CN112552280A - High-acid-yield sulfimide photo-acid generator - Google Patents

High-acid-yield sulfimide photo-acid generator Download PDF

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Publication number
CN112552280A
CN112552280A CN201910908579.4A CN201910908579A CN112552280A CN 112552280 A CN112552280 A CN 112552280A CN 201910908579 A CN201910908579 A CN 201910908579A CN 112552280 A CN112552280 A CN 112552280A
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alkyl
optionally
substituted
photoacid generator
replaced
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钱晓春
胡春青
龚艳
徐丽萍
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Changzhou Tronly New Electronic Materials Co Ltd
Changzhou Tronly Advanced Electronic Materials Co Ltd
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Changzhou Tronly New Electronic Materials Co Ltd
Changzhou Tronly Advanced Electronic Materials Co Ltd
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Priority to CN201910908579.4A priority Critical patent/CN112552280A/en
Priority to PCT/CN2020/117236 priority patent/WO2021057813A1/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • 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

Abstract

The invention discloses a high acid-producing sulfonyl imide photo-acid generator which has a structure shown in a general formula (A). The acid generator has high sensitivity to active energy rays with the wavelength of 300-450nm, particularly 365nm (I line) and 405nm (H line), and is a photoacid generator with good solubility and strong acid generation property.

Description

High-acid-yield sulfimide photo-acid generator
Technical Field
The invention belongs to the field of organic chemistry, and particularly relates to a sulfimide photoacid generator capable of generating acid at a high rate in the wavelength range of 300-450nm, and a preparation method and application thereof.
Background
As a resist material used in a photolithography process, a resin composition containing a resin such as a tert-butyl ester of carboxylic acid or a tert-butyl ester of phenol, silyl ether, and a photoacid generator is typically exemplified. When an active energy ray such as ultraviolet ray is irradiated, the photoacid generator is decomposed to generate a strong acid (optionally, heating (PEB) may be further performed after exposure), and the carboxylic acid derivative or the phenol derivative is deprotected by the strong acid to generate a carboxylic acid or a phenol. By this chemical change, the resin in the exposed portion becomes easily soluble in an alkaline developer, and then it reacts with the alkaline developer, and the formation of a pattern can be promoted.
Various types of photoacid generators used in chemically amplified resists are known, and can be classified into nonionic and ionic types. Among them, the ionic photoacid generator is often insufficient in compatibility with a solvent, and is likely to cause phase separation in a resist material, and thus cannot sufficiently function. Nonionic photoacid generators generally have problems such as insufficient sensitivity at long wavelengths and poor solubility in solvents.
Disclosure of Invention
The invention mainly aims to provide a photoacid generator which has high sensitivity to active energy rays with the wavelength of 300-450nm, particularly 365nm (I line) and 405nm (H line), and has good solubility and strong acid generation property.
To achieve the above object, a sulfonyl imide photoacid generator capable of generating acid at high levels on the I line and the H line has a structure represented by the following general formula (a):
Figure BDA0002214030360000021
wherein the content of the first and second substances,
R1is represented by C1-C20Linear or branched alkyl or fluoroalkyl, C6-C18Substituted or unsubstituted aryl, or camphoryl of (a);
R2-R7each independently represents the following group:
hydrogen;
halogen;
C1-C20is a straight or branched alkyl or haloalkyl group, optionally, wherein-CH2-may be substituted by-O-;
phenyl, optionally, in which at least one hydrogen atom may be replaced by C1-C8Alkyl or alkoxy of (a);
C7-C20optionally, at least one hydrogen atom on the phenyl group may be replaced by C1-C8Substituted by alkyl or alkoxy groups, -CH in alkyl2-may be substituted by-O-or-S-;
R1' -CO-, wherein R1' represents C1-C10Alkyl of (C)3-C10And optionally, at least one hydrogen atom in the phenyl group may be replaced by C1-C8Alkyl or alkoxy of (a);
R2’-CO-O-R3' -, wherein R2' represents C1-C10Alkyl, phenyl, R3' represents null, C1-C8Alkoxy of, or C3-C8Optionally, at least one hydrogen atom in the phenyl group may be replaced by C1-C8Alkyl of (a);
R4’-O-CO-R5' -, wherein R4' represents C1-C10Alkyl of R5' represents C1-C10And optionally, R4' and R5' of-CH2-may be substituted by-O-;
C2-C10linear or branched alkenyl of (a);
with C3-C10Cycloalkyl or C6-C20Aryl of (A) is end-capped C2-C8Alkenyl of (a);
C2-C10straight or branched alkynyl of (a);
C1-C10optionally, the hydrogen on the alkyl group may be substituted by a fluorine atom;
or C6-C20Arylsulfonyloxy of (a);
provided that R is2-R7Not hydrogen at the same time.
Preferably, in the structure represented by the general formula (A), R is1Is C1-C6Linear or branched perfluoroalkyl, perfluorophenyl, at least one hydrogen atom being replaced by C1-C6Phenyl substituted with an alkyl or fluoroalkyl group, or camphoryl. Illustratively, R1Can be selected from trifluoromethyl, perfluorobutyl, p-methylphenyl, hexafluorophenyl, camphoryl and the like.
Preferably, in the structure represented by the general formula (A), R is2、R4-R7Is hydrogen, R3Selected from the following groups:
halogen;
C1-C10is a straight or branched alkyl or haloalkyl group, optionally, wherein-CH2-may be substituted by-O-;
phenyl, optionally, in which at least one hydrogen atom may be replaced by C1-C4Alkyl or alkoxy of (a);
C7-C10optionally, at least one hydrogen atom on the phenyl group may be replaced by C1-C4Substituted by alkyl or alkoxy groups, -CH in alkyl2-may be substituted by-O-or-S-;
R1' -CO-, wherein R1' represents C1-C6Alkyl of (C)3-C6And optionally, at least one hydrogen atom in the phenyl group may be replaced by C1-C4Alkyl or alkoxy of (a);
R2’-CO-O-R3' -, wherein R2' represents C1-C8Alkyl, phenyl, R3' represents null, C1-C4Alkoxy of, or C3-C4Optionally, at least one hydrogen atom in the phenyl group may be replaced by C1-C4Alkyl of (a);
R4’-O-CO-R5' -, wherein R4' represents C1-C6Alkyl of R5' represents C1-C6And optionally, R4' and R5' of-CH2-may be substituted by-O-;
C2-C6linear or branched alkenyl of (a);
with C3-C6Cycloalkyl or C6-C10Aryl of (A) is end-capped C2-C4Alkenyl of (a);
C2-C6straight or branched alkynyl of (a);
C1-C6optionally, the hydrogen on the alkyl group may be substituted by a fluorine atom;
or C6-C10Arylsulfonyloxy of (a).
Illustratively, the photoacid generator of the present invention having a structure represented by the general formula (a) may be selected from the following structures:
Figure BDA0002214030360000051
Figure BDA0002214030360000061
Figure BDA0002214030360000071
Figure BDA0002214030360000081
the invention also relates to a preparation method of the sulfonyl imide photoacid generator, which comprises the following steps:
(1) 4-bromo-1, 8-naphthalic anhydride and indole derivative are subjected to coupling reaction to generate an intermediate 1, wherein the reaction formula is as follows:
Figure BDA0002214030360000091
(2) the intermediate 1 and hydroxylamine hydrochloride are subjected to a hydroxylamination reaction to generate an intermediate 2, wherein the reaction formula is as follows:
Figure BDA0002214030360000092
(3) intermediate 2 with sulfonic anhydride (R)1-SO2)2O or sulfonyl chloride R1-SO2-Cl to give compound A, of the formula:
Figure BDA0002214030360000093
the reactions involved in steps (1) - (3) are conventional in the art of organic synthesis, and specific reaction conditions are readily determined by those skilled in the art, given the synthetic routes disclosed herein.
Without limitation, the reaction of step (1) is carried out in an organic solvent. The organic solvent to be used is not particularly limited as long as it can dissolve the raw materials and does not adversely affect the reaction, and examples thereof include dioxane, dichloroethane, t-butanol, toluene, xylene, DMF and DMSO.
The hydroxylamination reaction in step (2) and the esterification reaction in step (3) are likewise carried out in an organic solvent. The organic solvent to be used is not particularly limited as long as it can dissolve the raw materials and does not adversely affect the reaction, and examples thereof include methylene chloride, dichloroethane, benzene, toluene, xylene, and the like.
The starting materials used in the above preparation processes are all known compounds in the art and can be prepared commercially or conveniently by known synthetic methods such as coupling, Friedel-crafts, etc.
The compound of the general formula (A) belongs to a non-ionic photoacid generator, has a light-absorbing group and an acid-generating group (acid generating unit), can realize long-wave absorption, has high sensitivity and strong absorption on active energy rays with the wavelength of 300-450nm, particularly 365nm (I line) and 405nm (H line), and can generate acid quickly under short-time irradiation. At the same time, it has good solubility.
In view of the above, the present invention also provides a method for producing an acid, characterized in that the compound of the general formula (a) as the photoacid generator is irradiated with an active energy ray.
The molecule of the compound of the general formula (A) contains a sulfonate group, and the sulfonate group is directly connected with an imide structure, and the structure has a photosensitive cracking characteristic and can be photolyzed under the irradiation of active energy rays to generate stronger sulfonic acid. The active energy ray is an active energy ray having a wavelength in the near ultraviolet region and the visible light region of 300-450nm, and particularly preferably active energy rays having a wavelength of 365nm (I line) and 405nm (H line).
The photoacid generator of the present invention can be used for any known uses of photoacid generators, for example, coatings, coating agents, inks, inkjet inks, resist films, liquid resists, negative resists, positive resists, resists for MEMS, negative photosensitive materials, materials for stereolithography and micro-stereolithography, and the like. It is most preferable to use the photoacid generator in a resist, together with an acid-dissociable resin, to prepare a resist for use in semiconductor lithography.
Compared with the prior art, the invention has the beneficial effects that: the photoacid generator can realize long-wave absorption, has high sensitivity to active energy rays with the wavelength of 300-450nm, particularly 365nm (I line) and 405nm (H line), and has strong absorption; photolysis can produce stronger sulfonic acid; and has good solubility.
Detailed Description
The invention will now be further illustrated by reference to specific examples, which are provided for illustration only and are not intended to limit the scope of the invention. Any insubstantial changes from the invention, as well as any alterations and substitutions made by those skilled in the art, are intended to be covered by the present invention.
The test conditions not specifically described in the examples can be generally carried out according to the conditions conventional in the art or according to the manufacturer's recommendations.
Preparation examples
Example 1
Synthesis of photoacid Generator (A1-1)
Figure BDA0002214030360000111
5.27g of 2-methylindole are introduced into a four-necked flask, dissolved in 200.19g of toluene, stirred with 13.90g of 4-bromo-1, 8-naphthalic anhydride, purged with nitrogen, then 0.58g of tetrakis (triphenylphosphine) palladium, 1mL (1mol/L) of tri-tert-butylphosphine and 13.56g of potassium carbonate, the temperature is raised to 110 ℃ under reflux, stirring is continued for 18h, HPLC is controlled and subsequently cooled to room temperature, the solution is brownish. Water was added thereto and stirred, insoluble matter was filtered off, liquid separation was carried out, the organic layer was washed with water 3 times, and then toluene was distilled off under reduced pressure at 60 ℃ to obtain 11.02g of a pale yellow solid.
6.58g of the obtained pale yellow solid was dissolved in 100.2g of methanol, 3.50g of hydroxylamine hydrochloride and 4.05g of triethylamine were added, and the mixture was stirred at 25 ℃ for 0.5 hour, then heated to 70 ℃ for 8 hours, cooled, washed with water 3 times, methanol was distilled off, and crystallized by adding toluene to obtain 4.85g of a solid.
3.02g of the obtained solid was put into 60.00g of dichloromethane, then 0.88g of pyridine and 2.72g of trifluoromethanesulfonic anhydride were added, the mixture was reacted at 0 to 5 ℃ for 1 hour, then the temperature was raised to room temperature, 1.0g of activated carbon was added for decolorization, the mixture was washed twice with room temperature water, the pH was adjusted to 2 with hydrochloric acid (35.0%), the mixture was washed twice with room temperature water, the pH was adjusted to 8 with ammonia water, the mixture was washed with water until the pH was 7, the mixture was distilled at 60 ℃ under normal pressure until 10g of dichloromethane remained, the temperature was reduced to 40 ℃ or less, 20.0g of methanol was added, the mixture was cooled to 5 to 10 ℃ again, the mixture was stirred for 0.5 hour, and the mixture. Drying in a forced air oven at 40 deg.C to obtain 1.62g of white solid, which is the compound shown in (A1-1).
By passing1H NMR on productThe structure was characterized and the results were as follows:
1H NMR(400MHz,CDCl3):δ8.40-8.30(m,2H),7.67–7.54(m,4H),7.46–7.41(m,1H),7.27–7.17(m,2H),7.00–6.96(m,1H),2.35(s,3H)。
example 2
Synthesis of photoacid Generator (A1-2)
Figure BDA0002214030360000121
Was synthesized in a similar manner by following the same procedure as a1-1, substituting 3-methylindole for 2-methylindole in 58% yield. This was the compound represented by (A1-2).
By passing1The product structure was characterized by H NMR as follows:
1H NMR(400MHz,CDCl3):δ8.39-8.30(m,2H),7.89(t,J＝0.8Hz,1H),7.78(dd,J＝7.5,1.7Hz,1H),7.69–7.60(m,2H),7.57(d,J＝7.5Hz,1H),7.49(d,J＝7.5Hz,1H),7.28(t,J＝7.5Hz,1H),7.09(td,J＝7.5,1.5Hz,1H),2.45(s,3H)。
example 3
Synthesis of photoacid Generator (A1-3)
Figure BDA0002214030360000131
Synthesized in a similar manner by following the same procedure as a1-1, replacing 2-methylindole with 4-methylindole, in 44% yield. This was the compound represented by (A1-3).
By passing1The product structure was characterized by H NMR as follows:
1H NMR(400MHz,CDCl3):δ8.39-8.35(m,2H),7.77(d,J＝7.5Hz,1H),7.67-7.63(m,2H),7.55(d,J＝8.8Hz,2H),7.18(t,J＝7.5Hz,1H),7.10-7.04(m,2H),2.48(d,J＝0.7Hz,3H)。
example 4
Synthesis of photoacid Generator (A1-4)
Figure BDA0002214030360000141
Was synthesized in a similar manner by following the same procedure as A1-1, replacing 2-methylindole with 5-methylindole, in 40% yield. This was the compound represented by (A1-4).
By passing1The product structure was characterized by H NMR as follows:
1H NMR(400MHz,CDCl3):δ8.39-8.34(m,2H),7.81(d,J＝7.5Hz,1H),7.68-7.63(m,2H),7.59–7.51(m,3H),7.19–7.14(m,1H),6.69(dd,J＝7.6,1.7Hz,1H),2.48(s,3H)。
example 5
Synthesis of photoacid Generator (A1-5)
Figure BDA0002214030360000142
Was synthesized in a similar manner by following the same procedure as A1-1, replacing 2-methylindole with 6-methylindole, in 36% yield. This was the compound represented by (A1-5).
By passing1The product structure was characterized by H NMR as follows:
1H NMR(400MHz,CDCl3):δ8.39-8.35(m,2H),7.81(d,J＝7.5Hz,1H),7.67-7.63(m,2H),7.56-7.52(m,2H),7.43–7.39(m,1H),7.10–7.04(m,1H),6.72–6.67(m,1H),2.38(d,J＝0.8Hz,3H)。
example 6
Synthesis of photoacid Generator (A1-6)
Figure BDA0002214030360000151
Was synthesized in a similar manner by following the same procedure as A1-1, substituting 7-methylindole for 2-methylindole in 46% yield. This was the compound represented by (A1-6).
By passing1H NMR on the product StructureThe results were characterized as follows:
1H NMR(400MHz,CDCl3):δ8.39-8.30(m,2H),7.78–7.70(m,2H),7.69–7.60(m,2H),7.57(d,J＝7.5Hz,1H),7.32(t,J＝7.5Hz,1H),7.15(d,J＝7.5Hz,1H),6.69(dd,J＝7.5,1.4Hz,1H),2.41(d,J＝0.7Hz,3H)。
example 7
Synthesis of photoacid Generator (A2-2)
Figure BDA0002214030360000152
6.51g of 3-methoxymethyl indole was charged in a four-necked flask, dissolved in 200.10g of toluene, and while stirring, 13.87g of 4-bromo-1, 8-naphthalenic anhydride was added, nitrogen was passed through, and then 0.12g of palladium acetate, 1mL (1mol/L) of tri-tert-butylphosphine and 18.54g of potassium phosphate were added, the mixture was heated to 110 ℃ and refluxed, and stirring was continued for 12 hours, controlled by HPLC, and then cooled to room temperature, and the solution was brownish. Water was added thereto and stirred, insoluble matter was filtered off, liquid separation was carried out, the organic layer was washed with water 3 times, and then toluene was distilled off under reduced pressure at 60 ℃ to obtain 12.02g of a pale yellow solid.
7.02g of the obtained pale yellow solid was dissolved in 100.20g of methanol, 3.42g of hydroxylamine hydrochloride and 3.67g of triethylamine were added, and the mixture was stirred at 20 ℃ for 0.5 hour, then heated to 80 ℃ for 6 hours, cooled, washed with water 3 times, methanol was distilled off, and crystallized by adding toluene to obtain 5.07g of a solid.
4.05g of the obtained solid was put into 100.10g of dichloromethane, 1.11g of pyridine and 3.62g of perfluoro-1-butanesulfonic acid were added, the mixture was reacted at 5 to 10 ℃ for 2 hours, the temperature was raised to room temperature, 0.95g of activated carbon was added to decolorize the mixture, the mixture was washed twice with room temperature water, the pH was adjusted to 2 with hydrochloric acid (35.0%), the mixture was washed twice with room temperature water, the mixture was washed with ammonia water to 8, the pH was adjusted to 7 with water, the mixture was distilled at 60 ℃ under normal pressure until 10g of dichloromethane remained, the temperature was reduced to 40 ℃ or less, 20.00g of methanol was added, the mixture was cooled to 5 to 10 ℃ again, the mixture was stirred for 0.5 hour, and the mixture was. Drying in a forced air oven at 40 deg.C to obtain 3.55g of white solid, which is the compound shown in (A2-2).
By passing1The product structure was characterized by H NMR as follows:
1H NMR(400MHz,CDCl3):δ8.40-8.26(m,3H),8.06-7.71(m,2H),7.69–7.58(m,3H),7.27(t,J＝7.4Hz,1H),7.19(t,J＝7.5Hz,1H),4.54(s,2H),3.41(s,3H)。
example 8
Synthesis of photoacid Generator (A3-1)
Figure BDA0002214030360000161
Into a four-necked flask were charged 3.65g of 3-indoleformaldehyde as a white-like powder, 3.11g of benzyltriphenylphosphonium chloride, 3.12g of potassium tert-butoxide and 100mL of absolute ethanol, and the mixture was refluxed for 10 hours with stirring. After a part of ethanol is distilled off, the product is purified by silica gel column chromatography and recrystallized by ethanol to obtain 3.05g of off-white solid.
By passing1The structure of the solid product was characterized by H NMR as follows:
1H NMR(400MHz,CDCl3):δ9.93(d,J＝8.4Hz,1H),7.71–7.64(m,2H),7.56(d,J＝11.0Hz,1H),7.51–7.26(m,6H),7.22(t,J＝7.5Hz,1H),7.11(t,J＝7.5Hz,1H),6.54–6.50(m,1H)。
8.80g of off-white solid was added to a four-necked flask, dissolved in 200.30g of toluene, and stirred with 13.92g of 4-bromo-1, 8-naphthalic anhydride followed by 0.56g of tetrakis (triphenylphosphine) palladium, 11.21g of potassium tert-butoxide and 0.26g of triphenylphosphine, heated to 110 ℃ under reflux, stirred for 22h, controlled by HPLC, and then cooled to room temperature, giving a tan solution. Water was added thereto and stirred, insoluble matter was filtered off, liquid separation was carried out, the organic layer was washed with water 3 times, and then toluene was distilled off under reduced pressure at 60 ℃ to obtain 13.56g of a pale yellow solid.
The obtained pale yellow solid 8.35 is dissolved in 200.52g of methanol, 3.51g of hydroxylamine hydrochloride and 2.85g of diethylamine are added dropwise, after the dropwise addition is finished, the temperature is kept at 35 ℃ and stirred for 1h, then the temperature is raised to 80 ℃ and the mixture is cooled and washed for 3 times after 10h, the methanol is evaporated, and toluene is added for crystallization, so that 6.04g of solid is obtained.
5.01g of the obtained solid was put into 80.20g of dichloromethane, 1.35g of pyridine and 3.63g of trifluoromethanesulfonic anhydride were added, the mixture was reacted at 0 to 5 ℃ for 1 hour, the temperature was raised to room temperature, 1.05g of activated carbon was added to decolorize the mixture, the mixture was washed twice with room temperature water, the pH was adjusted to 2 with hydrochloric acid (35.0%), the mixture was washed twice with room temperature water, the pH was adjusted to 8 with ammonia water, the mixture was washed with water until the pH was 7, the mixture was distilled at 60 ℃ under normal pressure until 10g of dichloromethane remained, the temperature was lowered to 40 ℃ or below, 20.00g of methanol was added, the temperature was lowered to 5 to 10 ℃, the mixture was stirred for 0.5 hour, and the mixture was. Drying in a forced air oven at 40 deg.C to obtain 4.28g, which is the compound of (A3-1).
By passing1The product structure was characterized by H NMR as follows:
1H NMR(400MHz,CDCl3):δ8.39-8.35(m,2H),8.21(s,1H),7.86(d,J＝7.3Hz,1H),7.73–7.64(m,3H),7.58(dd,J＝7.5,1.6Hz,1H),7.53–7.47(m,2H),7.37–7.30(m,2H),7.29–7.16(m,4H),6.80–6.74(m,1H)。
example 9
Synthesis of photoacid Generator (A4-4)
Figure BDA0002214030360000181
Adding 100.10g of 3-methoxybutanol and 20.01g of indole-3-acetic acid into a four-neck flask, dropwise adding 20.05g of sulfuric acid at room temperature, heating to 150 ℃, stirring for reaction for 3 hours, cooling to room temperature, washing with water for three times, taking an organic layer, adding dichloromethane and pure water, washing for 2-3 times to neutrality, adding 1.02g of anhydrous sodium sulfate, carrying out suction filtration, and then carrying out reduced pressure distillation to obtain 27.25g of a solid.
By passing1The structure of the solid product was characterized by H NMR as follows:
1H NMR(400MHz,CDCl3):δ7.57–7.33(m,2H),7.21(d,J＝8.5Hz,1H),7.15–7.04(m,2H),4.17–4.09(m,2H),3.84–3.75(m,2H),3.67(h,J＝6.9Hz,1H),3.36(s,3H),1.90–1.76(m,2H),1.23(d,J＝6.8Hz,3H)。
10.80g of the obtained solid was charged into a four-necked flask, dissolved in 206.30g of toluene, and while stirring, 13.88g of 4-bromo-1, 8-naphthalic anhydride was added, followed by introduction of nitrogen gas, addition of 0.29g of bis (dibenzylideneacetone) palladium, 13.27g of potassium carbonate and 1mL (2mol/L) of tri-t-butylphosphine, warming to 110 ℃ for reflux, continuous stirring for 18 hours, HPLC neutralization, and subsequent cooling to room temperature, whereby the solution was brown. Water was added thereto, and stirring was carried out, insoluble matters were filtered off, liquid separation was carried out, the organic layer was washed with water 3 times, and then toluene was distilled off under reduced pressure at 60 ℃ to obtain 14.59g of a solid.
Dissolving the obtained solid 9.39 in 201.56g of methanol, dropwise adding 3.50g of hydroxylamine hydrochloride and 4.06g of triethylamine, keeping the temperature at 35 ℃ after dropwise adding, stirring for 1h, then heating to 80 ℃ for 10h, cooling, washing with water for 3 times, evaporating out methanol, adding toluene, and crystallizing to obtain 6.24g of a solid.
5.02g of the obtained solid was put into 100.05g of dichloromethane, 1.15g of pyridine and 3.23g of trifluoromethanesulfonic anhydride were added, the mixture was reacted at 0 to 5 ℃ for 1 hour, the temperature was raised to room temperature, 1.10g of activated carbon was added to decolorize the mixture, the mixture was washed twice with room temperature water, the pH was adjusted to 2 with hydrochloric acid (35.0%), the mixture was washed twice with room temperature water, the pH was adjusted to 8 with ammonia water, the mixture was washed with water until the pH was 7, the mixture was distilled at 60 ℃ under normal pressure until 10g of dichloromethane remained, the temperature was reduced to 40 ℃ or less, 20.10g of methanol was added, the mixture was cooled to 5 to 10 ℃ again, the mixture was stirred for 0.5 hour, and the. And (3) drying in a blast oven at 40 ℃ to obtain 4.17g of off-white solid, namely the compound shown in (A4-4).
By passing1The product structure was characterized by H NMR as follows:
1H NMR(400MHz,CDCl3):δ8.41–8.32(m,2H),8.00-7.86(m,2H),7.70-7.64(m,2H),7.56(dd,J＝7.5,1.6Hz,1H),7.47(dd,J＝7.5,1.4Hz,1H),7.32-7.20(m,2H),4.17(t,J＝12.5Hz,2H),3.80–3.63(m,3H),3.31(s,3H),1.87-1.76(m,2H),1.25(d,J＝6.8Hz,3H)。
example 10
Synthesis of photoacid Generator (A5-3)
Figure BDA0002214030360000201
In a four-necked flask were placed 8.82g of 3-bromoindole, 0.27g of triphenylphosphine, 10.12g of triethylamine and 200ml of THF, and then 0.48g of CuI and 0.35g of Pd (PPh) were added thereto after introducing nitrogen gas3)2Cl2. The mixture was heated to reflux and a solution of 9.81g of propargyl acetate in THF was added dropwise, the mixture was subjected to HPLC control, stirred under reflux for 15h and then cooled to room temperature.Washing with water, and evaporating the organic phase to remove the solvent to obtain brown solid; the dichloromethane was dissolved, washed with water and then the dichloromethane was evaporated and acetonitrile was recrystallized to give 6.73g of a solid.
By passing1The structure of the solid product was characterized by H NMR as follows:
1H NMR(400MHz,CDCl3):δ9.92(d,J＝7.3Hz,1H),7.83(dd,J＝7.4,1.8Hz,1H),7.65–7.50(m,2H),7.19(d,J＝7.4Hz,2H),4.83(s,2H),2.10(s,3H)。
8.60g of the obtained solid was charged into a four-necked flask, dissolved in 201.95g of xylene, and while stirring, 13.92g of 4-bromo-1, 8-naphthalic anhydride was added, nitrogen was introduced, and then 0.29g of bis (dibenzylideneacetone) palladium, 13.53g of potassium carbonate and 1mL (2mol/L) of tri-t-butylphosphine were added, and the mixture was heated to 140 ℃ for reflux, stirred continuously for 20 hours, subjected to HPLC control, then cooled to room temperature, stirred with water, filtered, separated, washed with water for 3 times, and then xylene was distilled off under reduced pressure at 60 ℃ to obtain 14.00g of a solid.
8.20g of the obtained solid is dissolved in 150.18g of methanol, 2.35g of hydroxylamine hydrochloride and 2.77g of triethylamine are added dropwise, after the dropwise addition is finished, the temperature is kept at 25 ℃ and stirred for 1h, then the temperature is raised to 80 ℃ and the temperature is raised for 12h, after cooling, the solid is washed for 3 times, the methanol is evaporated, and the toluene is recrystallized to obtain 5.59g of the solid.
5.01g of the obtained solid was put into 100.20g of dichloromethane, 1.21g of pyridine and 3.66g of trifluoromethanesulfonic anhydride were added, the mixture was reacted at 0 to 5 ℃ for 1 hour, then the temperature was raised to room temperature, 0.98g of activated carbon was added for decolorization, the mixture was washed twice with room temperature water, the pH was adjusted to 2 with hydrochloric acid (35.0%), the mixture was washed twice with room temperature water, the pH was adjusted to 8 with ammonia water, the mixture was washed with water until the pH was 7, the mixture was distilled at 60 ℃ under normal pressure until 10g of dichloromethane remained, the temperature was reduced to 40 ℃ or less, 20.25g of methanol was added, the mixture was cooled to 5 to 10 ℃ again, the mixture was stirred for 0.5 hour, and the mixture was. And (3) drying in a blast oven at 40 ℃ to obtain 4.92g of off-white solid, namely the compound shown in (A5-3).
By passing1The product structure was characterized by H NMR as follows:
1H NMR(400MHz,CDCl3):δ8.39-8.35(m,2H),7.86-7.82(m,2H),7.69-7.65(m,2H),7.64–7.58(m,1H),7.54(dd,J＝7.4,1.7Hz,1H),7.31-7.25(m,2H),4.84(s,2H),2.10(s,3H)。
example 11
Synthesis of photoacid Generator (A6-3)
Figure BDA0002214030360000211
In a four-necked flask, 100.33g of dioxane and 6.67g of 3-hydroxyindole were charged, and 5.08g of dihydropyran was added dropwise while stirring at room temperature, 0.20g of p-toluenesulfonic acid was then added thereto, and after 2 hours of reaction, the mixture was washed with water to neutrality, extracted with dichloromethane, and then the dichloromethane was distilled off to precipitate 9.73g of a solid.
By passing1The structure of the solid product was characterized by H NMR as follows:
1H NMR(400MHz,CDCl3):δ9.96(d,J＝7.5Hz,1H)，7.78(d,J＝7.5Hz,1H),7.27(d,J＝9.0Hz,1H),7.16(td,J＝7.4,1.5Hz,1H),7.13–7.03(m,2H),5.69–5.63(m,1H),3.79–3.63(m,2H),1.97–1.83(m,2H),1.75–1.59(m,4H)。
in a four-necked flask, 8.71g of off-white solid was charged, dissolved in 200.36g of toluene, and while stirring, 13.92g of 4-bromo-1, 8-naphthalic anhydride was added, nitrogen was passed, then 0.59g of tetrakis (triphenylphosphine) palladium, 11.26g of potassium tert-butoxide and 0.28g of triphenylphosphine were added, the mixture was heated to 110 ℃ and refluxed, and stirring was continued for 25 hours, followed by HPLC control, cooling to room temperature, stirring with water, filtration and separation, washing of the organic layer with water 3 times, and then toluene was distilled off under reduced pressure at 60 ℃ to obtain 13.29g of a pale yellow solid.
The obtained solid 15.69 was dissolved in 300.21g of dichloromethane, 2.28g of hydroxylamine hydrochloride was added dropwise, stirred at room temperature for 6 hours, filtered, rinsed with methanol, and dried in a forced air oven at 40 ℃ to obtain 10.56g of a solid.
By passing1The structure of the solid product was characterized by H NMR as follows:
1H NMR(400MHz,CDCl3):δ9.52(d,J＝9.4Hz,1H),8.23(s,1H),7.85–7.81(m,1H),7.25–7.17(m,2H),7.12–7.03(m,2H)。
dissolving 13.9g of the solid in 203.29g of methanol, adding 6.95g of methanesulfonyl chloride and 7.54g of triethylamine, reacting for 12h at 65 ℃, then dropwise adding 2.28g of hydroxylamine hydrochloride and 2.35g of triethylamine, then adding 100.76g of methanol, keeping the temperature and stirring for 0.5h at 15 ℃, then heating to 80 ℃, filtering after cooling after 10h, washing for 2-3 times by using dilute hydrochloric acid and water respectively, and drying at 40 ℃ by using a blast oven to obtain 5.89g of the solid.
By passing1The structure of the solid product was characterized by H NMR as follows:
1H NMR(400MHz,CDCl3):δ9.87(s,1H),8.39-8.24(m,2H),7.95–7.86(m,2H),7.68–7.62(m,2H),7.57(dd,J＝7.5,1.6Hz,2H),7.29(t,J＝7.4Hz,1H),7.11(t,J＝7.5Hz,1H),3.22(s,3H)。
8.45g of the obtained solid was put into 60.09g of dichloromethane, then 2.76g of pyridine was added, then a dichloromethane solution of camphorsulfonyl chloride (5.91 g of camphorsulfonyl chloride, 60.19g of dichloromethane) was added dropwise at room temperature, after completion of the addition, stirring was performed at 40 ℃ with heat preservation for 5 hours, then 1.00g of activated carbon was added for decolorization, washing was performed twice at room temperature, the pH was adjusted to 2 with hydrochloric acid (35.0%), washing was performed twice at room temperature, the pH was adjusted to 8 with ammonia water, washing was performed until the pH was 7, distillation was performed at 60 ℃ under normal pressure until 10g of dichloromethane remained, the temperature was reduced to 40 ℃ or less, 20.50g of methanol was added, the temperature was further reduced to 5 to 10 ℃, stirring was performed for 0.5 hours, and suction filtration. And (3) drying in a blast oven at 40 ℃ to obtain 4.27g of solid, namely the compound shown in (A6-3).
By passing1The product structure was characterized by H NMR as follows:
1H NMR(400MHz,CDCl3):δ8.39-8.25(m,2H),7.92-7.87(m,2H),7.69–7.60(m,3H),7.56(dd,J＝7.6,1.5Hz,1H),7.30(t,J＝7.5Hz,1H),7.09(d,J＝7.5Hz,1H)，3.45-3.32(m,2H),3.22(s,3H),2.30-2.20(m,2H),2.09(d,J＝8.5Hz,1H),1.88–1.60(m,4H),1.04(d,J＝1.6Hz,3H),0.99(d,J＝1.4Hz,3H)。
example 12
Synthesis of photoacid Generator (A7-1)
Figure BDA0002214030360000241
7.9g of 3-bromoindole was charged in a four-necked flask, dissolved in 201.72g of xylene, and while stirring, 13.95g of 4-bromo-1, 8-naphthalic anhydride was added, nitrogen was passed through, and then 0.32g of bis (dibenzylideneacetone) palladium, 1mL (1mol/L) of tri-t-butylphosphine and 21.39g of potassium phosphate were added, and the mixture was heated to 140 ℃ for reflux, stirred continuously for 12 hours, subjected to HPLC control, and then cooled to room temperature, whereby the solution was brownish. Water was added thereto and stirred, insoluble matter was filtered off, liquid separation was carried out, the organic layer was washed with water 3 times, and toluene was distilled off under reduced pressure at 60 ℃ to obtain 13.12g of a solid.
7.88g of the obtained solid was dissolved in 100.88g of methanol, 2.11g of hydroxylamine hydrochloride and 2.23g of triethylamine were added, and the mixture was stirred at 20 ℃ for 0.5 hour, then heated to 80 ℃ for 6 hours, cooled, washed with water for 3 times, methanol was distilled off, and toluene was added to crystallize to obtain 5.37g of a solid.
5.01g of the obtained solid was put into 101.02g of dichloromethane, 1.30g of pyridine and 3.49g of trifluoromethanesulfonic anhydride were added, the mixture was reacted at 0 to 5 ℃ for 1 hour, then the temperature was raised to room temperature, 1.29g of activated carbon was added to decolorize the mixture, the mixture was washed twice with room temperature water, the pH was adjusted to 2 with hydrochloric acid (35.0%), the mixture was washed twice with room temperature water, the mixture was adjusted to 8 with ammonia water, the mixture was washed with water until the pH was 7, the mixture was distilled at 60 ℃ under normal pressure until 10g of dichloromethane remained, the temperature was reduced to 40 ℃ or less, 20.12g of methanol was added, the mixture was cooled to 5 to 10 ℃ again, the mixture was stirred for 0.5 hour, and the. Drying in a forced air oven at 40 deg.C to obtain 4.36g of white solid, which is the compound shown in (A7-1).
By passing1The product structure was characterized by H NMR as follows:
1H NMR(400MHz,CDCl3):δ8.39-8.24(m,3H),7.94(dd,J＝7.4,1.5Hz,1H),7.71(d,J＝7.5Hz,1H),7.64-7.59(m,3H),7.34(t,J＝7.4Hz,1H),7.27(t,J＝7.5Hz,1H)。
example 13
Synthesis of photoacid Generator (A8-1)
Figure BDA0002214030360000251
Adding 15.11 g of p-methylbenzyl chloride, 11.72g of indole, 14.70g of aluminum trichloride and 155.06g of benzene into a four-neck flask, stirring at 0-4 ℃ for reacting for 8 hours, heating to 30 ℃, stirring for 1 hour, and washing with water for three times at 25 ℃ until the pH value is 5-6; concentrating under reduced pressure, adding methanol, cooling to 2-6 deg.C, and separating out solid. The mixture was washed with water to neutrality, and then crystallized by adding methanol to give 15.95g of a solid.
By passing1The structure of the solid product was characterized by H NMR as follows:
1H NMR(400MHz,CDCl3):δ7.58(d,J＝7.5Hz,1H),7.37(d,J＝7.5Hz,1H),7.22–6.96(m,8H),3.98–3.79(m,2H),2.32(d,J＝1.0Hz,3H)。
adding 8.89g of the obtained solid into a four-neck flask, dissolving the solid with 207.80g of xylene, adding 13.95g of 4-bromo-1, 8-naphthalic anhydride while stirring, introducing nitrogen, then adding 0.29g of bis (dibenzylideneacetone) palladium, 21.25g of potassium phosphate and 0.62g of triphenylphosphine, heating to 140 ℃, refluxing, continuously stirring for 18h, performing HPLC (high performance liquid chromatography) control, and then cooling to room temperature; water was added thereto and stirred, insoluble matter was filtered off, liquid separation was carried out, the organic layer was washed with water 3 times, and xylene was distilled off under reduced pressure to obtain 16.92g of a solid.
8.35g of the obtained solid is dissolved in 204.29g of methanol, 2.24g of hydroxylamine hydrochloride and 2.56g of triethylamine are added dropwise, after the dropwise addition is finished, the mixture is stirred for 1h at 25 ℃, then the temperature is raised to 80 ℃ for 10h, the mixture is cooled and washed with water for 3 times, methanol is evaporated, and toluene is added for crystallization to obtain 5.83g of the solid.
5.00g of the obtained solid was put into 60.53g of dichloromethane, 1.16g of pyridine was added, a dichloromethane solution of p-toluenesulfonyl chloride (2.41 g of p-toluenesulfonyl chloride, 61.27g of dichloromethane) was added dropwise, after the dropwise addition, stirring was carried out under heat preservation at 40 ℃ for 6 hours, after cooling, 1.06g of activated carbon was added for decolorization, washing was carried out twice at room temperature, the pH was adjusted to 2 with hydrochloric acid (35.0%), washing was carried out twice at room temperature, the pH was adjusted to 8 with ammonia water, washing was carried out until the pH was 7, distillation was carried out at 60 ℃ under normal pressure until 10g of dichloromethane remained, cooling was carried out below 40 ℃, 20.43g of methanol was added, cooling was carried out again to 5 to 10 ℃, stirring was carried out for 0.5. And (3) drying in a blast oven at 40 ℃ to obtain 4.02g of off-white solid, namely the compound shown in (A8-1).
By passing1The product structure was characterized by H NMR as follows:
1H NMR(400MHz,CDCl3):δ8.39-8.30(m,2H),7.80–7.74(m,3H),7.69–7.60(m,3H),7.57(d,J＝7.5Hz,2H),7.39–7.33(m,2H),7.26(td,J＝7.4,1.6Hz,1H),7.15–7.05(m,5H),3.90(t,J＝1.0Hz,2H),2.43(d,J＝0.8Hz,3H),2.34(d,J＝0.9Hz,3H)。
example 14
Synthesis of photoacid Generator (A9-1)
Figure BDA0002214030360000271
Adding 6.82g of anhydrous zinc chloride, 100mL of dichloroethane and 14.13g of acetyl chloride into a four-mouth bottle, stirring at room temperature for reaction for 30min, and slowly dropwise adding 5.83g of indole solution dissolved in 50mL of dichloroethane; reacting at normal temperature for 1h, heating to 50 ℃ for continuous reaction, adding 13.58g of anhydrous zinc chloride powder in 3 times in the reaction process, controlling by TLC, reacting for 3h, completely converting the raw materials, evaporating dichloroethane, adding 150mL of 50% potassium hydroxide aqueous solution, extracting for 3 times by using anhydrous ether, combining organic layers, drying over night by using anhydrous magnesium sulfate, removing ether solvent, and recrystallizing by using dichloromethane/petroleum ether to obtain 5.81g of light yellow needle-shaped crystals.
By passing1The crystal product structure was characterized by H NMR as follows:
1H NMR(400MHz,CDCl3):δ8.97(d,J＝8.4Hz,1H),8.25–8.17(m,2H),7.44(d,J＝7.5Hz,1H),7.31–7.26(m,2H),2.55(s,3H)。
6.93g of the obtained pale yellow solid was charged into a four-necked flask, and dissolved in 202.25g of toluene, and 13.90g of 4-bromo-1, 8-naphthalic anhydride was added under stirring, followed by introduction of nitrogen, addition of 0.29g of bis (dibenzylideneacetone) palladium, 10.23g of triethylamine and 1mL (2mol/L) of tri-tert-butylphosphine, heating to 110 ℃ for reflux, continuous stirring for 12 hours, control by HPLC, cooling to room temperature, stirring with water, filtration, liquid separation, washing of the organic layer with water 3 times, and distillation of toluene under reduced pressure at 60 ℃ to obtain 12.68g of a solid.
The obtained solid 7.32 is dissolved in 201.53g of methanol, 2.45g of hydroxylamine hydrochloride and 3.23g of triethylamine are added dropwise, after the dropwise addition is finished, the mixture is stirred for 1h at 25 ℃, then the temperature is raised to 70 ℃, after 6h, the mixture is cooled and washed for 3 times, methanol is evaporated, and toluene is added for crystallization, so that 5.17g of the solid is obtained.
Adding 3.82g of the obtained solid into 60.21g of dichloromethane, adding 0.95g of pyridine, dropwise adding a dichloromethane solution of pentafluorobenzenesulfonyl chloride (3.07 g of pentafluorobenzenesulfonyl chloride and 61.65g of dichloromethane), keeping the temperature at 40 ℃ after dropwise adding, stirring for 4 hours, cooling, adding 1.09g of activated carbon for decolorization, washing twice at room temperature, adjusting the pH to 2 with hydrochloric acid (35.0%), washing twice at room temperature, adjusting the pH to 8 with ammonia water, washing to pH 7, distilling at 60 ℃ under normal pressure until 10g of dichloromethane remains, cooling to below 40 ℃, adding 20.46g of methanol, cooling to 5-10 ℃, stirring for 0.5 hour, and carrying out suction filtration. And (3) drying in a forced air oven at 40 ℃ to obtain 3.22g of off-white solid, namely the compound shown in (A9-1).
By passing1The product structure was characterized by H NMR as follows:
1H NMR(400MHz,CDCl3):δ8.56-8.31(m,4H),8.15–8.08(m,1H),7.69(d,J＝7.5Hz,1H),7.65(t,J＝7.5Hz,1H),7.56(dd,J＝7.6,1.6Hz,1H),7.34–7.25(m,2H),2.63(s,3H)。
comparative example Compound
Comparative example 1
Nonionic photoacid generator (B-1)
Figure BDA0002214030360000281
Comparative example 2
Nonionic photoacid generator (B-2)
Figure BDA0002214030360000291
Evaluation of Performance
The photoacid generator compounds synthesized in examples and the compounds of comparative examples were evaluated for their performance, respectively, and the evaluation indices included molar absorption coefficient, acid generation, solubility, and resist hardening properties.
(1) Molar absorptivity
The compound was diluted to 0.25mmol/L with acetonitrile, and the absorbance at a cell length of 1cm was measured in the range of 200-500nm using a UV-visible spectrophotometer (UpG-752, UpG, Up. Molar absorptivity (. epsilon.) of line I (365nm) and line H (405nm) was calculated from the following equation365) And (ε)405)。
ε365(L·mol-1·cm-1)＝A365/(0.00025mol/L*1cm)
In the formula, A365The absorbance at 365nm was shown.
ε405(L·mol-1·cm-1)＝A405/(0.00025mol/L*1cm)
In the formula, A405The absorbance at 405nm is shown.
The results are shown in table 1.
TABLE 1
Figure BDA0002214030360000292
Figure BDA0002214030360000301
(2) Acid generating property
10mg of each compound was weighed on a glass dish, and 100mg of methylene chloride was added to prepare a solution. Monochromatic light at 365nm (I line) and 405nm (H line) is selected as an exposure light source, which is irradiated by an ultraviolet irradiation light source device (IWATA UV-100D) with a specific exposure intensity through band pass filters (103 Mw/cm) at 365nm and 405nm2) And (4) obtaining. A0.04 w/v% thymol blue solution was added dropwise to the irradiated solution to confirm the presence or absence of acid generation. When the color of the solution appeared red, the solution showed sufficient acidity at pH 1.2 or less by the generation of acid, and was evaluated as "o"; when the color of the solution was yellow, the pH was 2.8 to 8.0, and the solution was not sufficiently acidic and evaluated as "X".
(3) Solubility in water
The high solubility not only facilitates the purification of the photoacid generator compound, but also allows for an extended range of concentrations of the photoacid generator compound to be used in photoresists and different solvent systems. 1.0000g of the photoacid generator compound product was taken, and the solvents (PGMEA, butyl acetate and cyclohexanone) were gradually added at 25 ℃ until the solids in each tube were completely dissolved, and the mass of the solvent used was recorded, and the solubility was represented by the following formula.
Figure BDA0002214030360000311
(4) Hardening of resist
A resin solution of 75 parts of P-hydroxystyrene resin (Maruka LINKER S-2P, Japan pill chemical), 25 parts of melamine curing agent (Benoke Biotech), 1 part of photoacid generator and 200 parts of Propylene Glycol Monomethyl Ether Acetate (PGMEA) was coated on a glass substrate (diameter 10cm) using a spin coater at 100 rpm/10S. Then, vacuum drying was performed at 25 ℃ for 5min, and drying was performed on a hot plate at 80 ℃ for 3min, thereby forming a resist film having a film thickness of about 3 μm. The resist film was exposed using an ultraviolet irradiation apparatus (IWATA UV-100D) fitted with a filter. Cumulative exposure measurements were performed at a wavelength of 365 nm. Subsequently, the substrate was exposed to light and heated (PEB) for 10min in a dryer at 120 ℃, and then immersed in 0.5% potassium hydroxide for 30 seconds to develop the substrate, and immediately washed with water and dried. The resist film thickness was measured using a shape measuring microscope (Kinzhi VK-8500). The resist hardening was evaluated based on the minimum exposure amount at which the film thickness of the resist before and after development was changed to 10% or less, based on the following criteria.
As follows: the minimum exposure amount is 200mJ/cm2The following;
o: the lowest exposure is more than 200mJ/cm2And at 250mJ/cm2The following;
x: the lowest exposure is more than 250mJ/cm2。
The evaluation results are shown in Table 2.
TABLE 2
Figure BDA0002214030360000312
Figure BDA0002214030360000321
The test results in tables 1 and 2 show that the photoacid generator of the present invention has significantly higher molar absorptivity at both line I and line H and much higher absorbance than the comparative example, compared to the comparative example compound. Meanwhile, the photoacid generator compound of the present invention is excellent in acid generation, and also has significant advantages in solubility and resist hardening properties.
Further, the acid generator compounds shown in examples 1 to 6 are different only in the positions of the substituent groups on the indole group, that is, 2-, 3-, 4-, 5-, 6-and 7-positions, respectively. The test results of tables 1 and 2 show that the compound of example 2 (i.e., containing a substituent at position 3 on the indole group) has significantly higher molar absorption coefficients in both line I and line H, and is superior in solubility and resist hardening properties, as compared to other sites.
Still further, other example compounds containing a substituent at position 3 on the indole group were characterized and the results are listed in table 3.
TABLE 3
Figure BDA0002214030360000322
Figure BDA0002214030360000331
As is clear from Table 3, examples 7 to 14 have high molar absorptivity and solubility of 30% or more, and thus provide sufficient possibilities for photoresists.
Industrial applicability
The photoacid generator having a structure represented by the general formula (a) of the present invention has high sensitivity to I-rays and H-rays, and is useful for paints, coating agents, inks, inkjet inks, resist films, liquid resists, negative resists, positive resists, resists for MEMS, negative photosensitive materials, materials for stereolithography and micro-stereolithography, and the like, in which the wavelength range is 300nm to 450 nm.

Claims (8)

1. A sulfonyl imide photoacid generator capable of generating acid at high levels on an I line and an H line, having a structure represented by the following general formula (A):
Figure FDA0002214030350000011
wherein the content of the first and second substances,
R1is represented by C1-C20Linear or branched alkyl or fluoroalkyl, C6-C18Substituted or unsubstituted aryl, or camphoryl of (a);
R2-R7each independently represents the following group:
hydrogen;
halogen;
C1-C20is a straight or branched alkyl or haloalkyl group, optionally, wherein-CH2-may be substituted by-O-;
phenyl, optionally, in which at least one hydrogen atom may be replaced by C1-C8Alkyl or alkoxy of (a);
C7-C20optionally, at least one hydrogen atom on the phenyl group may be replaced by C1-C8Substituted by alkyl or alkoxy groups, -CH in alkyl2-may be substituted by-O-or-S-;
R1' -CO-, wherein R1' represents C1-C10Alkyl of (C)3-C10And optionally, at least one hydrogen atom in the phenyl group may be replaced by C1-C8Alkyl or alkoxy of (a);
R2’-CO-O-R3' -, wherein R2' represents C1-C10Alkyl, phenyl, R3' represents null, C1-C8Alkoxy group of,Or C3-C8Optionally, at least one hydrogen atom in the phenyl group may be replaced by C1-C8Alkyl of (a);
R4’-O-CO-R5' -, wherein R4' represents C1-C10Alkyl of R5' represents C1-C10And optionally, R4' and R5' of-CH2-may be substituted by-O-;
C2-C10linear or branched alkenyl of (a);
with C3-C10Cycloalkyl or C6-C20Aryl of (A) is end-capped C2-C8Alkenyl of (a);
C2-C10straight or branched alkynyl of (a);
C1-C10optionally, the hydrogen on the alkyl group may be substituted by a fluorine atom;
or C6-C20Arylsulfonyloxy of (a);
provided that R is2-R7Not hydrogen at the same time.
2. The sulfonyl imide-based photoacid generator according to claim 1, wherein: r1Is C1-C6Linear or branched perfluoroalkyl, perfluorophenyl, at least one hydrogen atom being replaced by C1-C6Phenyl substituted with an alkyl or fluoroalkyl group, or camphoryl.
3. The sulfonyl imide-based photoacid generator according to claim 1, wherein: r2、R4-R7Is hydrogen, R3Selected from the following groups:
halogen;
C1-C10is a straight or branched alkyl or haloalkyl group, optionally, wherein-CH2-may be substituted by-O-;
phenyl, optionally, in which at least one hydrogen atom may be replaced byC1-C4Alkyl or alkoxy of (a);
C7-C10optionally, at least one hydrogen atom on the phenyl group may be replaced by C1-C4Substituted by alkyl or alkoxy groups, -CH in alkyl2-may be substituted by-O-or-S-;
R1' -CO-, wherein R1' represents C1-C6Alkyl of (C)3-C6And optionally, at least one hydrogen atom in the phenyl group may be replaced by C1-C4Alkyl or alkoxy of (a);
R2’-CO-O-R3' -, wherein R2' represents C1-C8Alkyl, phenyl, R3' represents null, C1-C4Alkoxy of, or C3-C4Optionally, at least one hydrogen atom in the phenyl group may be replaced by C1-C4Alkyl of (a);
R4’-O-CO-R5' -, wherein R4' represents C1-C6Alkyl of R5' represents C1-C6And optionally, R4' and R5' of-CH2-may be substituted by-O-;
C2-C6linear or branched alkenyl of (a);
with C3-C6Cycloalkyl or C6-C10Aryl of (A) is end-capped C2-C4Alkenyl of (a);
C2-C6straight or branched alkynyl of (a);
C1-C6optionally, the hydrogen on the alkyl group may be substituted by a fluorine atom;
or C6-C10Arylsulfonyloxy of (a).
4. The method for producing the sulfoximine-based photoacid generator according to any one of claims 1 to 3, comprising the steps of:
(1) 4-bromo-1, 8-naphthalic anhydride and indole derivative are subjected to coupling reaction to generate an intermediate 1, wherein the reaction formula is as follows:
Figure FDA0002214030350000041
(2) the intermediate 1 and hydroxylamine hydrochloride are subjected to a hydroxylamination reaction to generate an intermediate 2, wherein the reaction formula is as follows:
Figure FDA0002214030350000042
(3) intermediate 2 with sulfonic anhydride (R)1-SO2)2O or sulfonyl chloride R1-SO2-Cl to give compound A, of the formula:
Figure FDA0002214030350000043
5. a method for producing an acid, characterized in that the sulfonyl imide photoacid generator according to any one of claims 1 to 3 is irradiated with active energy rays.
6. The acid generation process of claim 5, wherein: the active energy ray is an active energy ray with the wavelength between 300-450nm in the near ultraviolet region and the visible light region.
7. The acid production method according to claim 5 or 6, characterized in that: the active energy rays are active energy rays having wavelengths of 365nm (I line) and 405nm (H line).
8. Use of the sulfonyl imide-based photoacid generator according to any one of claims 1 to 3 for producing a coating material, a coating agent, an ink, an inkjet ink, a resist film, a liquid resist, a negative resist, a positive resist, a resist for MEMS, a negative photosensitive material, a material for stereolithography and micro stereolithography.
CN201910908579.4A 2019-09-25 2019-09-25 High-acid-yield sulfimide photo-acid generator Pending CN112552280A (en)

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