CN111303418A - Photocrosslinkable polyimide resin - Google Patents

Photocrosslinkable polyimide resin Download PDF

Info

Publication number
CN111303418A
CN111303418A CN201911111096.8A CN201911111096A CN111303418A CN 111303418 A CN111303418 A CN 111303418A CN 201911111096 A CN201911111096 A CN 201911111096A CN 111303418 A CN111303418 A CN 111303418A
Authority
CN
China
Prior art keywords
hours
polyimide resin
diamine monomer
group
diamine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201911111096.8A
Other languages
Chinese (zh)
Other versions
CN111303418B (en
Inventor
不公告发明人
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Jizi Technology Co Ltd
Original Assignee
Shanghai Jizi Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Jizi Technology Co Ltd filed Critical Shanghai Jizi Technology Co Ltd
Priority to CN201911111096.8A priority Critical patent/CN111303418B/en
Publication of CN111303418A publication Critical patent/CN111303418A/en
Application granted granted Critical
Publication of CN111303418B publication Critical patent/CN111303418B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • 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
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
    • 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
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0387—Polyamides or polyimides

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

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 figure, wherein Ar1Is 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

Photocrosslinkable polyimide resin
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
In recent years, polyimides have been widely used in the fields of plastic engineering, aerospace, microelectronics, and the like because of their excellent properties. Among them, photosensitive polyimide (PSPI) is gaining attention in the field of photolithography, and particularly, a self-sensitizing system without adding a photoinitiator and a sensitizer is not used, because the self-sensitizing polyimide system has no micromolecule residue with low molecular weight after photocrosslinking, the mechanical property, the electrical property, the thermal property and the like of the photoresist are not affected.
Since the first report of self-sensitizing polyimide synthesized from ketoanhydride (BTDA) in 1985 by j. Pfeifer, researchers have been working on improving the photosensitivity of self-sensitizing polyimides. Since the polyimide main chain is highly rigid and is less likely to undergo chain movement to cause a photochemical reaction, the ketone group must be present in the main chain to limit the photosensitivity of the polyimide. Self-sensitized negative photosensitive polyimides have been attracting much attention from researchers, and patents such as CN200610020873.4, CN200610023217.x and CN02137747.2 have all been 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 polyimide can be used as a negative photoresist resin.
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 750957DEST_PATH_IMAGE001
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 329706DEST_PATH_IMAGE002
，
Figure 685470DEST_PATH_IMAGE003
,
Figure 84090DEST_PATH_IMAGE004
,
Figure 684967DEST_PATH_IMAGE005
,
Figure 993588DEST_PATH_IMAGE006
,
Figure 333303DEST_PATH_IMAGE007
。
ar is2Type diamine monomers include, but are not limited to, the following 8:
Ar2=
Figure 140591DEST_PATH_IMAGE008
，
Figure 325584DEST_PATH_IMAGE009
，
Figure 364079DEST_PATH_IMAGE010
,
Figure 812378DEST_PATH_IMAGE011
，
Figure 592115DEST_PATH_IMAGE012
，
Figure 626805DEST_PATH_IMAGE013
,
Figure 644439DEST_PATH_IMAGE014
,
Figure 342268DEST_PATH_IMAGE015
。
the photocrosslinkable polyimide resin related to the invention has a structure in which a group Q can be: hydrogen atom-H, phenyl
Figure 78143DEST_PATH_IMAGE016
methyl-CH3methoxy-OCH3Biphenyl radical
Figure 808201DEST_PATH_IMAGE017
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 579543DEST_PATH_IMAGE018
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 104065DEST_PATH_IMAGE019
wherein the group Q may be: hydrogen atom-H, phenyl
Figure 937023DEST_PATH_IMAGE020
methyl-CH3methoxy-OCH3Biphenyl radical
Figure 674035DEST_PATH_IMAGE021
And so on, 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 790895DEST_PATH_IMAGE022
，
Figure 470007DEST_PATH_IMAGE023
，
Figure 570687DEST_PATH_IMAGE024
，
Figure 658860DEST_PATH_IMAGE025
，
Figure 364648DEST_PATH_IMAGE026
,
Figure 434235DEST_PATH_IMAGE027
,
Figure 943583DEST_PATH_IMAGE028
,
Figure 881452DEST_PATH_IMAGE029
。
in the reaction equation of fig. 2, the chemical structural formula of the dianhydride monomer is as follows:
Figure 458058DEST_PATH_IMAGE030
,
Figure 760863DEST_PATH_IMAGE031
，
Figure 711502DEST_PATH_IMAGE032
，
Figure 780958DEST_PATH_IMAGE033
，
Figure 44361DEST_PATH_IMAGE034
，
Figure 190171DEST_PATH_IMAGE035
。
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, using DMSO deuteration reagent 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 500mJ/cm by using i-line 365 nanometer exposure2And 5% -60% gray scale plate, and observation sensitivity.
Description of the drawings:
FIG. 1 is an infrared spectrum of a photosensitive polyimide resin according to a preferred embodiment of the present invention;
FIG. 2 is an infrared spectrum of another photosensitive polyimide resin according to a preferred embodiment of the present invention;
FIG. 3 is a photo of a lithographic pattern made from a polyimide photoresist according to a preferred embodiment of the present invention;
FIG. 4 is a photo of a lithographic pattern made from another polyimide photoresist according to the preferred embodiment of the present invention;
FIG. 5 shows a general structural formula of a photo-crosslinkable polyimide resin disclosed in 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 3.003 g (6mmol) of 1, 4-bis (4-aminophenoxy) -2, 5-dibenzoylbenzene, slowly adding 7.992 g (18 mmol) of 4, 4' - (hexafluoroisopropylidene) bis (phthalic anhydride) in portions after all the gamma-butyrolactone is dissolved, reacting at room temperature, keeping stirring for 8-12 hours, adding an imidization reagent which is in molar excess of amino, acetic anhydride and triethylamine, maintaining nitrogen for 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 as a solvent is charged 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 3.916g (6mmol) of 1, 4-bis (4-aminophenoxy) -2,5- (4-phenylbenzoyl) benzene are then added, after complete dissolution, 7.992 g (18 mmol) of 4, 4' - (hexafluoroisopropylidene) bis (phthalic anhydride) are slowly added in portions, the mixture is reacted at room temperature while stirring is maintained for 8 to 12 hours, toluene is slowly added dropwise, the temperature is raised to 160 ℃, and toluene is evaporated off and kept 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
50ml of N, N-dimethylacetamide as a solvent was charged into a dry, clean glass bottle, nitrogen-protected, 2.54g of 4,4 '-methylenebis (2, 6-dimethylaniline) (10mmol) and 1.682 g (3 mmol) of 1, 4-bis (4-aminophenoxy) -2, 5-bis (4-methoxybenzoyl) benzene were added, after complete dissolution 5.772 g (13mmol) 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 the 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. 3 to be detected.
Example 4
100ml of N-methylpyrrolidinone as a solvent is charged into a dry and clean glass bottle, nitrogen is introduced for protection, 3.048g of 4,4 '-methylenebis (2, 6-dimethylaniline) (12mmol) and 4.505g (9 mmol) of 1, 4-bis (4-aminophenoxy) -2, 5-dibenzoylbenzene are then added, after complete dissolution, 9.324 g (21mmol) of 4, 4' - (hexafluoroisopropylidene) bis (phthalic anhydride) are slowly added in portions, the mixture is reacted at room temperature and stirred for 12 hours, toluene is slowly added dropwise, the temperature is raised to 180 ℃ and the toluene is evaporated off and kept 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. 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, 2.856g of 3,3 ', 5' -tetramethylbenzidine (12mmol) and 3.003 g (6mmol) of 1, 4-bis (4-aminophenoxy) -2, 5-dibenzoylbenzene are added, after all the components are dissolved, 3.924 g (18 mmol) 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 the amino group, 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 as a 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 3.1716g (6mmol) of 1, 4-bis (4-aminophenoxy) -2, 5-bis (4-methylbenzoyl) benzene are then added, after complete dissolution, 5.292 g (18 mmol) of biphenyltetracarboxylic dianhydride are slowly added in portions, the mixture is reacted at room temperature and kept stirring 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, nitrogen-protected, 2.38g of 3,3 ', 5 ' -tetramethylbenzidine (10mmol) and 1.0572g (2 mmol) of 1, 4-bis (4-aminophenoxy) -2, 5-bis (4-methylbenzoyl) benzene were added, after complete dissolution, 5.328 g (12mmol) of 4,4 ' - (hexafluoroisopropylidene) bis (phthalic anhydride) were slowly added in portions, the mixture was reacted at room temperature and kept under stirring for 12 hours, an imidizing agent in molar excess of the amino groups, acetic anhydride and triethylamine were added, nitrogen protection 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 5.874 g (9 mmol) of 1, 4-bis (4-aminophenoxy) -2, 5-bis (4-phenylbenzoyl) benzene are added, after all the materials are dissolved, 6.846 g (21mmol) of diphenyl ether tetracarboxylic dianhydride are 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. 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) (18 mmol) and 1.305 g (2 mmol) of 1, 4-bis (4-aminophenoxy) -2, 5-bis (4-phenylbenzoyl) benzene are then added, after complete dissolution, 6.52 g (20mmol) of diphenyl ether tetracarboxylic dianhydride are slowly added in portions, reaction is carried out at room temperature and stirring is kept 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
60ml of N-methyl pyrrolidone as a solvent is added into a dry and clean glass bottle, nitrogen is introduced for protection, then 0.254g of 4, 4' -methylenebis (2, 6-dimethylaniline) (1 mmol) and 5.874 g (9 mmol) of 1, 4-bis (4-aminophenoxy) -2, 5-bis (4-phenylbenzoyl) benzene are added, after all the materials are dissolved, 3.26 g (10mmol) of diphenyl ether tetracarboxylic dianhydride are 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. 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 769051DEST_PATH_IMAGE036
Note: + represents very good solubility, + -represents heat soluble, -represents not soluble.

Claims (16)

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 DEST_PATH_IMAGE001
wherein Ar is1Is a dianhydride monomer fragment, Ar2Is diamine monomer segment containing active hydrogen, x = 0.1-0.9, and n = 5-200.
2. Wherein the imine rings may both be para to the ether linkage or both be meta to the ether linkage.
3. Further, said Ar1Type dianhydride monomers include, but are not limited to, the following 6:
in the formula, Ar1=
Figure 931603DEST_PATH_IMAGE002
，
Figure 457262DEST_PATH_IMAGE004
,
Figure DEST_PATH_IMAGE005
,
Figure 395131DEST_PATH_IMAGE006
,
Figure DEST_PATH_IMAGE007
,
Figure 17743DEST_PATH_IMAGE008
。
4. Ar is2Type diamine monomers include, but are not limited to, the following 8:
Ar2=
Figure DEST_PATH_IMAGE009
，
Figure 586127DEST_PATH_IMAGE010
，
Figure DEST_PATH_IMAGE011
,
Figure DEST_PATH_IMAGE013
，
Figure 192558DEST_PATH_IMAGE014
，
Figure DEST_PATH_IMAGE015
,
Figure 934118DEST_PATH_IMAGE016
,
Figure DEST_PATH_IMAGE017
。
5. 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 DEST_PATH_IMAGE019
methyl-CH3methoxy-OCH3Biphenyl radical
Figure DEST_PATH_IMAGE021
And so on.
6. 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.
7. 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.
8. 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.
9. After the reaction was complete, the resulting highly viscous polymer solution was taken.
10. The diamine monomer of claim 3, having a benzophenone structure pendant from the diamine monomer, having the structure:
Figure 61168DEST_PATH_IMAGE022
wherein the group Q may be: hydrogen atom-H, phenyl
Figure 597192DEST_PATH_IMAGE024
methyl-CH3methoxy-OCH3Biphenyl radical
Figure 566285DEST_PATH_IMAGE026
And so on.
11. Wherein the amino group may be in the para position or meta position relative to the ether linkage.
12. An abstractable active hydrogen-containing diamine monomer having the formula:
Figure DEST_PATH_IMAGE027
，
Figure DEST_PATH_IMAGE029
，
Figure 111536DEST_PATH_IMAGE030
，
Figure 115264DEST_PATH_IMAGE032
，
Figure DEST_PATH_IMAGE033
,
Figure 25451DEST_PATH_IMAGE034
,
Figure DEST_PATH_IMAGE035
,
Figure 75316DEST_PATH_IMAGE036
。
13. the chemical structure of the dianhydride monomer is as follows:
Figure DEST_PATH_IMAGE037
,
Figure 158678DEST_PATH_IMAGE038
，
Figure DEST_PATH_IMAGE039
，
Figure 344809DEST_PATH_IMAGE040
，
Figure DEST_PATH_IMAGE041
，
Figure 425897DEST_PATH_IMAGE042
。
14. 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.
15. 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.
16. The method of claim 5, wherein the total concentration of dianhydride and diamine monomers in the organic solvent is: 5-40 w/v%.
CN201911111096.8A 2019-11-14 2019-11-14 Photo-crosslinkable polyimide resin Active CN111303418B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911111096.8A CN111303418B (en) 2019-11-14 2019-11-14 Photo-crosslinkable polyimide resin

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911111096.8A CN111303418B (en) 2019-11-14 2019-11-14 Photo-crosslinkable polyimide resin

Publications (2)

Publication Number Publication Date
CN111303418A true CN111303418A (en) 2020-06-19
CN111303418B CN111303418B (en) 2023-05-09

Family

ID=71158157

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911111096.8A Active CN111303418B (en) 2019-11-14 2019-11-14 Photo-crosslinkable polyimide resin

Country Status (1)

Country Link
CN (1) CN111303418B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115304768A (en) * 2022-09-16 2022-11-08 明士新材料有限公司 Method for researching amplification process for producing high-quality PSPI resin

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
JP2014162801A (en) * 2013-02-21 2014-09-08 Toray Ind Inc Polyimide resin, resin composition containing the same, and multilayer film and laminate obtained by using the composition
CN108640846A (en) * 2018-04-25 2018-10-12 哈尔滨工业大学 A kind of flexible aromatic diamine monomers of the side group containing aromatic ring and preparation method thereof

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
JP2014162801A (en) * 2013-02-21 2014-09-08 Toray Ind Inc Polyimide resin, resin composition containing the same, and multilayer film and laminate obtained by using the composition
CN108640846A (en) * 2018-04-25 2018-10-12 哈尔滨工业大学 A kind of flexible aromatic diamine monomers of the side group containing aromatic ring and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
李芳等: ""一种新型光致抗蚀剂——负性自增感光敏聚酰亚胺"", 《化工新型材料》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115304768A (en) * 2022-09-16 2022-11-08 明士新材料有限公司 Method for researching amplification process for producing high-quality PSPI resin

Also Published As

Publication number Publication date
CN111303418B (en) 2023-05-09

Similar Documents

Publication Publication Date Title
KR102091496B1 (en) Positive photosensitive resin composition, and method for producing semiconductor device containing a cured film using said composition
US4778859A (en) Tetramine derived polyimide with pendant unsaturation, and various photosensitive compositions therefrom
CN107312173B (en) polyimide precursor and use thereof
KR101804308B1 (en) Process for production of polyhydroxyimide
JP7431050B2 (en) Resin composition, cured film, laminate, method for producing cured film, and semiconductor device
CN111303417B (en) Photocrosslinkable polyimide resin
TW201820033A (en) Photosensitive composition and method for forming cured film capable of suppressing the generation of foreign matters in the photosensitive composition and allows for fine pattern analysis
CN111303418B (en) Photo-crosslinkable polyimide resin
CN111303419B (en) Photocrosslinkable polyimide resin structure
JP7196121B2 (en) Pattern forming method, photosensitive resin composition, laminate manufacturing method, and electronic device manufacturing method
Hsu et al. Synthesis and characterization of novel negative-working aqueous base developable photosensitive polyimide precursors
CN115073732B (en) Block type photosensitive polyimide precursor resin, preparation method thereof and block type photosensitive resin composition
CN114634429B (en) Photosensitive diamine monomer and preparation method thereof, resin containing photosensitive diamine monomer and photosensitive resin composition
CN111423582B (en) Polyimide resin for positive photoresist and preparation method thereof
US5055549A (en) Process for preparing photosensitive heat-resistant polymer
Chen et al. Preparation of Auto-Photosensitive Hyperbranched Co-polyimide by the Condensation of 4, 4'-(Hexafluoroisopropy1idene) diphthalic Anhydride and 3, 3', 4, 4'-Benzophenonetetracarboxylic Dianhydride with 1, 3, 5-Tris (4-aminophenoxy) benzene through a Stage Addition Reaction Method
JPH1192660A (en) Photosensitive resin composition
CN112979949B (en) Transparent photosensitive polyimide resin, polyimide film and preparation method thereof
Berrada et al. Novel negative-type soluble photosensitive polyimides: synthesis and characterization
CN111965940B (en) Positive photosensitive polyimide resin composition, preparation method of resin composition and application of resin composition
CN114755891A (en) Positive photosensitive resin composition and preparation method thereof
JP3913022B2 (en) Negative photosensitive resin composition
WO2015019802A1 (en) Photosensitive resin composition, relief pattern film thereof, method for producing relief pattern film, electronic component or optical product including relief pattern film, and adhesive including photosensitive resin composition
CN111333837B (en) Positive photosensitive polyimide resin and preparation method thereof
JPH0827538B2 (en) Photosensitive resin composition

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant