CN111303419A - Photo-crosslinkable polyimide resin structure - Google Patents

Photo-crosslinkable polyimide resin structure Download PDF

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CN111303419A
CN111303419A CN201911114161.2A CN201911114161A CN111303419A CN 111303419 A CN111303419 A CN 111303419A CN 201911114161 A CN201911114161 A CN 201911114161A CN 111303419 A CN111303419 A CN 111303419A
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polyimide resin
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Shanghai Jizi Technology Co Ltd
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
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    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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Abstract

The invention relates to a polyimide resin structure with a benzophenone-containing side group, which can generate free radicals and deprive hydrogen on diamine at a nearby position under the irradiation of ultraviolet light so as to generate a photocrosslinking reaction, and has wide application prospect in the field of negative polyimide photoresist. The structure of the photo-crosslinking polyimide resin disclosed by the invention is shown in the attached figure 1 in the specification, wherein Ar is1Is a dianhydride monomer fragment, Ar2The structure of the negative photosensitive polyimide is diamine monomer segment containing active hydrogen, x =0.1-1.0, n =5-200, and the negative photosensitive polyimide obtained by the structure has better solubility, higher sensitivity, better resolution and contrast than the negative polyimide with ketone carbonyl on the main chain.

Description

Photo-crosslinkable polyimide resin structure
Technical Field
The invention relates to the field of negative photoresist, in particular to a photo-crosslinking polyimide resin (PSPI) structure and a preparation method thereof.
Background
Polyimide materials are functional materials with excellent performance, particularly high temperature resistance, insulating property and dielectric property, and therefore are widely applied to the fields of military industry and aerospace, and as civil products, polyimide is widely applied to the field of microelectronics, wherein photosensitive polyimide (PSPI) is used as a buffer layer, a passivation layer and an α particle barrier layer of an integrated circuit.
In many photosensitive polyimide systems, a small molecule photoinitiator needs to be added, but only part of the photoinitiator is utilized by the exposure process, so that a large amount of small molecule photoinitiator remains in the photoresist. The residue of small molecules can affect the thermal stability, mechanical properties, dielectric properties and water absorption of the photoresist. Therefore, the self-photosensitive polyimide has attracted more and more attention from researchers. Polyimide with a photo-crosslinking structure, which is developed successfully by Pfeifer and the like, is photosensitive polyimide with benzophenone in a main chain, wherein the photosensitive polyimide is prepared by polymerizing 3,3 ', 4, 4' -Benzophenone Tetracarboxylic Dianhydride (BTDA) and diamine with alkyl substituent groups at the ortho-position of amino groups (namely diamine with active hydrogen for free radical abstraction), and the structure is sensitive to i-line, namely 365nm ultraviolet light and performs a photo-crosslinking reaction under the irradiation of the ultraviolet light. Its sensitization mechanism can be summarized as: the ketone carbonyl on the polyimide macromolecular chain is excited by ultraviolet light to generate a triplet excited state, active hydrogen on imine ortho-alkyl is captured to be reduced, two free radicals are generated simultaneously, one is on the ortho-alkyl and the other is on the carbonyl, and then the two free radicals are combined to form intermolecular crosslinking, so that an exposed area is insoluble, the polyimide macromolecular chain belongs to a negative photosensitive material, small molecules do not escape, the film does not shrink, and the pattern appearance is good. However, because the benzophenone structure is in the main chain of the polyimide, the photosensitivity of the benzophenone structure is limited, so that the self-sensitized negative photosensitive polyimide has been paid attention by many researchers, for example, patents with application numbers of CN200610020873.4, cn200610023217.x and CN02137747.2 are all developed around the subject of sensitization.
The invention aims to keep the self-photosensitive characteristic of benzophenone PSPI, and under the premise of not adding a photoinitiator, the structure of polyimide is improved, dianhydride BTDA is not used, diamine with benzophenone as a side group is introduced, and a benzophenone photosensitive group is transferred to the side group of the polyimide, so that the photosensitive sensitivity of polyimide photo-crosslinking is greatly improved, and the negative photoresist with good comprehensive performance can be obtained.
Disclosure of Invention
The invention relates to a photo-crosslinking polyimide resin and a preparation method thereof, which is characterized in that a side group of the photo-crosslinking polyimide resin contains a benzophenone structure, and the chemical structural formula of the negative photosensitive polyimide resin is as follows:
Figure RE-DEST_PATH_IMAGE002
wherein Ar is1Is a dianhydride monomer fragment, Ar2Is diamine monomer segment containing active hydrogen, x = 0.1-0.9, and n = 5-200.
Wherein the imine rings may both be para to the ether linkage or both be meta to the ether linkage.
Further, said Ar1Type dianhydride monomers include, but are not limited to, the following 6:
Ar1=
Figure RE-DEST_PATH_IMAGE004
，
Figure RE-DEST_PATH_IMAGE006
,
Figure RE-DEST_PATH_IMAGE007
,
Figure RE-DEST_PATH_IMAGE008
,
Figure RE-DEST_PATH_IMAGE009
,
Figure RE-DEST_PATH_IMAGE011
。
ar is2Type diamine monomers include, but are not limited to, the following 8:
Ar2=
Figure RE-DEST_PATH_IMAGE013
，
Figure RE-DEST_PATH_IMAGE015
，
Figure RE-DEST_PATH_IMAGE017
,
Figure RE-DEST_PATH_IMAGE019
，
Figure RE-DEST_PATH_IMAGE021
，
Figure RE-DEST_PATH_IMAGE023
,
Figure RE-DEST_PATH_IMAGE025
,
Figure RE-DEST_PATH_IMAGE027
。
the photocrosslinkable polyimide resin related to the invention has a structure in which a group Q can be: hydrogen atom-H, phenyl
Figure RE-DEST_PATH_IMAGE029
methyl-CH3methoxy-OCH3Biphenyl radical
Figure RE-DEST_PATH_IMAGE031
And so on.
The preparation method of the photocrosslinkable polyimide comprises the following steps (shown in figure 2):
under the protection of nitrogen, sequentially adding a diamine monomer with a benzophenone structure as a side group, a diamine monomer containing abstractable active hydrogen, a dianhydride monomer and an organic solvent into a dry three-necked bottle, stirring for 2-12 hours at room temperature, then slowly dropwise adding a mixture of triethylamine and acetic anhydride into the reaction bottle, and continuously reacting for 4-18 hours at room temperature. After the reaction was completed, the resulting highly viscous polymer solution was slowly poured into a large amount of methanol, and the precipitated solid was sufficiently washed with methanol and dried in a vacuum oven for 5 hours.
Or sequentially adding a diamine monomer with a benzophenone structure as a side group, a diamine monomer containing abstractable active hydrogen, a dianhydride monomer and an organic solvent into a dry three-necked bottle under the protection of nitrogen, stirring for 2-12 hours at room temperature, then continuously and slowly dripping toluene into the reaction bottle, heating to 160 ℃, keeping the temperature at 160 ℃ and continuously reacting for 4-8 hours to ensure that the toluene and the water are removed by azeotropy. After the reaction was complete, the resulting highly viscous polymer solution was taken.
Figure RE-DEST_PATH_IMAGE033
FIG. 2 equation for preparing photosensitive polyimide containing benzophenone as side group
In the reaction equation of fig. 2, the diamine monomer having a benzophenone structure as a pendant group has the following structure:
Figure RE-DEST_PATH_IMAGE035
wherein the group Q may be: hydrogen atom-H, phenyl
Figure RE-DEST_PATH_IMAGE037
methyl-CH3methoxy-OCH3Biphenyl radical
Figure RE-DEST_PATH_IMAGE039
Etc. etc
The amino group is para or meta to the ether linkage.
In the reaction equation of fig. 2, the diamine monomer containing an abstractable active hydrogen has the following chemical formula:
Figure RE-DEST_PATH_IMAGE041
，
Figure RE-DEST_PATH_IMAGE043
，
Figure RE-DEST_PATH_IMAGE045
，
Figure RE-DEST_PATH_IMAGE047
，
Figure RE-DEST_PATH_IMAGE049
,
Figure RE-DEST_PATH_IMAGE051
,
Figure RE-DEST_PATH_IMAGE053
,
Figure RE-DEST_PATH_IMAGE055
。
in the reaction equation of fig. 2, the chemical structural formula of the dianhydride monomer is as follows:
Figure RE-DEST_PATH_IMAGE057
,
Figure RE-DEST_PATH_IMAGE059
，
Figure RE-DEST_PATH_IMAGE061
，
Figure RE-DEST_PATH_IMAGE063
，
Figure RE-DEST_PATH_IMAGE065
，
Figure RE-DEST_PATH_IMAGE067
。
the invention relates to a photo-crosslinkable polyimide resin, wherein the molar ratio of a diamine monomer with a benzophenone structure as a side group to a diamine monomer with abstractable active hydrogen is as follows: 1:9-9: 1.
The invention relates to a photo-crosslinkable polyimide resin, and the preparation method thereof uses the following organic solvents: one or more mixed solvents of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, Propylene Glycol Methyl Ether Acetate (PGMEA) and gamma-butyrolactone. The total concentration of all dianhydride and diamine monomers in the organic solvent is: 5-40 w/v%.
The test method comprises the following steps:
1. solubility, 0.5g of the polymer was placed in 5ml of a solvent, and it was observed at room temperature whether or not the polymer was completely dissolved to give a transparent solution.
2. Nuclear magnetic hydrogen spectrum NMR1H, Bruker 400MHz, usingDMSO deuterogen dissolution test.
3. Infrared Spectroscopy (FT-IR), Perkin-Elmer Paragon 1000 Fourier transform Infrared Spectrophotometer, either KBr pellet or thin film.
4. And (3) testing the photosensitive sensitivity: and coating the film on a silicon wafer in a rotating manner to obtain a film with the thickness of 9-10 microns. The exposure intensity is 1500mJ/cm by using i-line 365 nanometer exposure2And 5% -60% gray scale plate, and observation sensitivity.
Description of the drawings:
FIG. 1 is a photo-crosslinkable polyimide resin structure disclosed in the present invention;
FIG. 2 is an infrared spectrum of a photosensitive polyimide resin in a preferred embodiment of the present invention;
FIG. 3 is a diagram showing an ultraviolet absorption spectrum of a photosensitive polyimide resin in a preferred embodiment of the present invention
FIG. 4 is a photograph of a lithographic pattern made of a polyimide photoresist according to a preferred embodiment of the present invention;
FIG. 5 is a photograph of a lithographic pattern made from another polyimide photoresist in accordance with a preferred embodiment of the present invention.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The following examples are specific illustrations of the synthesis of hyperbranched polyimide resins without limiting the scope of the invention.
Example 1
Adding 70ml of gamma-butyrolactone serving as a solvent into a dry and clean glass bottle, introducing nitrogen for protection, then adding 3.048g of 4,4 '-methylenebis (2, 6-dimethylaniline) (12mmol) and 3.456 g (6 mmol) of 2, 2' -dibenzoyl-4, 4 '-bis (4-aminophenoxy) biphenyl, slowly adding 7.992 g (18mmol) of 4, 4' - (hexafluoroisopropylidene) bis (phthalic anhydride) in batches after all the materials are dissolved, reacting at room temperature, keeping stirring for 8-12 hours, adding an imidizing agent which is in molar excess of amino, acetic anhydride and triethylamine, maintaining nitrogen protection, and continuing stirring at room temperature for 10-20 hours. Precipitating the obtained polymer solution into methanol, stirring and washing the solution, and drying the solution in a vacuum oven for 8 hours to obtain the photo-crosslinking polyimide resin with the side group of benzophenone, namely the sample No. 1 to be detected.
Example 2
60ml of gamma-butyrolactone solvent is added into a dry and clean glass bottle with a water separator, nitrogen is introduced for protection, then 3.048g of 4,4 ' -methylenebis (2, 6-dimethylaniline) (12mmol) and 4.368g (6 mmol) of 2,2 ' -bibenzoyl-4, 4 ' -bis (4-aminophenoxy) biphenyl are added, after all the 4,4 ' - (hexafluoroisopropylidene) bis (phthalic anhydride) is slowly added in portions, 7.992 g (18mmol) of 4,4 ' - (hexafluoroisopropylidene) bis (phthalic anhydride) is added after all the materials are dissolved, the mixture is reacted at room temperature and kept stirring for 8-12 hours, toluene is slowly dropped into the mixture, the temperature is raised to 160 ℃, and toluene is evaporated and dehydrated for 6 hours. Precipitating the obtained polymer solution into methanol, stirring and washing the solution, and drying the solution in a vacuum oven for 5 hours to obtain the photo-crosslinking polyimide resin with the side group of benzophenone, namely the sample No. 2 to be detected.
Example 3
A dry clean glass bottle was charged with 50ml of N, N-dimethylacetamide as a solvent, purged with nitrogen, followed by 2.54g of 4,4 '-methylenebis (2, 6-dimethylaniline) (10mmol) and 1.908 g (3 mmol) of 2, 2' -bis (4-methoxybenzoyl) -4,4 '-bis (4-aminophenoxy) biphenyl, after complete dissolution, 5.328 g (12mmol) of 4, 4' - (hexafluoroisopropylidene) bis (phthalic anhydride) were slowly added in portions, reacted at room temperature and kept stirring for 12 hours, imidizing agent in molar excess of amino groups, acetic anhydride and triethylamine were added, nitrogen blanket was maintained, and stirring was continued at room temperature for 7 hours. Precipitating the obtained polymer solution into methanol, stirring and washing the solution, and drying the solution in a vacuum oven for 5 hours to obtain the photo-crosslinking polyimide resin with the side group of benzophenone, namely the sample No. 3 to be detected.
Example 4
100ml of N-methyl pyrrolidone as a solvent was charged in a dry and clean glass bottle, nitrogen-purged, followed by 3.048g of 4,4 '-methylenebis (2, 6-dimethylaniline) (12mmol) and 5.436g (9 mmol) of 2, 2' -bis (4-methylbenzoyl) -4,4 '-bis (4-aminophenoxy) biphenyl, after complete dissolution, 8.88 g (20mmol) of 4, 4' - (hexafluoroisopropylidene) bis (phthalic anhydride) were slowly added in portions, reacted at room temperature while maintaining stirring for 12 hours, toluene was slowly dropped thereinto to raise the temperature to 180 ℃ and dehydrated and maintained for 5 hours by evaporating toluene. Precipitating the obtained polymer solution into methanol, stirring and washing the solution, and drying the solution in a vacuum oven for 6 hours to obtain the photo-crosslinking polyimide resin with the side group of benzophenone, namely the sample No. 4 to be detected.
Example 5
70ml of gamma-butyrolactone as a solvent is added into a dry and clean glass bottle, nitrogen protection is carried out, then 2.856g of 3,3 ', 5' -tetramethylbenzidine (12mmol) and 3.624 g (6 mmol) of 2,2 '-bis (4-methylbenzoyl) -4, 4' -bis (3-aminophenoxy) biphenyl are added, after all the 3,3 ', 5' -tetramethylbenzidine is dissolved, 3.924 g (18mmol) of pyromellitic dianhydride are slowly added in portions, the reaction is carried out at room temperature and stirring is kept for 12 hours, an imidizing agent in molar excess of amino groups, acetic anhydride and triethylamine are added, nitrogen protection is maintained, and stirring is continued for 10 hours at room temperature. The obtained polymer solution is precipitated into methanol, stirred and washed, and dried in a vacuum oven for 6 hours to obtain the photo-crosslinking polyimide resin with the side group of benzophenone, namely the sample No. 5 to be detected.
Example 6
60ml of gamma-butyrolactone solvent is added into a dry and clean glass bottle with a water separator, nitrogen is introduced for protection, 3.048g of 4,4 ' -methylenebis (2, 6-dimethylaniline) (12mmol) and 3.816g (6 mmol) of 2,2 ' -bis (4-methoxybenzoyl) -4,4 ' -bis (3-aminophenoxy) biphenyl are then added, after complete dissolution, 5.292 g (18mmol) of biphenyltetracarboxylic dianhydride are slowly added in portions, the reaction is carried out at room temperature and stirring is maintained for 12 hours, toluene is slowly added dropwise, the temperature is raised to 160 ℃, and toluene is evaporated and dehydrated for 5 hours. Precipitating the obtained polymer solution into methanol, stirring and washing the solution, and drying the solution in a vacuum oven for 6 hours to obtain the photo-crosslinking polyimide resin with the side group of benzophenone, namely the sample No. 6 to be detected.
Example 7
50ml of N, N-dimethylacetamide as a solvent was charged into a dry clean glass bottle and nitrogen-protected, then 2.38g of 3,3 ', 5 ' -tetramethylbenzidine (10mmol) and 1.152g (2 mmol) of 2,2 ' -dibenzoyl-4, 4 ' -bis (3-aminophenoxy) biphenyl were added, after complete dissolution 5.328 g (12mmol) of 4,4 ' - (hexafluoroisopropylidene) bis (phthalic anhydride) were slowly added in portions and allowed to react at room temperature and stirring was maintained for 12 hours, imidizing agent in molar excess of amino groups, acetic anhydride and triethylamine were added, nitrogen-protected was maintained and stirring was continued at room temperature for 7 hours. Precipitating the obtained polymer solution into methanol, stirring and washing the solution, and drying the solution in a vacuum oven for 5 hours to obtain the photo-crosslinking polyimide resin with the side group of benzophenone, namely the sample No. 7 to be detected.
Example 8
60ml of N-methyl pyrrolidone as a solvent is added into a dry and clean glass bottle, nitrogen is introduced for protection, then 3.048g of 4,4 '-methylenebis (2, 6-dimethylaniline) (12mmol) and 6.552g (9 mmol) of 2, 2' -bibenzoyl-4, 4 '-bis (3-aminophenoxy) biphenyl are added, after all the 4, 4' -methylenebis (2, 6-dimethylaniline) is dissolved, 6.2 g (20mmol) of diphenyl ether tetracarboxylic dianhydride is slowly added in portions, the reaction is carried out at room temperature and the stirring is kept for 8 hours, toluene is slowly dropped into the mixture, the temperature is raised to 180 ℃, and the toluene is dehydrated and kept for 10 hours. Precipitating the obtained polymer solution into methanol, stirring and washing, and drying in a vacuum oven for 8-10 hours to obtain the photo-crosslinking polyimide resin with the side group of benzophenone, namely the sample No. 8 to be detected.
Example 9
60ml of N-methyl pyrrolidone as a solvent is added into a dry and clean glass bottle, nitrogen is introduced for protection, 4.572g of 4,4 '-methylenebis (2, 6-dimethylaniline) (18mmol) and 1.272 g (2 mmol) of 2, 2' -bis (4-methoxybenzoyl) -4,4 '-bis (4-aminophenoxy) biphenyl are added, after all the 4, 4' -methylenebis (2, 6-dimethylaniline) is dissolved, 6.52 g (20mmol) of diphenyl ether tetracarboxylic dianhydride is slowly added in portions, the mixture is reacted at room temperature and kept stirring for 8 hours, toluene is slowly dropped into the mixture, the temperature is raised to 180 ℃, and toluene is evaporated and dehydrated for 10 hours. Precipitating the obtained polymer solution into methanol, stirring and washing, and drying in a vacuum oven for 8-10 hours to obtain the photo-crosslinking polyimide resin with the side group of benzophenone, namely the sample No. 9 to be detected.
Example 10
A dry clean glass bottle is charged with 60ml of N-methyl pyrrolidone as a solvent, nitrogen is introduced for protection, then 0.254g of 4,4 ' -methylenebis (2, 6-dimethylaniline) (1 mmol) and 5.184 g (9 mmol) of 2,2 ' -dibenzoyl-4, 4 ' -bis (3-aminophenoxy) biphenyl are added, after complete dissolution, 2.18 g (10mmol) of pyromellitic dianhydride are slowly added in portions, the reaction is carried out at room temperature and stirring is maintained for 8 hours, toluene is slowly dropped, the temperature is raised to 180 ℃, and toluene is evaporated and dehydrated for 10 hours. Precipitating the obtained polymer solution into methanol, stirring and washing, and drying in a vacuum oven for 8-10 hours to obtain the photo-crosslinking polyimide resin with the side group of benzophenone, namely the sample No. 10 to be detected.
The solubility and photosensitivity of the polymers obtained in the examples are shown in the following Table.
Table one example solubility and photosensitivity of PSPI resin with benzophenone as pendant group
Figure RE-DEST_PATH_IMAGE069
Note: + represents very good solubility, + -represents heat soluble, -represents not soluble.

Claims (7)

1. A photo-crosslinkable polyimide resin and a preparation method thereof are characterized in that a side group of the photo-crosslinkable polyimide resin contains a benzophenone structure, and the chemical structural formula of the negative photosensitive polyimide resin is as follows:
Figure RE-RE-DEST_PATH_IMAGE002
wherein Ar is1Is a dianhydride monomer fragment, Ar2Is diamine monomer segment containing active hydrogen, x = 0.1-0.9, and n = 5-200.
Wherein the imine rings may both be para to the ether linkage or both be meta to the ether linkage.
Further, said Ar1Type dianhydride monomers include, but are not limited to, the following 6:
in the formula, Ar1=
Figure RE-RE-DEST_PATH_IMAGE004
，
Figure RE-RE-DEST_PATH_IMAGE006
,
Figure RE-RE-DEST_PATH_IMAGE007
,
Figure RE-RE-DEST_PATH_IMAGE008
,
Figure RE-RE-DEST_PATH_IMAGE009
,
Figure RE-RE-DEST_PATH_IMAGE011
。
Ar is2Type diamine monomers include, but are not limited to, the following 8:
Ar2=
Figure RE-RE-DEST_PATH_IMAGE013
，
Figure RE-RE-DEST_PATH_IMAGE015
，
Figure RE-RE-DEST_PATH_IMAGE017
,
Figure RE-RE-DEST_PATH_IMAGE019
，
Figure RE-RE-DEST_PATH_IMAGE021
，
Figure RE-RE-DEST_PATH_IMAGE023
,
Figure RE-RE-DEST_PATH_IMAGE025
,
Figure RE-RE-DEST_PATH_IMAGE027
。
2. the photocrosslinkable polyimide resin of claim 1 wherein the photosensitive group is a ketocarbonyl group pendant from the polyimide backbone, wherein the group Q can be: hydrogen atom-H, phenyl
Figure RE-RE-DEST_PATH_IMAGE029
methyl-CH3methoxy-OCH3Biphenyl radical
Figure RE-RE-DEST_PATH_IMAGE031
And so on.
3. The photo-crosslinkable polyimide resin as set forth in claim 1, which is prepared by a method comprising the steps of:
under the protection of nitrogen, sequentially adding a diamine monomer with a benzophenone structure as a side group, a diamine monomer containing abstractable active hydrogen, a dianhydride monomer and an organic solvent into a dry three-necked bottle, stirring for 2-12 hours at room temperature, then slowly dropwise adding a mixture of triethylamine and acetic anhydride into the reaction bottle, and continuously reacting for 4-18 hours at room temperature. After the reaction was completed, the resulting highly viscous polymer solution was slowly poured into a large amount of methanol, and the precipitated solid was sufficiently washed with methanol and dried in a vacuum oven for 5 hours.
Or sequentially adding a diamine monomer with a benzophenone structure as a side group, a diamine monomer containing abstractable active hydrogen, a dianhydride monomer and an organic solvent into a dry three-necked bottle under the protection of nitrogen, stirring for 2-12 hours at room temperature, then continuously and slowly dripping toluene into the reaction bottle, heating to 160 ℃, keeping the temperature at 160 ℃ and continuously reacting for 4-8 hours to ensure that the toluene and the water are removed by azeotropy. After the reaction was complete, the resulting highly viscous polymer solution was taken.
4. The diamine monomer of claim 3, having a benzophenone structure pendant from the diamine monomer, having the structure:
Figure RE-RE-DEST_PATH_IMAGE033
wherein the group Q may be: hydrogen atom-H, phenyl
Figure RE-RE-DEST_PATH_IMAGE035
methyl-CH3methoxy-OCH3Biphenyl radical
Figure RE-RE-DEST_PATH_IMAGE037
And so on.
Wherein the amino group may be in the para position or meta position relative to the ether linkage.
An abstractable active hydrogen-containing diamine monomer having the formula:
Figure RE-RE-DEST_PATH_IMAGE039
，
Figure RE-RE-DEST_PATH_IMAGE041
，
Figure RE-RE-DEST_PATH_IMAGE043
，
Figure RE-RE-DEST_PATH_IMAGE045
，
Figure RE-RE-DEST_PATH_IMAGE047
,
Figure RE-RE-DEST_PATH_IMAGE049
,
Figure RE-RE-DEST_PATH_IMAGE051
,
Figure RE-RE-DEST_PATH_IMAGE053
。
the chemical structure of the dianhydride monomer is as follows:
Figure RE-RE-DEST_PATH_IMAGE055
,
Figure RE-RE-DEST_PATH_IMAGE057
，
Figure RE-RE-DEST_PATH_IMAGE059
，
Figure RE-RE-DEST_PATH_IMAGE061
，
Figure RE-RE-DEST_PATH_IMAGE063
，
Figure RE-RE-DEST_PATH_IMAGE065
。
5. the process according to claim 5, wherein the molar ratio of the diamine monomer having a benzophenone structure as a pendant group to the diamine monomer having an abstractable active hydrogen is: 1:9-9:1.
6. The process according to claim 5, wherein the organic solvent is: one or more mixed solvents of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, Propylene Glycol Methyl Ether Acetate (PGMEA) and gamma-butyrolactone.
7. The method of claim 5, wherein the total concentration of dianhydride and diamine monomers in the organic solvent is: 5-40 w/v%.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114853714A (en) * 2022-05-13 2022-08-05 大连理工大学 Novel photo-crosslinkable photosensitive material and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1807398A (en) * 2006-01-26 2006-07-26 上海交通大学 Diamine containing benzophenone structure and its preparation method
CN1850782A (en) * 2006-05-25 2006-10-25 上海交通大学 Diethylenetriamine containing diphenyl ether and diphenyl ketone, and its preparing method
US20100167208A1 (en) * 2008-12-30 2010-07-01 Wang Jen Fu Water soluble photosensitive polymide polymer, its preparation and photoresist containing the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1807398A (en) * 2006-01-26 2006-07-26 上海交通大学 Diamine containing benzophenone structure and its preparation method
CN1850782A (en) * 2006-05-25 2006-10-25 上海交通大学 Diethylenetriamine containing diphenyl ether and diphenyl ketone, and its preparing method
US20100167208A1 (en) * 2008-12-30 2010-07-01 Wang Jen Fu Water soluble photosensitive polymide polymer, its preparation and photoresist containing the same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
杨丽芳 等: "自增感光敏聚酰亚胺的制备及研究", 《功能材料》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114853714A (en) * 2022-05-13 2022-08-05 大连理工大学 Novel photo-crosslinkable photosensitive material and application thereof
CN114853714B (en) * 2022-05-13 2024-04-16 大连理工大学 Photo-crosslinkable photosensitive material and application thereof

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