 20 hours, obtains polyamic acid (PAA) solution of solids content 10% under nitrogen protection.With 50 gram diacetyl oxide-pyridine mixtures (5/4, v/v) join in the PAA solution, reactant stirs 12hr, pours in the excessive methanol solution, separates out the white solid polymkeric substance.The white solid polymkeric substance in 80 ℃ of following vacuum-dryings, is obtained the Intrinsical fluorinated photosensitive polyimide solid resin.
10 gram polyimide solid resins and photosensitizer additive benzophenone 4 grams are dissolved in the 30 gram gamma-butyrolactones, it are dissolved fully obtain transparent homogeneous resin solution.Adopt spin-coating method to be coated in the surface of silicon chip this solution, toasted 5 minutes down at 90 ℃ and 110 ℃ respectively; Place optical mask plate on resin coating film, utilize the exposure of uv-exposure machine, exposure energy is 200 milli Jiao/square centimeters; Use CHCl
3/ tetrahydrofuran (THF) (2/1, v/v) develop, in 180 ℃ of curing, obtain final litho pattern then.The volumetric shrinkage of this figure＜10% does not occur subsiding, degradation phenomena such as distortion.
Embodiment 14
With 40 grams 1, two (4 '-amino-3 ', 5 '-3,5-dimethylphenyl)-1-(3 ' of 1-; 5 '-two (trifluoromethyl) phenyl)-2; 2,2-Halothane and 40 gram BTDA are dissolved in the 750 gram meta-cresols fully, drip the mixture of 2 gram isoquinoline 99.9 and 50 gram toluene under nitrogen protection.After dropwising, reaction mixture is heated to 180 ℃, constant temperature stirred 3 hours; After reactant is cooled to room temperature, pour in the excessive methanol, separate out white solid precipitates; White depositions obtains Intrinsical fluorinated photosensitive polyimide resin with methanol wash, 80 ℃ of following vacuum-dryings.
10 gram polyimide solid resins are dissolved in 30 gram gamma-butyrolactone/1, in the 2-ethylene dichloride (1/1 v/v), it are dissolved fully obtain transparent homogeneous resin solution.Adopt spin-coating method to be coated in the surface of silicon chip this solution, toasted 15 minutes down at 80 ℃ and 120 ℃ respectively; Place optical mask plate on resin coating film, utilize the exposure of uv-exposure machine, exposure energy is 200 milli Jiao/square centimeters; (2/1, v/v) development in 200 ℃ of curing, obtains final litho pattern then with the DMF/ tetrahydrofuran (THF).Subsiding does not appear in the volumetric shrinkage of this figure＜12%, degradation phenomenas such as distortion.
Embodiment 15
With 40 grams 1, two (4 '-amino-3 ', 5 '-3,5-dimethylphenyl)-1-(4 '-trifluoromethyl)-2,2 of 1-, 2-Halothane and molecular weight regulator Tetra hydro Phthalic anhydride 2 grams are dissolved in the 670 gram tetrahydrofuran (THF)s.In mixing solutions, add 38 gram BTDA and other 50 gram tetrahydrofuran (THF)s again.Mixture in stirring at room 20 hours, obtains polyamic acid (PAA) solution of solids content 10% under nitrogen protection.With 50 the gram diacetyl oxide-pyridine mixtures (5/4, v/v) join in the PAA solution.Reactant stirs 12hr, pours in the excessive methanol solution, separates out the white solid polymkeric substance.The white solid polymkeric substance in 80 ℃ of following vacuum-dryings, is obtained the Intrinsical fluorinated photosensitive polyimide solid resin.
10 gram polyimide solid resins and photosensitizer additive benzophenone 4 grams are dissolved in the 30 gram gamma-butyrolactones, it are dissolved fully obtain transparent homogeneous resin solution.Adopt spin-coating method to be coated in the surface of silicon chip this solution, toasted 5 minutes down at 90 ℃ and 110 ℃ respectively; Place optical mask plate on resin coating film, utilize the exposure of uv-exposure machine, exposure energy is 200 milli Jiao/square centimeters; (2/1, v/v) development in 180 ℃ of curing, obtains final litho pattern then with chloroform/tetrahydrofuran (THF).The volumetric shrinkage of this figure＜14% does not occur subsiding, degradation phenomena such as distortion.
Embodiment 156
With 40 grams 1, two (4 '-amino-3 ', 5 '-3,5-dimethylphenyl)-1-(3 '-trifluoromethyl)-2 of 1-; 2; the 2-Halothane, 2 gram Tetra hydro Phthalic anhydrides and 38 gram BTDA are dissolved in the 750 gram meta-cresols fully, drip the mixture of 2 gram isoquinoline 99.9 and 50 gram toluene under nitrogen protection.After dropwising, reaction mixture is heated to 180 ℃, constant temperature stirred 3 hours; After reactant is cooled to room temperature, pour in the excessive methanol, separate out white solid precipitates; White depositions obtains Intrinsical fluorinated photosensitive polyimide resin with methanol wash, 80 ℃ of following vacuum-dryings.
10 gram polyimide solid resins are dissolved in 30 gram gamma-butyrolactone/1, the 2-ethylene dichloride (1/1, v/v) in, it is dissolved fully obtains transparent homogeneous resin solution.Adopt spin-coating method to be coated in the surface of silicon chip this solution, toasted 15 minutes down at 80 ℃ and 120 ℃ respectively; Place optical mask plate on resin coating film, utilize the exposure of uv-exposure machine, exposure energy is 200 milli Jiao/square centimeters; (2/1, v/v) development in 200 ℃ of curing, obtains final litho pattern then with the DMF/ tetrahydrofuran (THF).Subsiding does not appear in the volumetric shrinkage of this figure＜15%, degradation phenomenas such as distortion.
Embodiment 17
With 35 grams 1,1-two (4 '-amino-3 ', 5 '-3,5-dimethylphenyl)-1-(4 '-trifluoromethyl)-2,2,2-Halothane and 5 grams 3,3 '-dimethyl-4,4 '-diaminodiphenylmethane is dissolved in 750 gram N, in the dinethylformamide, add 40 gram BTDA and other 50 gram N again, dinethylformamide.Mixture in stirring at room 20 hours, obtains polyamic acid (PAA) solution of solids content 25% under nitrogen protection.With 100 the gram diacetyl oxide-pyridine mixtures (5/4, v/v) join in the PAA solution; Reactant heated 4 hours down for 60 ℃, poured in the excessive methanol solution, separated out the white solid polymkeric substance.The white solid polymkeric substance in 80 ℃ of following vacuum-dryings, is obtained the Intrinsical fluorinated photosensitive polyimide solid resin.
10 gram polyimide solid resins are dissolved in the 30 gram Y-butyrolactone, it are dissolved fully obtain transparent homogeneous resin solution.Adopt spin-coating method to be coated in the surface of monocrystalline silicon piece this solution, toasted 5-10 minute down at 90 ℃ and 115 ℃ respectively; Place optical mask plate on resin coating film, utilize the exposure of uv-exposure machine, exposure energy is 220 milli Jiao/square centimeters; Use CHCl
3/ tetrahydrofuran (THF) (2/1, v/v) develop, in 180 ℃ of curing, obtain final litho pattern then.The volumetric shrinkage of this figure＜13% does not occur subsiding, degradation phenomena such as distortion.
Embodiment 18
With 28 grams 1, two (4 '-amino-3 ', 5 '-3,5-dimethylphenyl)-1-(4 '-trifluoromethyl)-2,2 of 1-, 2-Halothane and 12 grams 3,3 ', 5,5 '-tetraethyl--4,4 '-diaminodiphenylmethane is dissolved in 750 gram N, in the dinethylformamide, add 47 gram BTDA and other 50 gram N again, dinethylformamide.Mixture in stirring at room 20 hours, obtains polyamic acid (PAA) solution under nitrogen protection.With 100 the gram diacetyl oxide-pyridine mixtures (5/4, v/v) join in the PAA solution; Reactant heated 4 hours down for 60 ℃, poured in the excessive methanol solution, separated out the white solid polymkeric substance.The white solid polymkeric substance in 80 ℃ of following vacuum-dryings, is obtained the Intrinsical fluorinated photosensitive polyimide solid resin.
10 gram polyimide solid resins are dissolved in the 30 gram Y-butyrolactone, it are dissolved fully obtain transparent homogeneous resin solution.Adopt spin-coating method to be coated in the surface of monocrystalline silicon piece this solution, toasted 5-10 minute down at 90 ℃ and 115 ℃ respectively; Place optical mask plate on resin coating film, utilize the exposure of uv-exposure machine, exposure energy is 220 milli Jiao/square centimeters; Use CHCl
3/ tetrahydrofuran (THF) (2/1, v/v) develop, in 180 ℃ of curing, obtain final litho pattern then.The volumetric shrinkage of this figure＜13% does not occur subsiding, degradation phenomena such as distortion.
Embodiment 19
With 40 grams 1, two (4 '-amino-3 ', 5 '-3,5-dimethylphenyl)-1-(4 '-trifluoromethyl)-2 of 1-, 2,2-Halothane and 1.5 grams 2,4 '-diaminodiphenyl oxide are dissolved in 750 gram N, in the dinethylformamide, add 40 gram BTDA and other 50 gram N again, dinethylformamide.Mixture in stirring at room 20 hours, obtains polyamic acid (PAA) solution under nitrogen protection.With 100 the gram diacetyl oxide-pyridine mixtures (5/4, v/v) join in the PAA solution; Reactant heated 4 hours down for 60 ℃, poured in the excessive methanol solution, separated out the white solid polymkeric substance.The white solid polymkeric substance in 80 ℃ of following vacuum-dryings, is obtained the Intrinsical fluorinated photosensitive polyimide solid resin.
10 gram polyimide solid resins are dissolved in the 30 gram Y-butyrolactone, it are dissolved fully obtain transparent homogeneous resin solution.Adopt spin-coating method to be coated in the surface of monocrystalline silicon piece this solution, toasted 5-10 minute down at 90 ℃ and 115 ℃ respectively; Place optical mask plate on resin coating film, utilize the exposure of uv-exposure machine, exposure energy is 220 milli Jiao/square centimeters; Use CHCl
3/ tetrahydrofuran (THF) (2/1, v/v) develop, in 180 ℃ of curing, obtain final litho pattern then.The volumetric shrinkage of this figure＜13% does not occur subsiding, degradation phenomena such as distortion.
Embodiment 20
With 40 grams 1, two (4 '-amino-3 ', 5 '-3,5-dimethylphenyl)-1-(4 '-trifluoromethyl)-2,2 of 1-, the 2-Halothane is dissolved in the 670 gram tetrahydrofuran (THF)s.In mixing solutions, add 38 gram BTDA and molecular weight regulator phenylacetylene phthalic anhydride 2 grams and other 50 gram tetrahydrofuran (THF)s again.Mixture in stirring at room 20 hours, obtains polyamic acid (PAA) solution of solids content 10% under nitrogen protection.With 50 the gram diacetyl oxide-pyridine mixtures (5/4, v/v) join in the PAA solution.Reactant stirs 12hr, pours in the excessive methanol solution, separates out the white solid polymkeric substance.The white solid polymkeric substance in 80 ℃ of following vacuum-dryings, is obtained the Intrinsical fluorinated photosensitive polyimide solid resin.
10 gram polyimide solid resins and photosensitizer additive benzophenone 4 grams are dissolved in the 30 gram gamma-butyrolactones, it are dissolved fully obtain transparent homogeneous resin solution.Adopt spin-coating method to be coated in the surface of silicon chip this solution, toasted 5 minutes down at 90 ℃ and 110 ℃ respectively; Place optical mask plate on resin coating film, utilize the exposure of uv-exposure machine, exposure energy is 200 milli Jiao/square centimeters; (2/1, v/v) development in 180 ℃ of curing, obtains final litho pattern then with chloroform/tetrahydrofuran (THF).The volumetric shrinkage of this figure＜14% does not occur subsiding, degradation phenomena such as distortion.
Embodiment 21
With 40 grams 1, two (4 '-amino-3 ', 5 '-3,5-dimethylphenyl)-1-(4 '-trifluoromethyl)-2,2 of 1-, 2-Halothane and molecular weight regulator phenylacetylene aniline 2 grams are dissolved in the 670 gram dimethyl sulfoxide (DMSO).In mixing solutions, add 38 gram BTDA and other 50 gram dimethyl sulfoxide (DMSO) again.Mixture in stirring at room 20 hours, obtains polyamic acid (PAA) solution of solids content 10% under nitrogen protection.With 50 the gram diacetyl oxide-pyridine mixtures (5/4, v/v) join in the PAA solution.Reactant stirs 12hr, pours in the excessive methanol solution, separates out the white solid polymkeric substance.The white solid polymkeric substance in 80 ℃ of following vacuum-dryings, is obtained the Intrinsical fluorinated photosensitive polyimide solid resin.
10 gram polyimide solid resins and photosensitizer additive benzophenone 4 grams are dissolved in the 30 gram gamma-butyrolactones, it are dissolved fully obtain transparent homogeneous resin solution.Adopt spin-coating method to be coated in the surface of silicon chip this solution, toasted 5 minutes down at 90 ℃ and 110 ℃ respectively; Place optical mask plate on resin coating film, utilize the exposure of uv-exposure machine, exposure energy is 200 milli Jiao/square centimeters; (2/1, v/v) development in 180 ℃ of curing, obtains final litho pattern then with chloroform/tetrahydrofuran (THF).The volumetric shrinkage of this figure＜14% does not occur subsiding, degradation phenomena such as distortion.
Embodiment 22
With 40 grams 1,1-two (4 '-amino-3 ', 5 '-3,5-dimethylphenyl)-1-(4 '-trifluoromethyl)-2,2,2-Halothane and molecular weight regulator be two-and (γ-ammonia butyl) tetramethyl-silica alkane 1.5 grams are dissolved in 670 gram N, in the dinethylformamide.In mixing solutions, add 38 gram BTDA and other 50 gram N again, dinethylformamide.Mixture in stirring at room 20 hours, obtains polyamic acid (PAA) solution of solids content 10% under nitrogen protection.With 50 the gram diacetyl oxide-pyridine mixtures (5/4, v/v) join in the PAA solution.Reactant stirs 12hr, pours in the excessive methanol solution, separates out the white solid polymkeric substance.The white solid polymkeric substance in 80 ℃ of following vacuum-dryings, is obtained the Intrinsical fluorinated photosensitive polyimide solid resin.
10 gram polyimide solid resins and photosensitizer additive 4,4 '-two (dimethylamino) benzophenone 1 gram are dissolved in the 30 gram gamma-butyrolactones, it are dissolved fully obtain transparent homogeneous resin solution.Adopt spin-coating method to be coated in the surface of silicon chip this solution, toasted 5 minutes down at 90 ℃ and 110 ℃ respectively; Place optical mask plate on resin coating film, utilize the exposure of uv-exposure machine, exposure energy is 200 milli Jiao/square centimeters; (2/1, v/v) development in 180 ℃ of curing, obtains final litho pattern then with chloroform/tetrahydrofuran (THF).The volumetric shrinkage of this figure＜14% does not occur subsiding, degradation phenomena such as distortion.
Embodiment 23
With 40 grams 1,1-two (4 '-amino-3 ', 5 '-3,5-dimethylphenyl)-1-(3 '-trifluoromethyl)-2,2,2-Halothane and molecular weight regulator be two-and (γ-ammonia butyl) tetraphenyl polysiloxane 1.5 grams are dissolved in 670 gram N, in the dinethylformamide.In mixing solutions, add 38 gram BTDA and other 50 gram N again, dinethylformamide.Mixture in stirring at room 20 hours, obtains polyamic acid (PAA) solution of solids content 10% under nitrogen protection.With 50 the gram diacetyl oxide-pyridine mixtures (5/4, v/v) join in the PAA solution.Reactant stirs 12hr, pours in the excessive methanol solution, separates out the white solid polymkeric substance.The white solid polymkeric substance in 80 ℃ of following vacuum-dryings, is obtained the Intrinsical fluorinated photosensitive polyimide solid resin.
With 10 gram polyimide solid resin and photosensitizer additives 2, two (4 '-diethylin benzyl) pimelinketone 0.2 grams of 6-are dissolved in the 30 gram gamma-butyrolactones, it is dissolved fully obtain transparent homogeneous resin solution.Adopt spin-coating method to be coated in the surface of silicon chip this solution, toasted 5 minutes down at 90 ℃ and 110 ℃ respectively; Place optical mask plate on resin coating film, utilize the exposure of uv-exposure machine, exposure energy is 200 milli Jiao/square centimeters; (2/1, v/v) development in 180 ℃ of curing, obtains final litho pattern then with chloroform/tetrahydrofuran (THF).The volumetric shrinkage of this figure＜14% does not occur subsiding, degradation phenomena such as distortion.
Claims (9)
1, a kind of Intrinsical fluorinated photosensitive polyimide resin is mainly formed by polycondensation by following parts by weight of component:
3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride 40,
The methane diamines 20-42 of polyalkyl-substituted aromatic family of the fluorinated aromatic pendant of formula I structure;
Among the formula I, A, B, C, D are that carbonatoms is the alkyl of 1-10; E, F, G are H atom or trifluoromethyl.
2, Intrinsical fluorinated photosensitive polyimide resin according to claim 1 is characterized in that: A, B, C, D are methyl, ethyl or sec.-propyl.
3, Intrinsical fluorinated photosensitive polyimide resin according to claim 1 and 2 is characterized in that: describedly carry out the component that polycondensation also has following weight part:
Aromatic diamine 0-20,
Molecular weight regulator 0-50.
4, Intrinsical fluorinated photosensitive polyimide resin according to claim 3, it is characterized in that: described aromatic diamine is a Ursol D, mphenylenediamine, 2, the 5-diaminotoluene, 2, the 6-diaminotoluene, 4,4 '-diaminodiphenyl oxide, 3,4 '-diaminodiphenyl oxide, 3,3 '-diaminodiphenyl oxide, 2,4 '-diaminodiphenyl oxide, 4,4 '-diaminodiphenylsulfone(DDS), 4,4 '-diaminodiphenylmethane, 3,3 '-dimethyl-4,4 '-diaminodiphenylmethane, 3,3 ', 5,5 '-tetramethyl--4,4 '-diaminodiphenylmethane, 3,3 ', 5,5 '-tetraethyl--4,4 '-diaminodiphenylmethane, 4,4 '-two (4-amino-benzene oxygen) propane, 4,4 '-two (4-amino-benzene oxygen) benzene, 4,4 '-two (4-amino-benzene oxygen) sulfobenzides and the mixture that mixes by arbitrary proportion thereof;
Described molecular weight regulator is a Tetra hydro Phthalic anhydride, the phenylacetylene phthalic anhydride, phenylacetylene aniline, norbornene dicarboxylic anhydride, aniline, γ-An Bingjisanyiyangjiguiwan, γ-An Bingjisanjiayangjiguiwan, two-(γ-aminopropyl) tetramethyl-silica alkane, two-(γ-ammonia butyl) tetramethyl-silica alkane, two-(γ-aminopropyl) tetramethyl-polysiloxane, two-(γ-aminopropyl) tetraphenyl silica alkane, two-(γ-aminopropyl) tetraphenyl polysiloxane, two-(γ-ammonia butyl) tetraphenyl silica alkane, two-(γ-ammonia butyl) tetraphenyl polysiloxane and the mixture that mixes by arbitrary proportion thereof.
5, the preparation method of the described Intrinsical fluorinated photosensitive polyimide resin of claim 1 comprises the steps:
1) polyalkyl-substituted aromatic family methane diamines and the 0-20 weight part aromatic diamine with the fluorinated aromatic pendant of 20-42 weight part formula I structure is dissolved in the 300-800 weight part organic solvent, under nitrogen protection, add 40 weight 3 again, 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride and 0-50 weight part molecular weight regulator, in nitrogen atmosphere stirring at room 12-24 hour then, obtain polyamic acid solution;
2) add 28-100 weight part diacetyl oxide-pyridine mixtures in above-mentioned solution, diacetyl oxide in this mixture/pyridine volume ratio is 5/4, at 25 ℃ of-60 ℃ of following stirring reaction 4-12 hours, obtains described eigenmode photosensitive polyimide resin.
6, preparation method according to claim 5, it is characterized in that: described aromatic diamine is a Ursol D, mphenylenediamine, 2, the 5-diaminotoluene, 2, the 6-diaminotoluene, 4,4 '-diaminodiphenyl oxide, 3,4 '-diaminodiphenyl oxide, 3,3 '-diaminodiphenyl oxide, 2,4 '-diaminodiphenyl oxide, 4,4 '-diaminodiphenylsulfone(DDS), 4,4 '-diaminodiphenylmethane, 3,3 '-dimethyl-4,4 '-diaminodiphenylmethane, 3,3 ', 5,5 '-tetramethyl--4,4 '-diaminodiphenylmethane, 3,3 ', 5,5 '-tetraethyl--4,4 '-diaminodiphenylmethane, 4,4 '-two (4-amino-benzene oxygen) propane, 4,4 '-two (4-amino-benzene oxygen) benzene, 4,4 '-two (4-amino-benzene oxygen) sulfobenzides and the mixture that mixes by arbitrary proportion thereof;
Described molecular weight regulator is a Tetra hydro Phthalic anhydride, the phenylacetylene phthalic anhydride, phenylacetylene aniline, norbornene dicarboxylic anhydride, aniline, γ-An Bingjisanyiyangjiguiwan, γ-An Bingjisanjiayangjiguiwan, two-(γ-aminopropyl) tetramethyl-silica alkane, two-(γ-ammonia butyl) tetramethyl-silica alkane, two-(γ-aminopropyl) tetramethyl-polysiloxane, two-(γ-aminopropyl) tetraphenyl silica alkane, two-(γ-aminopropyl) tetraphenyl polysiloxane, two-(γ-ammonia butyl) tetraphenyl silica alkane, two-(γ-ammonia butyl) tetraphenyl polysiloxane and the mixture that mixes by arbitrary proportion thereof.
7, according to claim 5 or 6 described preparation methods, it is characterized in that: described organic solvent is N-Methyl pyrrolidone, N, N-N,N-DIMETHYLACETAMIDE, N, dinethylformamide, dimethyl sulfoxide (DMSO), gamma-butyrolactone, chloroform, 1,2-ethylene dichloride, tetrahydrofuran (THF), acetone and the mixing solutions that mixes by arbitrary proportion thereof.
8; the preparation method of the described Intrinsical fluorinated photosensitive polyimide resin of claim 1; it is polyalkyl-substituted aromatic family methane diamines with the fluorinated aromatic pendant of 20-42 weight part formula I structure; 0-20 weight part aromatic diamine; 0-50 weight part molecular weight regulator and 40 weight parts 3; 3 '; 4; 4 '-benzophenone tetracarboxylic dianhydride is dissolved in the 400-850 weight part meta-cresol; under nitrogen protection, drip 1-5 weight part isoquinoline 99.9 and 50-200 parts by weight of toluene; reaction mixture is heated to 160-180 ℃ of reaction 3-9 hour, obtains described eigenmode photosensitive polyimide resin.
9, preparation method according to claim 8 is characterized in that: described aromatic diamine is a Ursol D, mphenylenediamine, 2, the 5-diaminotoluene, 2, the 6-diaminotoluene, 4,4 '-diaminodiphenyl oxide, 3,4 '-diaminodiphenyl oxide, 3,3 '-diaminodiphenyl oxide, 2,4 '-diaminodiphenyl oxide, 4,4 '-diaminodiphenylsulfone(DDS), 4,4 '-diaminodiphenylmethane, 3,3 '-dimethyl-4,4 '-diaminodiphenylmethane, 3,3 ', 5,5 '-tetramethyl--4,4 '-diaminodiphenylmethane, 3,3 ', 5,5 '-tetraethyl--4,4 '-diaminodiphenylmethane, 4,4 '-two (4-amino-benzene oxygen) propane, 4,4 '-two (4-amino-benzene oxygen) benzene, 4,4 ,-two (4-amino-benzene oxygen) sulfobenzides and the mixture that mixes by arbitrary proportion thereof;
Described molecular weight regulator is a Tetra hydro Phthalic anhydride, the phenylacetylene phthalic anhydride, phenylacetylene aniline, norbornene dicarboxylic anhydride, aniline, γ-An Bingjisanyiyangjiguiwan, γ-An Bingjisanjiayangjiguiwan, two-(γ-aminopropyl) tetramethyl-silica alkane, two-(γ-ammonia butyl) tetramethyl-silica alkane, two-(γ-aminopropyl) tetramethyl-polysiloxane, two-(γ-aminopropyl) tetraphenyl silica alkane, two-(γ-aminopropyl) tetraphenyl polysiloxane, two-(γ-ammonia butyl) tetraphenyl silica alkane, two-(γ-ammonia butyl) tetraphenyl polysiloxane and the mixture that mixes by arbitrary proportion thereof.
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| WO2013144856A1 (en) * | 2012-03-28 | 2013-10-03 | Basf Se | Polyimides as dielectrics |
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| CN106292205A (en) * | 2015-06-24 | 2017-01-04 | 东京应化工业株式会社 | Pattern Formation Method |
| CN110092908A (en) * | 2019-04-03 | 2019-08-06 | 中国科学院化学研究所 | A kind of Kapton and its preparation method and application |
| WO2020200229A1 (en) * | 2019-04-03 | 2020-10-08 | 中国科学院化学研究所 | Polyimide thin film and preparation method and application thereof |
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