End-capping reagent containing crosslinkable group, modified polyimide precursor resin, photosensitive resin composition and application thereof

A polyimide precursor and cross-linking group technology, applied in the field of photolithography, can solve the problems of poor heat resistance of cross-linking agents, limited improvement in thermal properties of materials, improved peel strength and mechanical properties, etc., to improve thermal stability. , the effect of reducing the amount of overflow

Pending Publication Date: 2020-11-10
BEIJING ETERNAL MATERIAL TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] However, as mentioned above, the method of introducing cross-linking agent has been used in the prior art to improve the molecular weight of the resin and form a network structure to improve its physical properties, but there are the following problems: (1) adding a small molecule cross-linking agent is very difficult. It is difficult to react completely and there are residues; (2) The heat resistance of the crosslinking agent itself is poor, which will affect the thermal stability of the system, resulting in limited improvement of the thermal properties of the material, and at the same time lead to an increase in small molecule volatiles
Therefore, it leads to the difficulty of improving the thermal stability, peel strength and mechanical properties of photoresist, and this problem has also become a problem to be solved urgently by those skilled in the art.

Method used

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  • End-capping reagent containing crosslinkable group, modified polyimide precursor resin, photosensitive resin composition and application thereof
  • End-capping reagent containing crosslinkable group, modified polyimide precursor resin, photosensitive resin composition and application thereof
  • End-capping reagent containing crosslinkable group, modified polyimide precursor resin, photosensitive resin composition and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Synthetic example 1

[0078] Synthesis of hydroxyl-containing dianhydride monomer 1:

[0079]

[0080] Under a nitrogen atmosphere, dissolve 10.8g (0.05mol) of 3,3'-dihydroxy-4,4'-benzidine in 50mL of γ-butyrolactone, cool down to -15°C, and then dissolve 22.1g (0.105mol) ) 1,2,4-Trimellitic anhydride acid chloride was dissolved in 50mL γ-butyrolactone, and the latter was added dropwise to the previous solution (the reaction was exothermic, the reaction temperature should be kept below -5°C during the dropwise addition), after the dropwise addition Continue to react for 5h. Most of the solvent was removed by a rotary evaporator, and the concentrate was poured into 300 mL of toluene for precipitation to obtain the corresponding hydroxyl-containing dianhydride monomer 1.

[0081] Structural characterization: method: Fourier transform infrared spectroscopy (the instruments used for Fourier transform infrared spectroscopy characterization in the present invention are Spectrum One infrared spectrome...

Synthetic example 2

[0083] Synthesis of hydroxyl-containing dianhydride monomer 2:

[0084]

[0085]The difference from Preparation Example 1 is that 3,3'-dihydroxy-4,4'-benzidine is replaced by 5,5'-(1,4-phenylene bis(oxo)) Two (2-aminophenol), to obtain the hydroxyl-containing dianhydride monomer 2.

[0086] Structural characterization: method: Fourier transform infrared spectroscopy, characteristic peak: 1850cm -1 The characteristic peak of acid anhydride group is at 3400cm -1 The characteristic peak of -OH is at 1650cm -1 The place is the characteristic peak of amide group, 1240cm -1 is the characteristic peak of aromatic C-O-C.

Synthetic example 3

[0088] Synthesis of capping agent 1 containing crosslinkable groups:

[0089]

[0090] Take 1.39g (10mmol) m-nitrophenol, dissolve it in 20mL of DMSO solvent, then add 1.18g (5mmol) p-dibromobenzene and 3.69g (22mmol) CsOH·H 2 O, react in an oil bath at 150°C for 36 hours, follow the reaction by TLC, after the reaction is complete, the product is purified by column chromatography to obtain intermediate I;

[0091] Take 2.94g (10mmol) of intermediate I, dissolve it in 20mL of DMSO solvent, then add 1.54g (10mmol) of 3,5-dimethylolphenol and 3.69g (22mmol) of CsOH·H 2 O, 150 ° C oil bath reaction 36h, TLC tracking reaction, after the reaction is complete, the product was purified by column chromatography to obtain intermediate II.

[0092] Take 0.72g (30mmol) of sodium hydride, add it to 20mL of dry anisole solution, take another 3.67g (10mmol) of intermediate II, add 30mL of dry anisole solvent, add dropwise to the former solution, and reflux after the dropwise addition Af...

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Abstract

The invention provides an end-capping reagent containing a crosslinkable group, modified polyimide precursor resin, a photosensitive resin composition and application thereof. The cross-linkable group-containing end-capping reagent has the effect of a cross-linking agent during high-temperature curing, can be applied to polyimide precursor resin synthesis to obtain modified polyimide precursor resin with a cross-linking function. The odified polyimide precursor resin has a self-crosslinking function, and does not need an additional cross-linking agent; in the high-temperature curing process, the cross-linking group of the end-capping reagent can realize cross-linking among polyimide resin molecules to form a network cross-linked structure, so the overall heat resistance of the photoresistis improved, and meanwhile, the effects of improving the stripping resistance, reducing the amount of micromolecular volatile matters, improving the glass transition temperature of the photoresist andthe like are achieved. Meanwhile, the crosslinkable group reacts with phenolic hydroxyl groups in a polyimide main chain, so all or part of hydroxyl groups are consumed, the hygroscopicity of the material can be reduced, and the stability of a device can be improved.

Description

technical field [0001] The invention belongs to the technical field of photolithography, and relates to an end-capping agent containing a crosslinkable group, a modified polyimide precursor resin, a photosensitive resin composition and applications thereof. Background technique [0002] Polyimide has excellent high and low temperature resistance, mechanical properties, dielectric properties, biocompatibility, low thermal expansion coefficient and many other properties, and is widely used in the electronic equipment industry, aerospace industry, advanced composite materials, fiber, engineering plastics, photoresist and other fields. Photosensitive polyimide is mainly used in photoresist in the field of microelectronics. Compared with ordinary polyimide, it can greatly simplify the photolithography process, and because it has good heat resistance and mechanical properties , electrical properties and corrosion resistance, etc., are widely used in large-scale integrated circuit...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C217/90C07C213/02C07C205/38C07C201/12C08G73/10G03F7/004
CPCC07C217/90C07C213/02C07C201/12C08G73/1017G03F7/004C07C205/38
Inventor 王旭王晓伟刘永祥韩红彦李青松
Owner BEIJING ETERNAL MATERIAL TECH
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