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CN120004805A - A photocurable blocked isocyanate compound and low-temperature curing photoresist - Google Patents

A photocurable blocked isocyanate compound and low-temperature curing photoresist Download PDF

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Publication number
CN120004805A
CN120004805A CN202510495436.0A CN202510495436A CN120004805A CN 120004805 A CN120004805 A CN 120004805A CN 202510495436 A CN202510495436 A CN 202510495436A CN 120004805 A CN120004805 A CN 120004805A
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parts
isocyanate compound
photocurable
ring
reaction
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汪瑾
游皓然
孙超
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Hefei University of Technology
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Hefei University of Technology
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
    • C07D249/18—Benzotriazoles
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention discloses a photo-curable closed isocyanate compound and a low-temperature curing photoresist, belonging to the field of semiconductor materials. The photo-curable closed isocyanate compound can participate in photo-curing reaction, can realize deblocking at 80 ℃ and cross-linking reaction with a system, effectively reduces the heat curing temperature of photoresist, can cure at a lower temperature of 80 ℃, can be widely applied to photoetching in the fields of display, PCB, semiconductor and the like, can effectively reduce the process temperature, and improves the mechanical property, the thermal stability and the like.

Description

Photo-curable closed isocyanate compound and low-temperature curing photoresist
Technical Field
The invention belongs to the field of semiconductor materials, and particularly relates to a photo-curable closed isocyanate compound and a low-temperature curing photoresist.
Background
Photoresist is a material sensitive to light of a specific wavelength, and is widely used in photolithography processes, and can be classified into positive photoresist and negative photoresist according to chemical properties. The acrylic acid ester photoresist is widely applied to negative photoresist, and has the advantages of high transparency and the like. Acrylic acid ester photoresist is usually compounded with a thermosetting epoxy composition to obtain a photo-thermal dual curing system so as to improve the performances of strength, heat resistance and the like, but the curing temperature of the epoxy resin is mostly above 130 ℃, so that the energy consumption is high, and the performance of electronic products is influenced. Therefore, it is important to develop a curing agent with low curing temperature and high curing rate.
The isocyanate (-NCO) group has high reactivity and can react with a plurality of groups containing active H, and in order to solve the problems of storage stability and reaction controllability, the preparation of the blocked isocyanate is a common means. And adding closed isocyanate into the acrylic photoresist, and deprotecting an-NCO group by a heating thermal sealing mode to realize a crosslinking reaction so as to replace the thermosetting reaction of epoxy resin. The existing common blocking agents comprise (1) alcohols and alcohols blocked isocyanate with extremely high blocking stability, wherein the deblocking temperature of the blocking agents generally exceeds the curing temperature of epoxy resin, (2) phenols and phenol blocking agents can obviously reduce the deblocking temperature of isocyanate due to electron-withdrawing effects of benzene rings and substituents on the benzene rings, but the strong electron-withdrawing effects cause the phenol blocking agents to react with isocyanate slowly, (3) amines, the high reactivity of the isocyanate on the amines causes the deblocking temperature of the amines to be higher, (4) oximes and oxime blocking agents with unsatisfactory deblocking efficiency and poor photostability, and (5) amides and amide blocking agents with unsatisfactory deblocking efficiency. The above problems limit the use of isocyanate curing agents in acrylic photoresists.
Disclosure of Invention
The invention provides a photo-curable closed isocyanate compound and a low-temperature curing photoresist, which are used for solving the problems of high deblocking temperature and low deblocking efficiency of closed isocyanate and realizing low-temperature curing of acrylic negative photoresist. The photo-curable closed isocyanate compound can participate in photo-curing reaction, can realize deblocking at 80 ℃ and cross-linking reaction with a system, effectively reduces the heat curing temperature of photoresist, and can be cured at a lower temperature of 80 ℃ and widely applied to lithography in the fields of display, PCB, semiconductors and the like. In addition, the blocked isocyanate compound can be applied to the fields of paint, adhesive and the like.
The invention relates to a photo-curable closed isocyanate compound, which has the following structural general formula:
In the general formula:
r 1 represents 、、、、Or (b);
R 2 represents、Or (b);
R 3 represents、、Or (b)。
The invention relates to a preparation method of a photo-curable blocked isocyanate compound, which comprises the steps of firstly, carrying out addition reaction on an alcohol monomer containing acryloyloxy group and a diisocyanate compound to obtain an isocyanate containing acryloyloxy group, and then carrying out addition reaction on the obtained product and an azole compound to obtain the photo-curable blocked isocyanate compound. The method specifically comprises the following steps:
Adding 80-120 parts by mass of diisocyanate, 0.1-0.2 part by mass of catalyst and 60-100 parts by mass of solvent into a reactor with a condensing reflux device, heating to 30-50 ℃, slowly dripping 40-60 parts by mass of alcohol monomer containing acryloyloxy, 0.4-0.6 part by mass of 4-Methoxyphenol (MEHQ) and 10-60 parts by mass of solvent into the reactor by using a constant pressure dropping funnel, and reacting for 1-3 hours to obtain a colorless transparent liquid product;
And 2, continuously adding 0.1-0.2 part by mass of catalyst into the product obtained in the step 1, slowly dripping 20-60 parts by mass of azole compound and 80-120 parts by mass of solvent into a reactor by using a constant pressure dropping funnel, heating to 50-70 ℃ for reacting for 1-2 hours, and performing reduced pressure distillation after the reaction is finished to obtain the target product.
The diisocyanate is selected from diphenylmethane diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate or m-xylylene isocyanate.
The alcohol monomer containing acryloxy is selected from hydroxyethyl acrylate, hydroxypropyl acrylate or pentaerythritol triacrylate.
The catalyst is selected from dibutyl tin dilaurate, stannous octoate, triethylamine, triethylenediamine (DABCO), N-methylmorpholine (NMM) or triethanolamine.
The azole compound is selected from 2-ethylimidazole, 2-propylimidazole, 3-methylpyrazole or methyl-1-H-benzotriazole.
The solvent is selected from one of acetone, tetrahydrofuran, ethyl acetate or chloroform.
The synthetic route is as follows:
The diisocyanate OCN-R 1 -NCO reacts with an alcohol monomer containing acryloyloxy to generate OCN-R 1-NHCO-O-R2, and then reacts with an azole compound to generate a target product R 3-O-CONH-R1-NHCO-O-R2.
The preparation method has mild reaction conditions, no need of expensive catalysts in the reaction process, simple process route and easily obtained reaction raw materials.
The photo-curable closed isocyanate compound structurally carries acryloyloxy groups, and homopolymerizes or copolymerizes with other acryloyloxy groups under the action of ultraviolet light.
The photocurable blocked isocyanate compound can be applied to a photo-thermal dual curing system containing hydroxyl.
The photo-thermal dual curing system comprises a coating, ink, an adhesive, photoresist and the like.
The invention relates to the use of photocurable blocked isocyanate compounds for producing negative photoresist.
Specifically, the photocurable closed isocyanate compound is used as a functional monomer to be added into a negative photoresist collagen component, and the negative photoresist is prepared by low-temperature curing.
The negative photoresist comprises the following raw material components in parts by mass:
10-30 parts of alkali-soluble acrylate resin, 5-30 parts of photo-curable blocked isocyanate compound, 1-5 parts of photoinitiator, 0.5-1 part of auxiliary agent and 50-70 parts of solvent.
The method specifically comprises the following steps:
Mixing a solvent, an alkali-soluble acrylate resin, a photo-curable closed isocyanate compound, a photoinitiator and an auxiliary agent according to a proportion, stirring the mixture at 25 ℃ until the mixture is uniformly mixed, spin-coating the mixture on a silicon wafer by using a spin-coating instrument, baking the silicon wafer on a 60 ℃ hot table for 70-120 s, then placing the silicon wafer under an exposure machine with gamma=365 nm and P=37 mJ/cm 2 for radiation curing, placing the exposed silicon wafer in a developing solution for developing for 25-40 s, and finally placing the silicon wafer on an 80 ℃ hot table for baking for 1-2 h.
Further, the alkali-soluble acrylate resin is an aliphatic acrylate resin, a bisphenol A acrylate resin or a phenolic acrylate resin with an acid value of 70-100 mgKOH/g.
Further, the photoinitiator is 1- [4- (phenylthio) phenyl ] -1, 2-octanedione 2- (O-benzoyl oxime) or 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl ] ethanone-O-acetyl oxime.
Further, the solvent is acetone, tetrahydrofuran, ethyl acetate or chloroform.
Further, the auxiliary agent is 3- (methacryloyloxy) propyl trimethoxysilane, 3-mercaptopropyl triethoxysilane, trimethoxy [2- (7-oxabicyclo [4.1.0] hept-3-yl) ethyl ] silane.
Further, the developing solution is 0.03-0.05% potassium hydroxide aqueous solution or 3-5% sodium carbonate aqueous solution.
Compared with the prior art, the invention has the beneficial technical effects that:
1. The photo-curable closed isocyanate compound is a photosensitive compound capable of being crosslinked and cured at a lower temperature (80 ℃), the molecular structure of the compound contains an acryloyloxy structure and an azole structure, the acryloyloxy structure enables the compound to have photo-curing characteristics, the azole structure can fall off at the lower temperature, and the compound is crosslinked and cured at the same time, so that the mechanical properties of the formula coating such as photoresist and the like are improved.
2. The photo-curable closed isocyanate compound has the characteristics of complete closing reaction and low deblocking temperature due to the fact that imidazole is used as a sealing agent in the molecular structure of the photo-curable closed isocyanate compound.
3. The molecular structure of the photo-curable closed isocyanate compound has acryloyloxy, and can participate in photo-curing reaction and realize quick curing.
4. The photocurable blocked isocyanate compound is applied to a photoresist system containing hydroxyl groups, and the resolution of the prepared photoresist reaches 4 mu m.
Drawings
FIG. 1 is a pattern after photoresist lithography in example 19.
Detailed Description
The technical scheme of the invention is further analyzed and described below by combining specific examples. The raw materials used in the following examples were all derived from commercially available products.
EXAMPLE 1 preparation of a photocurable blocked isocyanate Compound M1
1. 17.3G isophorone diisocyanate, 0.024g dibutyltin dilaurate and 20g ethyl acetate were added into a reactor with a condensing reflux device, the temperature was raised to 30 ℃, 9.0g hydroxyethyl acrylate, 0.082g 4-Methoxyphenol (MEHQ) and 10g ethyl acetate were slowly dropped into the reactor by a constant pressure dropping funnel, and a colorless transparent liquid product was obtained after reaction for 4 hours.
2. And (2) continuously adding 0.024g of dibutyltin dilaurate into the product obtained in the step (1), slowly dripping 7.4g of 2-ethylimidazole and 10g of ethyl acetate into a reactor by using a constant pressure dropping funnel, heating to 70 ℃ for reaction for 1h, and distilling under reduced pressure after the reaction is finished to obtain the product M1, wherein the yield is 94%. The structural formula is as follows:
。
1H NMR（CDCl3,δ ppm）：1.30(3H,CHHHCHHC-),2.85(2H,CHHHCHHC-),6.86(1H,-NCHCH-,ring),7.20(1H,-NCHCH-,ring),8.18(1H,-CHHNHCO-),2.94(1H,-CCHHNH-),2.69(1H,-CCHHNH-),0.94(3H,CHHCCHH-),1.32(1H,-CCHHC-,ring),1.07(1H,-CCHHC-,ring),0.87(2H,CHHCCHH-),0.87(2H,CHHCCHH-),1.67(1H,-CCHHCH-,ring),1.42(1H,-CCHHCH-,ring), 3.54(1H,-CHHCHCHH-,ring),1.67(1H,CCHHCH-,ring),1.42(1H,CCHHCH-,ring),7.67(1H,-CONHCH-),4.31(2H,-CHHCHHO-),6.30(1H,CHHCHCO-),6.21(1H,CHHCHCO-),5.91(1H,CHHCHCO-).
EXAMPLE 2 preparation of the photocurable blocked isocyanate Compound M2
1. 17.3G isophorone diisocyanate, 0.024g dibutyltin dilaurate and 20g ethyl acetate were added into a reactor with a condensing reflux device, the temperature was raised to 30 ℃, 9.0g hydroxyethyl acrylate, 0.082g 4-Methoxyphenol (MEHQ) and 10g ethyl acetate were slowly dropped into the reactor by a constant pressure dropping funnel, and a colorless transparent liquid product was obtained after reaction for 4 hours.
2. And (2) continuously adding 0.024g of dibutyltin dilaurate into the product obtained in the step (1), slowly dripping 8.7g of 2-propylimidazole and 10g of ethyl acetate into a reactor by using a constant pressure dropping funnel, heating to 55 ℃ for reaction for 2 hours, and distilling under reduced pressure after the reaction is finished to obtain the product M2, wherein the yield is 94%. The structural formula is as follows:
。
1H NMR（CDCl3,δ ppm）：0.95(3H,CHHHCHHCHH-),1.71(2H,CHHHCHHCHH-),2.87(2H,CHHHCHHCHH-),6.86(1H,-NCHCH-,ring),7.20(1H,-CONCH-,ring),8.18(1H,-CONHCHH-),2.94(1H,-NHCHHC-),2.69(1H,-NHCHHC-),0.94(3H,CHHHCCHH-),1.32(1H,-CCHHC-,ring),1.07(1H,-CCHHC-,ring),0.87(3H,CHHHCCHH-),0.87(3H,CHHHCCHH-),1.67(1H,-CHCHHC-,ring),1.42(1H,-CHCHHC-,ring),3.54(1H,-CHHCHCHH-,ring),1.67(1H,-CCHHCH-,ring),1.42(1H,-CCHHCH-,ring),7.67(1H,-CHNHCOO-),4.31(2H,-CHHCHHO-),2.92(2H,-COCHHCHH-),6.30(1H,-CHHCOCH-),5.91(1H,CHHCHCO-),6.21(1H,CHHCHCO-).
EXAMPLE 3 preparation of the photocurable blocked isocyanate Compound M3
1. 17.3G isophorone diisocyanate, 0.024g dibutyltin dilaurate and 20g ethyl acetate were added into a reactor with a condensing reflux device, the temperature was raised to 30 ℃, 9.0g hydroxyethyl acrylate, 0.082g 4-Methoxyphenol (MEHQ) and 10g ethyl acetate were slowly dropped into the reactor by a constant pressure dropping funnel, and a colorless transparent liquid product was obtained after reaction for 4 hours.
2. And (2) continuously adding 0.024g of dibutyltin dilaurate into the product obtained in the step (1), slowly dripping 6.4g of 3-methylpyrazole and 10g of ethyl acetate into a reactor by using a constant pressure dropping funnel, heating to 60 ℃ for reaction for 1h, and carrying out reduced pressure distillation after the reaction is finished to obtain the product M3 with the yield of 90%. The structural formula is as follows:
。
1H NMR（CDCl3,δ ppm）：2.30(3H,CHHHCN-),6.18(1H,CHHHCCH-,ring),8.19(1H,-NCHCH-,ring),8.18(1H,-CONHCHH-),2.94(1H,-NHCHHC-),2.69(1H,-NHCHHC-),0.94(CHHHCCHH-),1.32(1H,-CCHHC-,ring),1.07(1H,-CCHHC-,ring),0.87(3H,CHHHCCHH-),0.87(3H,CHHHCCHH-),1.67(1H,-CCHHCH-,ring),1.42(1H,-CCHHCH-,ring),3.54(1H,-NHCHCHH-,ring),1.67(1H,-CCHHCH-,ring),1.42(1H,-CCHHCH-,ring),7.67(1H,-CONHCH-),4.31(2H,-CHHCHHO-),2.92(2H,-COCH2CH2-),6.30(1H,CHHCHCO-),5.91(1H,CHHCHCO-),6.21(1H,CHHCHCO-).
EXAMPLE 4 preparation of the photocurable blocked isocyanate Compound M4
1. 17.3G isophorone diisocyanate, 0.024g dibutyltin dilaurate and 20g ethyl acetate were added into a reactor with a condensing reflux device, the temperature was raised to 30 ℃, 9.0g hydroxyethyl acrylate, 0.082g 4-Methoxyphenol (MEHQ) and 10g ethyl acetate were slowly dropped into the reactor by a constant pressure dropping funnel, and a colorless transparent liquid product was obtained after reaction for 4 hours.
2. And (2) continuously adding 0.024g of dibutyltin dilaurate into the product obtained in the step (1), slowly dripping 6.2g of methyl-1-H-benzotriazole and 10g of ethyl acetate into a reactor by using a constant pressure dropping funnel, heating to 70 ℃ for reaction for 2 hours, and distilling under reduced pressure after the reaction is finished to obtain the product M4 with the yield of 87%. The structural formula is as follows:
。
1H NMR（CDCl3,δ ppm）：2.45(3H,CHHHCCH-),8.12(1H,CHHHCCHCN-,Ph),7.80(1H,-CCHCH-,Ph),7.91(1H,-CHCHCN-,Ph),8.18(1H,-CONHCHH-),2.94(1H,-NHCHHC-),2.69(1H,-NHCHHC-),0.94(CHHHCCHH-),1.32(1H,-CCHHC-,ring),1.07(1H,-CCHHC-,ring),0.87(3H,CHHHCCHH-),0.87(3H,CHHHCCHH-),1.67(1H,-CCHHCH-,ring),1.42(1H,-CCHHCH-,ring),3.54(1H,-NHCHCHH-,ring),1.67(1H,-CCHHCH-,ring),1.42(1H,-CCHHCH-,ring),7.67(1H,-CONHCH-),4.31(2H,-CHHCHHO-),2.92(2H,-COCH2CH2-),6.30(1H,CHHCHCO-),5.91(1H,CHHCHCO-),6.21(1H,CHHCHCO-).
EXAMPLE 5 preparation of the photocurable blocked isocyanate Compound M5
1. 17.3G of isophorone diisocyanate, 0.024g of dibutyltin dilaurate and 20g of ethyl acetate are added into a reactor with a condensing reflux device, the temperature is raised to 50 ℃, 22.4g of pentaerythritol triacrylate, 0.082g of 4-Methoxyphenol (MEHQ) and 10g of ethyl acetate are slowly dripped into the reactor by using a constant pressure dripping funnel, and a colorless transparent liquid product is obtained after reaction for 5 hours.
2. And (2) continuously adding 0.024g of dibutyltin dilaurate into the product obtained in the step (1), slowly dripping 7.4g of 2-ethylimidazole and 10g of ethyl acetate into a reactor by using a constant pressure dropping funnel, heating to 70 ℃ for reaction for 1h, and distilling under reduced pressure after the reaction is finished to obtain the product M5, wherein the yield is 94%. The structural formula is as follows:
。
1H NMR（CDCl3,δ ppm）：1.30(3H,CH3CH2C-),2.85(2H,CH3CH2C-),6.86(1H,-NCHCH-,ring),7.20(1H,-CONCH-,ring),8.18(1H,-CONHCHH-),2.94(1H,-NHCHHC-),2.69(1H,-NHCHHC-),0.94(CHHHCCHH-),1.32(1H,-CCHHC-,ring),1.07(1H,-CCHHC-,ring),0.87(3H,CHHHCCHH-),0.87(3H,CHHHCCHH-),1.67(1H,-CCHHCH-,ring),1.42(1H,-CCHHCH-,ring),3.54(1H,-NHCHCHH-,ring),1.67(1H,-CCHHCH-,ring),1.42(1H,-CCHHCH-,ring),7.67(1H,-CONHCH-),4.31(2H,-OCHHC-),6.12(1H,CHHCHCO-),5.83(1H,CHHCHCO-),6.41 (1H,CHHCHCO-).
EXAMPLE 6 preparation of the photocurable blocked isocyanate Compound M6
1. 17.3G of isophorone diisocyanate, 0.024g of dibutyltin dilaurate and 20g of ethyl acetate are added into a reactor with a condensing reflux device, the temperature is raised to 50 ℃, 22.4g of pentaerythritol triacrylate, 0.082g of 4-Methoxyphenol (MEHQ) and 10g of ethyl acetate are slowly dripped into the reactor by using a constant pressure dripping funnel, and a colorless transparent liquid product is obtained after reaction for 5 hours.
2. And (2) continuously adding 0.024g of dibutyltin dilaurate into the product obtained in the step (1), slowly dripping 8.7g of 2-propylimidazole and 10g of ethyl acetate into a reactor by using a constant pressure dropping funnel, heating to 70 ℃ for reaction for 1h, and distilling under reduced pressure after the reaction is finished to obtain the product M6 with the yield of 94%. The structural formula is as follows:
。
1H NMR（CDCl3,δ ppm）：0.95(3H,CH3CH2CH2-),1.71(2H,CH3CH2CH2-),2.87(2H,-CH2CH2C-),6.86(1H,-NCHCH-,ring),7.20(1H,-CHCHN-,ring),8.18(1H,-CONHCHH-),2.94(1H,-NHCHHC-),2.69(1H,-NHCHHC-),0.94(CHHHCCHH-),1.32(1H,-CCHHC-,ring),1.07(1H,-CCHHC-,ring),0.87(3H,CHHHCCHH-),0.87(3H,CHHHCCHH-),1.67(1H,-CCHHCH-,ring),1.42(1H,-CCHHCH-,ring),3.54(1H,-NHCHCHH-,ring),1.67(1H,-CCHHCH-,ring),1.42(1H,-CCHHCH-,ring),7.67(1H,-CONHCH-),4.31(2H,-OCHHC-),6.12(1H,CHHCHCO-),5.83(1H,CHHCHCO-),6.41 (1H,CHHCHCO-).
EXAMPLE 7 preparation of a photocurable blocked isocyanate Compound M7
1. 17.3G of isophorone diisocyanate, 0.024g of dibutyltin dilaurate and 20g of ethyl acetate are added into a reactor with a condensing reflux device, the temperature is raised to 50 ℃, 22.4g of pentaerythritol triacrylate, 0.082g of 4-Methoxyphenol (MEHQ) and 10g of ethyl acetate are slowly dripped into the reactor by using a constant pressure dripping funnel, and a colorless transparent liquid product is obtained after reaction for 5 hours.
2. And (2) continuously adding 0.024g of dibutyltin dilaurate into the product obtained in the step (1), slowly dripping 6.4g of 3-methylpyrazole and 10g of ethyl acetate into a reactor by using a constant pressure dropping funnel, heating to 70 ℃ for reaction for 2 hours, and distilling under reduced pressure after the reaction is finished to obtain the product M7, wherein the yield is 89%. The structural formula is as follows:
。
1H NMR（CDCl3,δ ppm）：2.30(3H,CHHHCN-),6.18(1H,-CCHCH-,ring),8.19(1H,-CHNCO-,ring),8.18(1H,-CONHCHH-),2.94(1H,-NHCHHC-),2.69(1H,-NHCHHC-),0.94(CHHHCCHH-),1.32(1H,-CCHHC-,ring),1.07(1H,-CCHHC-,ring),0.87(3H,CHHHCCHH-),0.87(3H,CHHHCCHH-),1.67(1H,-CCHHCH-,ring),1.42(1H,-CCHHCH-,ring),3.54(1H,-NHCHCHH-,ring),1.67(1H,-CCHHCH-,ring),1.42(1H,-CCHHCH-,ring),7.67(1H,-CONHCH-),4.31(2H,-OCHHC-),6.12(1H,CHHCHCO-),5.83(1H,CHHCHCO-),6.41 (1H,CHHCHCO-).
EXAMPLE 8 preparation of the photocurable blocked isocyanate Compound M8
1. 17.3G of isophorone diisocyanate, 0.024g of dibutyltin dilaurate and 20g of ethyl acetate are added into a reactor with a condensing reflux device, the temperature is raised to 50 ℃, 22.4g of pentaerythritol triacrylate, 0.082g of 4-Methoxyphenol (MEHQ) and 10g of ethyl acetate are slowly dripped into the reactor by using a constant pressure dripping funnel, and a colorless transparent liquid product is obtained after reaction for 5 hours.
2. And (2) continuously adding 0.024g of dibutyltin dilaurate into the product obtained in the step (1), slowly dripping 6.2g of methyl-1-H-benzotriazole and 10g of ethyl acetate into a reactor by using a constant pressure dropping funnel, heating to 70 ℃ for reaction for 2 hours, and distilling under reduced pressure after the reaction is finished to obtain the product M8, wherein the yield is 87%. The structural formula is as follows:
。
1H NMR（CDCl3,δ ppm）：2.45(3H,CHHHCCH-),8.12(1H,-CCHCN-,ring),7.80(1H,-CCHCH-,ring),7.91(1H,-CHCN-,ring),8.18(1H,-CONHCHH-),2.94(1H,-NHCHHC-),2.69(1H,-NHCHHC-),0.94(CHHHCCHH-),1.32(1H,-CCHHC-,ring),1.07(1H,-CCHHC-,ring),0.87(3H,CHHHCCHH-),0.87(3H,CHHHCCHH-),1.67(1H,-CCHHCH-,ring),1.42(1H,-CCHHCH-,ring),3.54(1H,-NHCHCHH-,ring),1.67(1H,-CCHHCH-,ring),1.42(1H,-CCHHCH-,ring),7.67(1H,-CONHCH-),4.31(2H,-OCHHC-),6.12(1H,CHHCHCO-),5.83(1H,CHHCHCO-),6.41 (1H,CHHCHCO-).
EXAMPLE 9 preparation of the photocurable blocked isocyanate Compound M9
1. 19.5G of diphenylmethane diisocyanate, 0.024g of dibutyltin dilaurate and 20g of acetone are added into a reactor with a condensing reflux device, the temperature is raised to 30 ℃, 9.0g of hydroxyethyl acrylate, 0.082g of 4-Methoxyphenol (MEHQ) and 10g of ethyl acetate are slowly dripped into the reactor by using a constant pressure dripping funnel, and a colorless transparent liquid product is obtained after the reaction for 1 hour.
2. And (2) continuously adding 0.024g of dibutyltin dilaurate into the product obtained in the step (1), slowly dripping 7.4g of 2-ethylimidazole and 10g of acetone into a reactor by using a constant pressure dropping funnel, heating to 60 ℃ for reaction for 2 hours, and distilling under reduced pressure after the reaction is finished to obtain the product M9 with the yield of 92%. The structural formula is as follows:
。
1H NMR（CDCl3,δ ppm）：1.30(3H,CH3CH2C-),2.85(2H,CH3CH2C-),6.86(1H,-NCHCH-,ring),7.20(1H,-NCHCH-,ring),9.97(1H,-CONHC-),7.52(1H,-CCHCH-,Ph),7.10(1H,-CHCHC-,Ph),3.83(2H,-CCHC-),9.86(1H,-CNHCO-),4.31(2H,-CHHCHHO-),2.92(2H,-COCH2CH2-),6.30(1H,CHHCHCO-),5.91(1H,CHHCHCO-),6.21(1H,CHHCHCO-).
EXAMPLE 10 preparation of a photocurable blocked isocyanate Compound M10
1. 19.5G of diphenylmethane diisocyanate, 0.024g of dibutyltin dilaurate and 20g of ethyl acetate were charged into a reactor with a condensing reflux device, the temperature was raised to 30 ℃, 10.1g of hydroxypropyl acrylate, 0.082g of 4-Methoxyphenol (MEHQ) and 10g of ethyl acetate were slowly dropped into the reactor by using a constant pressure dropping funnel, and a colorless transparent liquid product was obtained after reaction for 1 hour.
2. And (2) continuously adding 0.024g of dibutyltin dilaurate into the product obtained in the step (1), slowly dripping 8.7g of 2-propylimidazole and 10g of ethyl acetate into a reactor by using a constant pressure dropping funnel, heating to 60 ℃ for reaction for 2 hours, and distilling under reduced pressure after the reaction is finished to obtain the product M10, wherein the yield is 92%. The structural formula is as follows:
。
1H NMR（CDCl3,δ ppm）：0.95(3H,CH3CH2CH2-),1.71(2H,CH3CH2CH2-),2.87(2H,-CH2CH2C-),6.86(1H,-NCHCH-,ring),7.20(1H,-CHCHN-,ring),9.97(1H,-CONHC-),7.52(1H,-CCHCH-,Ph),7.10(1H,-CHCHC-,Ph),3.83(2H,-CCHC-),9.86(1H,-CNHCO-),4.49(1H,-OCHHCH-),4.24(1H,-OCHHCH-),2.41(1H,-CHHCHCHH-),0.93(3H,CH3CHCH2-),2.98(1H,-CHCO-), 6.30(1H,CHHCHCO-),5.91(1H,CHHCHCO-),6.21(1H,CHHCHCO-).
EXAMPLE 11 preparation of the photocurable blocked isocyanate Compound M11
1. 19.5G of diphenylmethane diisocyanate, 0.024g of dibutyltin dilaurate and 20g of ethyl acetate were added into a reactor with a condensing reflux device, the temperature was raised to 30 ℃, 9.0g of hydroxyethyl acrylate, 0.082g of 4-Methoxyphenol (MEHQ) and 10g of ethyl acetate were slowly dropped into the reactor by using a constant pressure dropping funnel, and colorless transparent liquid products were obtained after reaction for 1 hour.
2. And (2) continuously adding 0.024g of dibutyltin dilaurate into the product obtained in the step (1), slowly dripping 6.4g of 3-methylpyrazole and 10g of ethyl acetate into a reactor by using a constant pressure dropping funnel, heating to 70 ℃ for reaction for 2 hours, and distilling under reduced pressure after the reaction is finished to obtain the product M11, wherein the yield is 90%. The structural formula is as follows:
。
1H NMR（CDCl3,δ ppm）：2.30(3H,CHHHCN-),6.18(1H,-CCHCH-,ring),8.19(1H,-CHNCO-,ring),9.97(1H,-CONHC-),7.52(1H,-CCHCH-,Ph),7.10(1H,-CHCHC-,Ph),3.83(2H,-CCHC-),9.86(1H,-CNHCO-),4.31(2H,-CHHCHHO-),2.92(2H,-COCH2CH2-),6.30(1H,CHHCHCO-),5.91(1H,CHHCHCO-),6.21(1H,CHHCHCO-).
EXAMPLE 12 preparation of the photocurable blocked isocyanate Compound M12
1. 19.5G of diphenylmethane diisocyanate, 0.024g of dibutyltin dilaurate and 20g of ethyl acetate were added into a reactor with a condensing reflux device, the temperature was raised to 30 ℃, 9.0g of hydroxyethyl acrylate, 0.082g of 4-Methoxyphenol (MEHQ) and 10g of ethyl acetate were slowly dropped into the reactor by using a constant pressure dropping funnel, and colorless transparent liquid products were obtained after reaction for 1 hour.
2. And (2) continuously adding 0.024g of dibutyltin dilaurate into the product obtained in the step (1), slowly dripping 6.2g of methyl-1-H-benzotriazole and 10g of ethyl acetate into a reactor by using a constant pressure dropping funnel, heating to 70 ℃ for reaction for 2 hours, and distilling under reduced pressure after the reaction is finished to obtain the product M12 with the yield of 88%. The structural formula is as follows:
。
1H NMR（CDCl3,δ ppm）：2.45(3H,CHHHCCH-),8.12(1H,-CCHCN-,ring),7.80(1H,-CCHCH-,ring),7.91(1H,-CHCN-,ring),9.97(1H,-CONHC-),7.52(1H,-CCHCH-,Ph),7.10(1H,-CHCHC-,Ph),3.83(2H,-CCHC-),9.86(1H,-CNHCO-),4.31(2H,-CHHCHHO-),2.92(2H,-COCH2CH2-),6.30(1H,CHHCHCO-),5.91(1H,CHHCHCO-),6.21(1H,CHHCHCO-).
EXAMPLE 13 preparation of the photocurable blocked isocyanate Compound M13
1. 19.5G of diphenylmethane diisocyanate, 0.024g of dibutyltin dilaurate and 20g of ethyl acetate are added into a reactor with a condensing reflux device, the temperature is raised to 30 ℃, 22.4g of pentaerythritol triacrylate, 0.082g of 4-Methoxyphenol (MEHQ) and 10g of ethyl acetate are slowly dripped into the reactor by using a constant pressure dripping funnel, and a colorless transparent liquid product is obtained after the reaction for 1 hour.
2. And (2) continuously adding 0.024g of dibutyltin dilaurate into the product obtained in the step (1), slowly dripping 7.4g of 2-ethylimidazole and 10g of ethyl acetate into a reactor by using a constant pressure dropping funnel, heating to 70 ℃ for reaction for 2 hours, and distilling under reduced pressure after the reaction is finished to obtain the product M13, wherein the yield is 95%. The structural formula is as follows:
。
1H NMR（CDCl3,δ ppm）：1.30(3H,CH3CH2C-),2.85(2H,CH3CH2C-),6.86(1H,-NCHCH-,ring),7.20(1H,-NCHCH-,ring),9.97(1H,-CONHC-),7.52(1H,-CCHCH-,Ph),7.10(1H,-CHCHC-,Ph),3.83(2H,-CCHC-),9.88(1H,-CNHCO-),4.31(2H,-OCHHC-),6.12(1H,CHHCHCO-),5.83(1H,CHHCHCO-),6.41 (1H,CHHCHCO-).
EXAMPLE 14 preparation of the photocurable blocked isocyanate Compound M14
1. 19.5G of diphenylmethane diisocyanate, 0.024g of dibutyltin dilaurate and 20g of ethyl acetate are added into a reactor with a condensing reflux device, the temperature is raised to 30 ℃, 22.4g of pentaerythritol triacrylate, 0.082g of 4-Methoxyphenol (MEHQ) and 10g of ethyl acetate are slowly dripped into the reactor by using a constant pressure dripping funnel, and a colorless transparent liquid product is obtained after the reaction for 1 hour.
2. And (2) continuously adding 0.024g of dibutyltin dilaurate into the product obtained in the step (1), slowly dripping 8.7g of 2-propylimidazole and 10g of ethyl acetate into a reactor by using a constant pressure dropping funnel, heating to 70 ℃ for reaction for 2 hours, and distilling under reduced pressure after the reaction is finished to obtain the product M14, wherein the yield is 93%. The structural formula is as follows:
。
1H NMR（CDCl3,δ ppm）：0.95(3H,CH3CH2CH2-),1.71(2H,CH3CH2CH2-),2.87(2H,-CH2CH2C-),6.86(1H,-NCHCH-,ring),7.20(1H,-CHCHN-,ring),9.97(1H,-CONHC-),7.52(1H,-CCHCH-,Ph),7.10(1H,-CHCHC-,Ph),3.83(2H,-CCHC-),9.88(1H,-CNHCO-),4.31(2H,-OCHHC-),6.12(1H,CHHCHCO-),5.83(1H,CHHCHCO-),6.41 (1H,CHHCHCO-).
EXAMPLE 15 preparation of the photocurable blocked isocyanate Compound M15
1. 14.6G of m-xylylene diisocyanate, 0.024g of dibutyltin dilaurate and 20g of ethyl acetate are added into a reactor with a condensing reflux device, the temperature is raised to 50 ℃, 22.4g of pentaerythritol triacrylate, 0.082g of 4-Methoxyphenol (MEHQ) and 10g of ethyl acetate are slowly dripped into the reactor by using a constant pressure dripping funnel, and colorless transparent liquid products are obtained after the reaction for 2 hours.
2. And (2) continuously adding 0.024g of dibutyltin dilaurate into the product obtained in the step (1), slowly dripping 6.4g of 3-methylpyrazole and 10g of ethyl acetate into a reactor by using a constant pressure dropping funnel, heating to 70 ℃ for reaction for 2 hours, and distilling under reduced pressure after the reaction is finished to obtain the product M15, wherein the yield is 90%. The structural formula is as follows:
。
1H NMR（CDCl3,δ ppm）：2.30(3H,CHHHCN-),6.18(1H,-CCHCH-,ring),8.19(1H,-CHNCO-,ring),9.97(1H,-CONHC-),7.52(1H,-CCHCH-,Ph),7.10(1H,-CHCHC-,Ph),3.83(2H,-CCHC-),9.88(1H,-CNHCO-),4.31(2H,-OCHHC-),6.12(1H,CHHCHCO-),5.83(1H,CHHCHCO-),6.41 (1H,CHHCHCO-).
EXAMPLE 16 preparation of the photocurable blocked isocyanate Compound M16
1. 13.5G of 2, 6-toluene diisocyanate, 0.024g of dibutyltin dilaurate and 20g of ethyl acetate were charged into a reactor equipped with a condensing reflux device, the temperature was raised to 50 ℃, 9.0g of hydroxyethyl acrylate, 0.082g of 4-Methoxyphenol (MEHQ) and 10g of ethyl acetate were slowly dropped into the reactor by using a constant pressure dropping funnel, and a colorless transparent liquid product was obtained after the reaction for 2 hours.
2. And (2) continuously adding 0.024g of dibutyltin dilaurate into the product obtained in the step (1), slowly dripping 6.2g of methyl-1-H-benzotriazole and 10g of ethyl acetate into a reactor by using a constant pressure dropping funnel, heating to 70 ℃ for reaction for 2 hours, and distilling under reduced pressure after the reaction is finished to obtain the product M16 with the yield of 85%. The structural formula is as follows:
。
1H NMR（CDCl3,δ ppm）：2.45(3H,CHHHCCH-),8.12(1H,-CCHCN-,ring),7.80(1H,-CCHCH-,ring),7.91(1H,-CHCN-,ring),9.97(1H,-CONHC-),7.52(1H,-CCHCH-,Ph),7.10(1H,-CHCHC-,Ph),3.83(2H,-CCHC-),9.88(1H,-CNHCO-),4.31(2H,-CHHCHHO-),6.12(1H,CHHCHCO-),5.83(1H,CHHCHCO-),6.41 (1H,CHHCHCO-).
EXAMPLE 17 preparation of the photocurable blocked isocyanate Compound M17
1. 13.5G of 2, 4-toluene diisocyanate, 0.024g of dibutyltin dilaurate and 20g of ethyl acetate were charged into a reactor equipped with a condensing reflux device, the temperature was raised to 50 ℃, 9.0g of hydroxyethyl acrylate, 0.082g of 4-Methoxyphenol (MEHQ) and 10g of ethyl acetate were slowly dropped into the reactor by using a constant pressure dropping funnel, and a colorless transparent liquid product was obtained after the reaction for 2 hours.
2. And (2) continuously adding 0.024g of dibutyltin dilaurate into the product obtained in the step (1), slowly dripping 7.4g of 2-ethylimidazole and 10g of ethyl acetate into a reactor by using a constant pressure dropping funnel, heating to 70 ℃ for reaction for 2 hours, and distilling under reduced pressure after the reaction is finished to obtain the product M17, wherein the yield is 91%. The structural formula is as follows:
。
1H NMR（CDCl3,δ ppm）：5.91(1H,CHHCHCO-),6.21(1H,CHHCHCO-),6.30(1H,CHHCHCO-),2.92(2H,-COCH2CH2-),4.31(2H,-CHHCHHO-),9.86(1H,-CONHC-),2.19(3H,CHHHCCH-),7.36(1H,CHHHCCH-,Ph),7.72(1H,-CCHC-,Ph),7.32(1H,-CHCHC-,Ph),9.97(1H,-CNHCO-),7.20(1H,-CONCH-,ring),6.86(1H,-CHCHN-,ring),2.85(2H,CH3CH2C-),1.30(3H,CH3CH2C-).
EXAMPLE 18 preparation of the photocurable blocked isocyanate Compound M18
1. 13.1G of hexamethylene diisocyanate, 0.024g of dibutyltin dilaurate and 20g of ethyl acetate were added into a reactor with a condensing reflux device, the temperature was raised to 50 ℃, 9.0g of hydroxyethyl acrylate, 0.082g of 4-Methoxyphenol (MEHQ) and 10g of ethyl acetate were slowly dropped into the reactor by using a constant pressure dropping funnel, and colorless transparent liquid products were obtained after reaction for 2 hours.
2. And (2) continuously adding 0.024g of dibutyltin dilaurate into the product obtained in the step (1), slowly dripping 8.7g of 2-propylimidazole and 10g of ethyl acetate into a reactor by using a constant pressure dropping funnel, heating to 70 ℃ for reaction for 2 hours, and distilling under reduced pressure after the reaction is finished to obtain the product M18, wherein the yield is 83%. The structural formula is as follows:
。
1H NMR（CDCl3,δ ppm）：5.91(1H,CHHCHCO-),6.21(1H,CHHCHCO-),6.30(1H,CHHCHCO-),2.92(2H,-COCH2CH2-),4.31(2H,-CHHCHHO-),6.76(1H,-CONHCHH-),3.18(2H,-NHCHHCHH-),1.50(2H,-CH2 CH2 CH2-),1.38(2H,- CH2 CH2),8.18(1H,-CHHNHCO-),7.20(1H,-CHCHN-,ring),6.86(1H,-NCHCH-,ring),2.87(2H,-CH2CH2C-),1.71(2H,CH3CH2CH2-),0.95(3H,CH3CH2CH2-).
EXAMPLE 19 preparation of Low temperature curing negative tone Photoresist composition A1
To a beaker, 30g of an alkali-soluble acrylate resin (commercially available, acid value=100, M w =8000, the same applies hereinafter), 15g of a photocurable blocked isocyanate compound M1, 2.2g of 1- [4- (phenylsulfanyl) phenyl ] -1, 2-octanedione 2- (O-benzoyloxime), 0.45g of 3- (methacryloyloxy) propyltrimethoxysilane, and 90g of ethyl acetate were added, and stirred for 10 minutes to obtain a low-temperature-curable negative photoresist composition A1.
Composition A1 was spin coated on a silicon wafer at a rotation speed of 800rpm for 30 s and the wafer was placed on a 60 ℃ hot stage for heating for 90 s, after which the wafer was placed under an exposure machine of γ=365 nm, p=37 mJ/cm 2 for radiation curing, the exposed wafer was developed in 0.04% aqueous potassium hydroxide for 25 s, and finally the wafer was placed on an 80 ℃ hot stage for baking for 1.5h.
Comparative example 1:
The photocurable blocked isocyanate compound M1 of example 19 was replaced with a curing agent of the type MF-K60X from Asahi Karakui Kaschin, the amounts of the other components and the process were the same, and the post-baking temperature required to achieve the same performance index was measured to be 90 ℃.
EXAMPLE 20 preparation of Low temperature curing negative tone Photoresist composition A2
To a beaker were added 30g of an alkali-soluble acrylate resin, 15g of a photocurable blocked isocyanate compound M2, 2.2 g of 1- [4- (phenylthio) phenyl ] -1, 2-octanedione 2- (O-benzoyloxime), 0.45g of 3- (methacryloyloxy) propyltrimethoxysilane and 90g of acetone, and stirred for 10 minutes to obtain a low-temperature-curable negative photoresist composition A2.
Composition A2 was spin coated on a silicon wafer at a rotation speed of 800rpm for 30 s and the wafer was placed on a 60 ℃ hot stage for heating for 90 s, after which the wafer was placed under an exposure machine of γ=365 nm, p=37 mJ/cm 2 for radiation curing, the exposed wafer was developed in 0.04% aqueous potassium hydroxide for 30 s, and finally the wafer was placed on a 90 ℃ hot stage for baking for 2 hours.
EXAMPLE 21 preparation of Low temperature curing negative tone Photoresist composition A3
To a beaker were added 30g of an alkali-soluble acrylate resin, 15g of a photocurable blocked isocyanate compound M5, 2.2g of 1- [4- (phenylthio) phenyl ] -1, 2-octanedione 2- (O-benzoyloxime), 0.45g of 3- (methacryloyloxy) propyltrimethoxysilane and 90g of ethyl acetate, and stirred for 10 minutes to obtain a low-temperature-curable negative photoresist composition A3.
Composition A3 was spin coated on a silicon wafer at a rotation speed of 1000rpm for 35 s and the silicon wafer was placed on a 60 ℃ hot stage for heating for 90 s, after which the silicon wafer was placed under an exposure machine of γ=365 nm, p=37 mJ/cm 2 for radiation curing, the exposed silicon wafer was developed in 0.04% aqueous potassium hydroxide for 40 s, and finally the silicon wafer was placed on an 80 ℃ hot stage for baking for 1.5 hours.
EXAMPLE 22 preparation of Low temperature curing negative tone Photoresist composition A4
To a beaker were added 30g of an alkali-soluble acrylate resin, 15g of a photocurable blocked isocyanate compound M14, 2.2g of 1- [4- (phenylthio) phenyl ] -1, 2-octanedione 2- (O-benzoyloxime), 0.45g of 3- (methacryloyloxy) propyltrimethoxysilane and 100g of ethyl acetate, and stirred for 10 minutes to obtain a low-temperature-curable negative photoresist composition A4.
Composition A4 was spin coated on a silicon wafer at 1200rpm for 40s and the wafer was placed on a 60 ℃ hot stage for heating to 100 s, after which the wafer was radiation cured by an exposure machine of γ=365 nm, p=37 mJ/cm 2, developed in 0.04% aqueous potassium hydroxide for 40s, and finally baked on an 80 ℃ hot stage for 2h.
Test 1 evaluation of resistance to chemical transformation
The silicon wafer with the photoresist pattern prepared in the example was put into a container filled with PGMEA, ethanol, acetone, methylene chloride, tetrahydrofuran, 10% aqueous sulfuric acid, 10% aqueous potassium hydroxide, respectively, and after immersing and immersing the sample in 24h, it was tested by the hundred method (see national standard GB/T9286-1998).
Test 2 resolution
The silicon wafer with the photoresist pattern prepared in the example is observed by a microscope to observe the pattern state, namely, if the silicon wafer is completely developed and the pattern is clear, the resolution can be considered to be achieved, if the silicon wafer is not completely developed and the pattern is not clear, the resolution can not be considered to be achieved, the pattern with larger size is continued until the pattern which is completely developed and the pattern is clear appears, and the size of the pattern at the moment is recorded as the resolution.
Test 3 thermal stability
The thermal decomposition temperature of the baked photoresist in the examples was measured by a thermogravimetric analyzer.

Claims (10)

1.一种可光固化的封闭型异氰酸酯化合物，其特征在于其结构通式如下所示：1. A photocurable blocked isocyanate compound, characterized in that its general structural formula is as follows: ； ; 上述通式中：In the above general formula: R1表示、、、、或；R 1 means , , , , or ; R2表示、或； R2 represents , or ; R3表示、、或。R 3 means , , or . 2.权利要求1所述可光固化的封闭型异氰酸酯化合物的制备方法，其特征在于：2. The method for preparing the photocurable blocked isocyanate compound according to claim 1, characterized in that: 首先通过含丙烯酰氧基的醇类单体与二异氰酸酯类化合物进行加成反应得到含丙烯酰氧基的异氰酸酯；所得产物再与唑类化合物进行加成反应，得到可光固化的封闭型异氰酸酯化合物，包括如下步骤：First, an alcohol monomer containing an acryloyloxy group is subjected to an addition reaction with a diisocyanate compound to obtain an isocyanate containing an acryloyloxy group; the obtained product is then subjected to an addition reaction with an azole compound to obtain a photocurable blocked isocyanate compound, comprising the following steps: 步骤1：将80~120质量份的二异氰酸酯、0.1~0.2质量份的催化剂、60~100质量份的溶剂加入带有冷凝回流装置的反应器中，升温至30~50℃，再用恒压滴液漏斗将40~60质量份的含丙烯酰氧基的醇类单体、0.4~0.6质量份的4-甲氧基酚、10~60质量份的溶剂缓慢滴入反应器中，反应1~3h得到无色透明液体产物；Step 1: add 80-120 parts by mass of diisocyanate, 0.1-0.2 parts by mass of catalyst, and 60-100 parts by mass of solvent into a reactor with a condensation reflux device, heat to 30-50° C., and then slowly drop 40-60 parts by mass of acryloxy-containing alcohol monomer, 0.4-0.6 parts by mass of 4-methoxyphenol, and 10-60 parts by mass of solvent into the reactor using a constant pressure dropping funnel, and react for 1-3 hours to obtain a colorless transparent liquid product; 步骤2：向上述步骤1得到的产物中继续加入0.1～0.2质量份的催化剂，再用恒压滴液漏斗将20~60质量份的唑类化合物、80~120质量份的溶剂缓慢滴入反应器中，加热至50~70℃反应1~2h，反应结束后减压蒸馏得到目标产物。Step 2: Continue to add 0.1-0.2 parts by mass of catalyst to the product obtained in the above step 1, and then slowly drip 20-60 parts by mass of azole compound and 80-120 parts by mass of solvent into the reactor using a constant pressure dropping funnel, heat to 50-70°C for reaction for 1-2 hours, and after the reaction is completed, perform reduced pressure distillation to obtain the target product. 3.根据权利要求2所述的制备方法，其特征在于：3. The preparation method according to claim 2, characterized in that: 所述二异氰酸酯选自二苯基甲烷二异氰酸酯、2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯或间苯二甲基异氰酸酯。The diisocyanate is selected from diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate or meta-xylylene diisocyanate. 4.根据权利要求2所述的制备方法，其特征在于：4. The preparation method according to claim 2, characterized in that: 所述含丙烯酰氧基的醇类单体选自丙烯酸羟乙酯、丙烯酸羟丙酯或季戊四醇三丙烯酸酯。The alcohol monomer containing an acryloxy group is selected from hydroxyethyl acrylate, hydroxypropyl acrylate or pentaerythritol triacrylate. 5.根据权利要求2所述的制备方法，其特征在于：5. The preparation method according to claim 2, characterized in that: 所述催化剂选自二月桂酸二丁基锡、辛酸亚锡、三乙胺、三亚乙基二胺、N-甲基吗啉或三乙醇胺。The catalyst is selected from dibutyltin dilaurate, stannous octoate, triethylamine, triethylenediamine, N-methylmorpholine or triethanolamine. 6.根据权利要求2所述的制备方法，其特征在于：6. The preparation method according to claim 2, characterized in that: 所述唑类化合物选自2-乙基咪唑、2-丙基咪唑、3-甲基吡唑或甲基-1-H-苯并三唑。The azole compound is selected from 2-ethylimidazole, 2-propylimidazole, 3-methylpyrazole or methyl-1-H-benzotriazole. 7.根据权利要求2所述的制备方法，其特征在于：7. The preparation method according to claim 2, characterized in that: 所述溶剂选自丙酮、四氢呋喃、乙酸乙酯或氯仿中的一种。The solvent is selected from one of acetone, tetrahydrofuran, ethyl acetate or chloroform. 8.权利要求1所述可光固化的封闭型异氰酸酯化合物在制备负性光刻胶中的应用。8. Use of the photocurable blocked isocyanate compound according to claim 1 in the preparation of negative photoresist. 9.根据权利要求8所述的应用，其特征在于：9. The use according to claim 8, characterized in that: 以所述可光固化的封闭型异氰酸酯化合物作为功能单体添加至负性光刻胶原料组分中，低温固化制备负性光刻胶；Adding the photocurable blocked isocyanate compound as a functional monomer to a negative photoresist raw material component, and curing at low temperature to prepare a negative photoresist; 所述负性光刻胶的原料组分按质量份数包括：The raw material components of the negative photoresist include, by mass: 碱溶性丙烯酸酯树脂10~30份，可光固化的封闭型异氰酸酯化合物5~30份，光引发剂1~5份，助剂0.5~1份，溶剂50~70份。10-30 parts of alkali-soluble acrylate resin, 5-30 parts of photocurable blocked isocyanate compound, 1-5 parts of photoinitiator, 0.5-1 parts of auxiliary agent, and 50-70 parts of solvent. 10.根据权利要求9所述的应用，其特征在于：10. The use according to claim 9, characterized in that: 将溶剂、碱溶性丙烯酸酯树脂、可光固化的封闭型异氰酸酯化合物、光引发剂和助剂按配比量混合，在25℃条件下搅拌至混合均匀，将所得混合物使用旋涂仪旋涂在硅片上，置于60℃热台上烘烤70~120 s，之后将硅片放置于γ=365 nm、P=37 mJ/cm2的曝光机下辐照固化，将曝光后的硅片置于显影液中显影25~40 s，最后将硅片放置于80℃热台上烘烤1~2h。The solvent, alkali-soluble acrylic resin, photocurable blocked isocyanate compound, photoinitiator and auxiliary agent are mixed according to the proportion, stirred at 25°C until the mixture is uniformly mixed, and the obtained mixture is spin-coated on a silicon wafer using a spin coater, and baked on a 60°C hot stage for 70-120 s. Then, the silicon wafer is placed in an exposure machine with γ=365 nm and P=37 mJ/ cm2 for radiation curing. The exposed silicon wafer is placed in a developer for development for 25-40 s, and finally, the silicon wafer is placed on a 80°C hot stage for baking for 1-2 h.
CN202510495436.0A 2025-04-21 2025-04-21 A photocurable blocked isocyanate compound and low-temperature curing photoresist Pending CN120004805A (en)

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