CN1405631A - Self-sensitizing type super-branched polyimide photo-sensitive material and its preparing method - Google Patents
Self-sensitizing type super-branched polyimide photo-sensitive material and its preparing method Download PDFInfo
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- CN1405631A CN1405631A CN 02137747 CN02137747A CN1405631A CN 1405631 A CN1405631 A CN 1405631A CN 02137747 CN02137747 CN 02137747 CN 02137747 A CN02137747 A CN 02137747A CN 1405631 A CN1405631 A CN 1405631A
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Abstract
This invention discloses a new type of photosensitive material of self-sensibilizing super-branching polyimide and its preparation method. Taking 1,3,5-tri(4-amido phenoxy) benzene and diacid anhydride monomer with ketone as the raw material (mole ratio=1/2) and dissolve the diacid anhydride monomer in solvent and add tianmino monomer solution slowly for polymerization to get super-branching polyamide acid with macromolecular chain end group as the acid anhydride group then to add ortho-substituted aniline to react with acid anhydride group for functionalization, further to get super-branching polyamide photosensitive material by the chemical imination method. The said polymer is a self-sensibilizing-type photosensitive polyimide with high photosnesitivity, resolution, fine thermal performance and organic dissolubility with wide applicable prospects in aviation and microelectronic fields.
Description
Technical field: the invention belongs to a kind of functional high molecule material and preparation method thereof, particularly have self-sensitizing type super-branched polyimide photo-sensitive material of UV photosensitive performance and preparation method thereof.
Background technology: polyimide is the high-performance polymer material that a class has good thermal stability, chemical stability, dielectric properties and mechanical property, in Modern High-Tech fields such as space industry and microelectronics industry very important application is arranged.For example in the microelectronics process industry, as all kinds of device passivation protection and interlayer dielectric etc.In the application in these areas, polyimide layer must form fine connecting through hole or connect window.Traditional practice is to be coated with the last layer photoresist on the polyimide film of non-photosensitivity, exposure obtains the photoresist figure then, figure makes masking layer with photoresist, adopt the polyimide of mordant corrosion lower floor, remove photoresist layer again, just can obtain the polyimide figure, the loaded down with trivial details poor efficiency of this technological process.Aggressiveness before the polyamic acid that present widely used polyimide light-sensitive material is the tool photosensitivity carries out hot imidization after being photo-etched into figure earlier again, and needed high temperature of hot imidization process and serious film shrink the application that has limited this class photochromics; There is the low shortcoming of lightsensitivity [M.K.Ghosh ﹠amp again in the self-sensitizing type light-sensitive polyimide of full imidization; K.L.Mittal Ed.Polyimides, Marcel Dekker, 1996].Therefore, it is of far-reaching significance that research and development has the polyimide light-sensitive material of full imidization of better photosensitivity.
Summary of the invention: the present invention prepares self-sensitizing type super-branched polyimide photo-sensitive material from Molecular Structure Design, and its constitutional repeating unit is shown below:
Wherein, polymerization degree n=1-50, m=1-50; Ar is:
R is:
Preparation were established of the present invention is as follows: with a kind of triamido monomer that contains the diphenyl ether structure is raw material, carrying out with the dicarboxylic anhydride monomer of ketone group containing that polymerization obtains with the acid anhydrides is aggressiveness before the ultrabranching polyamide acid of end group, then, with its end anhydride group of aniline modification that the ortho position replaces, the aroma type light-sensitive polyimide that obtains having excellent dissolution performance and thermal behavior after the chemical imidization.
Polyreaction equation of the present invention can be expressed as:
Wherein, polymerization degree n=1-50, m=1-50; Ar is:
R is:
The concrete preparation method of self-sensitizing type super-branched polyimide photo-sensitive material of the present invention is as follows: (a) at first prepare ultrabranching polyamide acid: with 1,3,5-three (4-amino-benzene oxygen) benzene is that the dicarboxylic anhydride of three amine monomers and ketone group containing is the dicarboxylic anhydride monomer, mol ratio is 1/2, under 40 ℃ of nitrogen protections, the dicarboxylic anhydride monomer is dissolved in the organic solvent, its concentration is 20-100mmol/L, adopt the way that drips, the organic solvent solution that slowly adds three amine monomers, its concentration is 10-50mmol/L, it is the ultrabranching polyamide acid of macromolecular chain end group that polymerization obtains with the anhydride group, and the reaction time is 5 hours; (b) then carry out end group functional: add the aniline that the ortho position replaces, the mol ratio of itself and three amine monomers is 1-1.5/1, reacts 5 hours under 40 ℃ of nitrogen protections with the end group anhydride group of ultrabranching polyamide acid; (c) carry out chemical imidization subsequently: add dewatering agent acetic anhydride and catalyst of triethylamine under 40 ℃ of nitrogen protections, the reaction time is 12 hours.Reaction precipitates in a large amount of precipitation agent methanol after finishing, and filters, and cleans, and three times repeatedly, 40 ℃ of following vacuum drying obtained target product in 48 hours.
The dewatering agent that the present invention uses is acetic anhydride, and catalyzer is a triethylamine; Dewatering agent and catalyst concentration are 5-10wt%, and the weight ratio of dewatering agent/catalyzer is 3/1.
The organic solvent that the present invention uses comprises N-methyl-pyrrolidone, N, dinethylformamide, N,N-dimethylacetamide.
The present invention uses 1,3, and 5-three (4-amino-benzene oxygen) benzene is three amine monomers, its structural formula as the formula (2):
The dicarboxylic anhydride monomer of the ketone group containing that the present invention uses comprises: benzophenone tetracarboxylic dianhydride, benzophenone based benzene tertacarbonic acid's dianhydride, two phenoxy group benzophenone tetracarboxylic dianhydrides, anthraquinone tetracarboxylic dianhydride, xanthone tetracarboxylic dianhydride, thio-xanthene-one tetracarboxylic dianhydride.Its structural formula is as the formula (3):
Wherein, Ar is:
The aniline that the ortho position that the present invention uses replaces comprises: o-toluidine, o ethyl aniline, adjacent isobutyl-aniline, 2,6-xylidin, 2-methyl-6-ethylaniline, 2,6-diethylaniline, o-aminoanisole, 2,6-dimethoxyaniline, methylmercapto aniline, 2,6-diformazan sulfenyl aniline.Its structural formula is as the formula (4):
Self-sensitizing type super-branched polyimide photo-sensitive material of the present invention, because its side group that photo-crosslinking takes place is in the peripheral ends of the hyperbranched macromolecular chain of three-dimensional chondritic, luminous sensitivity is greatly enhanced.It is again a kind of photochromics of full imidization, and the photoetching formation caudacoria shrinks very little.Simultaneously, dissaving polymer intrinsic three-dimensional ball-type molecular conformation, big molecule average-size is little, chain entanglement is few, makes this photochromics have high resolution.So it will have a wide range of applications in fields such as the more and more higher microelectronics industry of integrated degree, aircraft industry.
Embodiment: following embodiment further specifies of the present invention, rather than limits the scope of the invention.
Embodiment 1:
With 2.5mmol 3,3 ', 4,4 '-benzophenone dicarboxylic anhydride (BTDA) is dissolved in 30ml N-methyl-pyrrolidone, adopt the way that drips, the 30ml N-methyl-pyrrolidone solution that under 40 ℃ of nitrogen protections, slowly adds 1.25mmol three amine monomers, polymerization 5 hours, obtaining with the anhydride group is the ultrabranching polyamide acid of macromolecular chain end group; Then add the 1.5mmol o-toluidine, reaction is 5 hours under 40 ℃ of nitrogen protections; Add 7.5 gram acetic anhydrides and 2.5 gram triethylamines subsequently, reaction is 12 hours under 40 ℃ of nitrogen protections, after reaction finishes; precipitating is filtered washed with methanol three times in 800ml methyl alcohol; 40 ℃ of vacuum drying 48 hours obtain target product: super-branched polyimide photo-sensitive material 1.2 grams.
Embodiment 2:
With 2.5mmol 3,3 ', 4,4 '-benzophenone dicarboxylic anhydride (BTDA) is dissolved in 30ml N, and the N dimethyl acetamide adopts the way that drips, the 30ml N that under 40 ℃ of nitrogen protections, slowly adds 1.25mmol three amine monomers, the N dimethyl acetamide, polymerization 5 hours, obtaining with the anhydride group is the ultrabranching polyamide acid of macromolecular chain end group; Then add the adjacent isobutyl-aniline of 1.5mmol, reaction is 5 hours under 40 ℃ of nitrogen protections; Add 7.5 gram acetic anhydrides and 2.5 gram triethylamines subsequently, reaction is 12 hours under 40 ℃ of nitrogen protections, after reaction finishes; precipitating is filtered washed with methanol three times in 800ml methyl alcohol; 40 ℃ of vacuum drying 48 hours obtain target product: super-branched polyimide photo-sensitive material 1.2 grams.
Embodiment 3:
2.5mmol anthraquinone dicarboxylic anhydride (AQDA) is dissolved in 30ml N, the N dimethyl formamide, adopt the way that drips, the 30ml N N that under 40 ℃ of nitrogen protections, slowly adds 1.25mmol three amine monomers, the N dimethyl formamide, polymerization 5 hours, obtaining with the anhydride group is the ultrabranching polyamide acid of macromolecular chain end group; Then add 1.5mmol 2, the 6-dimethoxyaniline, reaction is 5 hours under 40 ℃ of nitrogen protections; Add 7.5 gram acetic anhydrides and 2.5 gram triethylamines subsequently, reaction is 12 hours under 40 ℃ of nitrogen protections, after reaction finishes; precipitating is filtered washed with methanol three times in 800ml methyl alcohol; 40 ℃ of vacuum drying 48 hours obtain target product: super-branched polyimide photo-sensitive material 1.3 grams.
Claims (6)
1. self-sensitizing type super-branched polyimide photo-sensitive material and preparation method thereof is characterized in that the constitutional repeating unit of polymkeric substance is:
Wherein, polymerization degree n=1-50, m=1-50; Ar is:
R is:
2. the preparation method of self-sensitizing type super-branched polyimide photo-sensitive material, it is characterized in that the preparation method is as follows: (a) at first prepare ultrabranching polyamide acid: with 1,3,5-three (4-amino-benzene oxygen) benzene is that the dicarboxylic anhydride of three amine monomers and ketone group containing is the dicarboxylic anhydride monomer, mol ratio is 1/2, under 40 ℃ of nitrogen protections, the dicarboxylic anhydride monomer is dissolved in the organic solvent, its concentration is 20-100mmol/L, adopt the way that drips, the organic solvent solution that slowly adds three amine monomers, its concentration is 10-50mmol/L, and it is the ultrabranching polyamide acid of macromolecular chain end group that polymerization obtains with the anhydride group, and the reaction time is 5 hours; (b) then carry out end group functional: add the aniline that the ortho position replaces, the mol ratio of itself and three amine monomers is 1-1.5/1, reacts 5 hours under 40 ℃ of nitrogen protections with the end group anhydride group of ultrabranching polyamide acid; (c) carry out chemical imidization subsequently: add dewatering agent acetic anhydride and catalyst of triethylamine under 40 ℃ of nitrogen protections, the reaction time is 12 hours.Reaction precipitates in a large amount of precipitation agent methanol after finishing, and filters, and cleans, and three times repeatedly, 40 ℃ of following vacuum drying obtained target product in 48 hours.
3. the preparation method of self-sensitizing type super-branched polyimide photo-sensitive material according to claim 2 is characterized in that the dicarboxylic anhydride of employed ketone group containing comprises: benzophenone tetracarboxylic dianhydride, benzophenone based benzene tertacarbonic acid's dianhydride, two phenoxy group benzophenone tetracarboxylic dianhydrides, anthraquinone tetracarboxylic dianhydride, xanthone tetracarboxylic dianhydride, thio-xanthene-one tetracarboxylic dianhydride.
4. the preparation method of self-sensitizing type super-branched polyimide photo-sensitive material according to claim 2, it is characterized in that the aniline that employed ortho position replaces comprises: o-toluidine, o ethyl aniline, adjacent isobutyl-aniline, 2,6-xylidin, 2-methyl-6-ethylaniline, 2,6-diethylaniline, o-aminoanisole, 2,6-dimethoxyaniline, methylmercapto aniline, 2,6-diformazan sulfenyl aniline.
5. the preparation method of self-sensitizing type super-branched polyimide photo-sensitive material according to claim 2 is characterized in that employed organic solvent comprises N-methyl-pyrrolidone, N, dinethylformamide, N, N dimethyl acetamide.
6. the preparation method of self-sensitizing type super-branched polyimide photo-sensitive material according to claim 2 is characterized in that employed dewatering agent is an acetic anhydride, and catalyzer is a triethylamine; Dewatering agent and catalyst concentration are 5-10wt%, and the weight ratio of dewatering agent/catalyzer is 3/1.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106519677A (en) * | 2016-11-04 | 2017-03-22 | 东华大学 | BTDA-type fluorine-containing branched polyimide resin film and preparation method thereof |
| CN106519673A (en) * | 2016-11-04 | 2017-03-22 | 东华大学 | BPDA type fluorine-containing branched polyimide resin film and preparation method thereof |
| CN106519678A (en) * | 2016-11-04 | 2017-03-22 | 东华大学 | ODPA-type bisphenol A tetramine branched polyimide resin film and preparation method thereof |
| CN106916305A (en) * | 2015-12-25 | 2017-07-04 | 宁波祢若电子科技有限公司 | A kind of super cladodification polyimides containing anthraquinone ring and preparation method thereof |
| CN109912618A (en) * | 2019-03-20 | 2019-06-21 | 浙江福斯特新材料研究院有限公司 | Multifunctional organic acid anhydride and low-dielectric-constant hyperbranched polyimide film |
-
2002
- 2002-10-31 CN CN 02137747 patent/CN1405631A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106916305A (en) * | 2015-12-25 | 2017-07-04 | 宁波祢若电子科技有限公司 | A kind of super cladodification polyimides containing anthraquinone ring and preparation method thereof |
| CN106916305B (en) * | 2015-12-25 | 2019-02-15 | 宁波祢若电子科技有限公司 | A kind of super cladodification polyimides and preparation method thereof containing anthraquinone ring |
| CN106519677A (en) * | 2016-11-04 | 2017-03-22 | 东华大学 | BTDA-type fluorine-containing branched polyimide resin film and preparation method thereof |
| CN106519673A (en) * | 2016-11-04 | 2017-03-22 | 东华大学 | BPDA type fluorine-containing branched polyimide resin film and preparation method thereof |
| CN106519678A (en) * | 2016-11-04 | 2017-03-22 | 东华大学 | ODPA-type bisphenol A tetramine branched polyimide resin film and preparation method thereof |
| CN109912618A (en) * | 2019-03-20 | 2019-06-21 | 浙江福斯特新材料研究院有限公司 | Multifunctional organic acid anhydride and low-dielectric-constant hyperbranched polyimide film |
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