WO2021057813A1 - Sulfimide photo-acid generator, photosensitive resin composition, patterning method, use of photosensitive resin composition - Google Patents

Abstract

Disclosed are a sulfimide photo-acid generator, a photosensitive resin composition, a patterning method, and a use of the photosensitive resin composition. The photosensitive resin composition comprises a resin component and an acid generator, wherein the acid generator is a sulfimide photo-acid generator, which has a structure as represented by general formula (A), which formula is as follows. Molecules of the sulfimide photo-acid generator of general formula (A) contain a sulfonate group, which group is directly linked with an imide structure. The structure has photosensitive cracking characteristics, and can be photolyzed under the irradiation of an active energy ray to produce stronger sulfonic acid. When the the photosensitive resin composition is applied to an alkali developing solution to dissolve an exposed positive-type photosensitive composition, a pattern with an excellent sensitivity and a good contrast ratio can be formed due to the increase in the photosensibility of the sulfimide photo-acid generator; even though a fine pattern is formed, same can also have a sufficiently high sensitivity.

Description

Sulfonimide photoacid generator, photosensitive resin composition, patterning method and application of photosensitive resin composition Technical field

The present invention relates to the technical field of photosensitive materials, in particular to a sulfonimide photoacid generator, a photosensitive resin composition, a patterning method and the application of the photosensitive resin composition.

Background technique

Photolithography technology refers to making a resist film from a resist material, coating and molding it on a substrate, so that the resist film is selectively exposed to light or electron beam radiation through a mask with a predetermined pattern formed thereon Then, a developing process is performed to form a resist pattern having a predetermined shape on the resist film. The resist material in which the exposed part is changed to dissolve in the developer is called a positive resist material, and the resist material in which the exposed part is changed to be insoluble in the developer is called a negative resist material.

With the demand for high integration and high speed of LSI, the refinement of pattern feature size is rapidly developing. As a refinement technology, it is generally necessary to shorten the wavelength of the exposure light source (high-energy radiation). For example, ultraviolet rays, which have been represented by g-line and i-line, are gradually converted to KrF excimer lasers or ArF excimer lasers for mass production of semiconductor elements. In addition, there are F2 excimer lasers, electron beams, EUV (extreme ultraviolet) and X-rays that have shorter wavelengths than these excimer lasers. With the shortening of the wavelength of the exposure light source, the resist composition is required to improve the lithographic characteristics so as to have a high sensitivity to the exposure light source and a resolution capable of reproducing the formation of fine-sized patterns. Therefore, the resist material must have lithographic characteristics such as sensitivity to the above-mentioned exposure light source and the ability to reproduce the resolution with fine-sized patterns. As a resist material that satisfies such requirements, chemically amplified resists containing alkaline resins can be used. The alkali solubility of the alkaline resins can be changed by the action of an acid. For example, chemically amplified positive resists include The base resin of the acid agent increases the alkali solubility by the acid generated by the acid generator. When the resist pattern is formed, the acid is generated from the acid generator by exposure, and the exposed area becomes soluble in the alkaline developer.

However, this type of positive resist composition still needs further improvement for miniaturization technology to adjust the sensitivity, sensitivity, resolution, and contrast of the formed pattern in the formation of the resist pattern.

As a resist material used in the photolithography process, one of the typical examples is a resin composition containing a resin and a photoacid generator. The resin may be, for example, t-butyl carboxylic acid or t-butyl ether of phenol, methyl Silyl ether and so on. When irradiated with active energy rays such as ultraviolet rays, the photoacid generator decomposes to produce strong acid (optionally, further heating (PEB) after exposure), under the action of strong acid, carboxylic acid derivatives or phenol derivatives are deprotected to produce carboxylic acid Or phenol. Through this chemical change, the resin in the exposed part becomes soluble in the alkaline developer, and then it is reacted with the alkaline developer to promote the formation of the pattern.

There are known many types of photoacid generators used in chemically amplified resists, which can be divided into two types: non-ionic and ionic. Among them, the ionic photoacid generator often has insufficient compatibility with the solvent, and is prone to phase separation in the resist material, so that it cannot fully function. Non-ionic photoacid generators usually have problems such as insufficient sensitivity at long wavelengths and poor solubility in solvents.

Summary of the invention

The main purpose of the present invention is to provide a photoacid generator with high sensitivity to active energy rays with wavelengths of 300-450nm, especially 365nm (I line) and 405nm (H line), good solubility and strong acid production.

To focus on the above objective, according to one aspect of the present invention, a sulfonimide photoacid generator capable of producing high acid at the I line and H line is provided, which has a structure represented by the following general formula (A):

Wherein, R ₁ represents a C ₁ -C ₂₀ linear or branched alkyl or fluoroalkyl group, a C ₆ -C ₁₈ substituted or unsubstituted aryl group, or a camphor group; R ₂ -R ₇ are each independently To represent the following groups: hydrogen; halogen; C ₁ -C ₂₀ linear or branched alkyl or haloalkyl, optionally in which -CH ₂ -may be substituted by -O-; phenyl, any Optionally, at least one hydrogen atom may be substituted by a C ₁ -C ₈ alkyl group or alkoxy group; a C ₇ -C ₂₀ phenyl alkyl group, optionally, at least one hydrogen atom on the phenyl group may be It is substituted with alkyl or alkoxy of C ₁ -C _8, alkyl -CH ₂ - may be substituted with -O- or -S-; R ₁ 'CO-, wherein R _1' represents a C ₁ -C ₁₀ alkyl group, C ₃ -C ₁₀ cycloalkyl group, phenyl group, and optionally, at least one hydrogen atom in the phenyl group may be substituted by a C ₁ -C ₈ alkyl group or alkoxy group; _{R 2 '-CO-oR 3'} -, wherein R ₂ 'represents C ₁ -C ₁₀ alkyl group, a phenyl group, R _3' represents a blank, C ₁ -C ₈ alkoxy or C ₃ -C ₈ alkynyl, optionally substituted phenyl, at least one hydrogen atom may be substituted with a C ₁ -C ₈ alkyl _{group; R 4 '-O-CO-} R 5' -, wherein R ₄ 'represents C ₁ - A C ₁₀ alkyl group, R ₅ ′ represents a C ₁ -C ₁₀ alkylene group, and optionally, -CH _{2 -in R 4} ′ and R ₅ ′ may be substituted by -O-; C ₂ -C ₁₀ linear or branched alkenyl; C ₃ -C ₁₀ cycloalkyl or C ₆ -C ₂₀ aryl terminated C ₂ -C ₈ alkenyl; C ₂ -C ₁₀ linear Or branched alkynyl group; C ₁ -C ₁₀ alkylsulfonyloxy group, optionally, the hydrogen on the alkyl group can be replaced by a fluorine atom; or C ₆ -C ₂₀ arylsulfonyloxy group; The premise is that R ₂ -R _{7 are} not hydrogen at the same time.

The compound of the general formula (A) of the present invention 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, and has a wavelength of 300-450nm, especially 365nm (I line ) And 405nm (H line) active energy rays have high sensitivity and strong absorption, and can produce acid quickly under short-time irradiation. At the same time, it also has good solubility.

In view of this, the present invention also provides an acid generation method, which irradiates the above-mentioned photoacid generator, that is, the compound of general formula (A) with active energy rays.

The molecule of the compound of general formula (A) contains a sulfonic acid ester group, which is directly connected to the imide structure. The structure has the characteristics of photo-decomposition and can be photodegraded to produce strong sulfonic acid under the irradiation of active energy rays. The active energy rays are active energy rays with a wavelength between 300-450 nm in the near-ultraviolet light region and visible light region, and active energy rays with wavelengths of 365 nm (I line) and 405 nm (H line) are particularly preferred.

The photoacid generator of the present invention can be used for any known application of the photoacid generator, such as paints, coating agents, inks, inkjet inks, resist films, liquid resists, negative resists, and positive resists. Etchants, resists for MEMS, negative photosensitive materials, materials for stereo lithography and micro stereo lithography, etc. It is most suitable as a photoacid generator in a resist, and a resist is prepared together with a resin having acid dissociation properties for use in semiconductor photolithography.

Compared with the prior art, the beneficial effect of the above-mentioned acid generator of the present invention is embodied in that the photoacid generator can achieve long-wave absorption, and has activity at wavelengths of 300-450nm, especially 365nm (I line) and 405nm (H line). Energy ray has high sensitivity and strong absorption; photolysis can produce strong sulfonic acid; and has good solubility.

Another main purpose of the present invention is to provide a photosensitive resin composition, a patterning method and application of the photosensitive resin composition to solve the problem of the sensitivity of the positive resist composition in the prior art when forming fine patterns. The problem of insufficient.

According to another aspect of the present invention, there is provided a photosensitive resin composition comprising a resin component and an acid generator, the acid generator being any one of the above-mentioned sulfonimide photoacid generators.

According to another aspect of the present invention, there is provided a patterning method, including mixing, forming a film and patterning a photosensitive resin composition, the photosensitive resin composition being any one of the above-mentioned photosensitive resin compositions .

According to another aspect of the present invention, there is provided an application of any of the above-mentioned photosensitive resin compositions. The application includes applying the photosensitive composition to protective films, interlayer insulating materials, and pattern transfer materials for electronic components. In preparation.

Applying the technical solution of the present invention, the sulfonimide photoacid generator with general formula (A) contains sulfonate ester group in its molecule, which is directly connected to the imide structure, and the structure has the characteristics of photosensitive cracking, which is effective in active energy. It can be photodegraded to produce strong sulfonic acid under radiation. When the photosensitive resin composition including the sulfonimide photoacid generator and the resin component is used for the positive photosensitive composition exposed by the dissolution of an alkali developer, during the patterning process, due to the sulfonimide The sensitivity of the photoacid generator is increased, so that patterns with excellent sensitivity and good contrast can be formed, and even fine patterns can be formed with sufficiently high sensitivity. The above-mentioned active energy rays are active energy rays with a wavelength between 300-450 nm in the near ultraviolet region and visible light region, and active energy rays with wavelengths of 365 nm (I line) and 405 nm (H line) are particularly preferred, so as to further improve the resolution and Sensitivity.

detailed description

It should be noted that the embodiments in this application and the features in the embodiments can be combined with each other if there is no conflict. Hereinafter, the present invention will be described in detail with reference to the embodiments.

The prior art positive resist composition has insufficient sensitivity when forming fine patterns. In order to solve this problem, the present application provides a sulfonimide photoacid generator, a photosensitive resin composition, and a patterning method And the application of photosensitive resin composition.

In a typical factual manner of this application, a sulfonimide photoacid generator capable of producing high acid at the I line and H line is provided, which has the structure shown in the following general formula (A):

Wherein, R ₁ represents a C ₁ -C ₂₀ linear or branched alkyl or fluoroalkyl group, a C ₆ -C ₁₈ substituted or unsubstituted aryl group, or a camphor group; R ₂ -R ₇ are each independently To represent the following groups: hydrogen; halogen; C ₁ -C ₂₀ linear or branched alkyl or haloalkyl, optionally in which -CH ₂ -may be substituted by -O-; phenyl, any Optionally, at least one hydrogen atom may be substituted by a C ₁ -C ₈ alkyl group or alkoxy group; a C ₇ -C ₂₀ phenyl alkyl group, optionally, at least one hydrogen atom on the phenyl group may be It is substituted with alkyl or alkoxy of C ₁ -C _8, alkyl -CH ₂ - may be substituted with -O- or -S-; R ₁ 'CO-, wherein R _1' represents a C ₁ -C ₁₀ alkyl group, C ₃ -C ₁₀ cycloalkyl group, phenyl group, and optionally, at least one hydrogen atom in the phenyl group may be substituted by a C ₁ -C ₈ alkyl group or alkoxy group; _{R 2 '-CO-oR 3'} -, wherein R ₂ 'represents C ₁ -C ₁₀ alkyl group, a phenyl group, R _3' represents a blank, C ₁ -C ₈ alkoxy or C ₃ -C ₈ alkynyl, optionally substituted phenyl, at least one hydrogen atom may be substituted with a C ₁ -C ₈ alkyl _{group; R 4 '-O-CO-} R 5' -, wherein R ₄ 'represents C ₁ - A C ₁₀ alkyl group, R ₅ ′ represents a C ₁ -C ₁₀ alkylene group, and optionally, -CH _{2 -in R 4} ′ and R ₅ ′ may be substituted by -O-; C ₂ -C ₁₀ linear or branched alkenyl; C ₃ -C ₁₀ cycloalkyl or C ₆ -C ₂₀ aryl terminated C ₂ -C ₈ alkenyl; C ₂ -C ₁₀ linear Or branched alkynyl group; C ₁ -C ₁₀ alkylsulfonyloxy group, optionally, the hydrogen on the alkyl group can be replaced by a fluorine atom; or C ₆ -C ₂₀ arylsulfonyloxy group; The premise is that R ₂ -R _{7 are} not hydrogen at the same time.

Compared with the prior art, the beneficial effect of the above-mentioned acid generator of the present invention is embodied in that the photoacid generator can achieve long-wave absorption, and has activity at wavelengths of 300-450nm, especially 365nm (I line) and 405nm (H line). Energy ray has high sensitivity and strong absorption; photolysis can produce strong sulfonic acid; and has good solubility.

In order to further improve the structural stability and performance of the sulfonimide photoacid generator, it is preferred that in the structure represented by the general formula (A), R ₁ is a C ₁ -C ₆ linear or branched perfluoro An alkyl group, a perfluorophenyl group, a phenyl group in which at least one hydrogen atom is substituted with a C ₁ -C ₆ alkyl group or a fluoroalkyl group, or a camphor group. Exemplarily, R ₁ may be selected from trifluoromethyl, perfluorobutyl, p-methylphenyl, pentafluorophenyl, camphor and the like. Preferably R ₁ is perfluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl, perfluorophenyl, camphoryl, p-methylphenyl or all Fluoromethylphenyl.

As a preferred technical solution, in the structure represented by the above general formula (A), R ₂ and R ₄ -R ₇ are hydrogen, and R _{3 is} selected from the following groups: halogen; C ₁ -C ₁₀ linear or branched Alkyl or haloalkyl, optionally, -CH ₂ -can be substituted by -O-; phenyl, optionally, at least one hydrogen atom can be C ₁ -C ₄ alkyl or alkoxy C ₇ -C ₁₀ phenyl alkyl group, optionally, at least one hydrogen atom on the phenyl group can be substituted by a C ₁ -C ₄ alkyl group or alkoxy group, the -CH in the alkyl group ₂ - may be substituted with -O- or -S-; R ₁ 'CO-, wherein R _1' represents a C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl group, a phenyl group, and either Alternatively, a phenyl group at least one hydrogen atom may be substituted with C ₁ -C ₄ alkyl or _{alkoxy; R 2 '-CO-oR 3} ' -, wherein R ₂ 'represents a C ₁ -C ₈ alkyl, phenyl, R ₃ 'represents a blank, C ₁ -C ₄ alkoxy or C ₃ -C ₄ alkynyl group, optionally, a phenyl group at least one hydrogen atom may by C ₁ -C ₄ alkyl _{substituted; R 4 '-O-CO-} R 5' -, wherein R ₄ 'represents a C ₁ -C ₆ alkyl group, R _5' represents a C ₁ -C ₆ alkyl alkylene, and any Optionally, -CH _{2 -in R 4} 'and R ₅ ' may be substituted by -O-; C ₂ -C ₆ linear or branched alkenyl; C ₃ -C ₆ cycloalkyl or The C ₆ -C ₁₀ aryl group is a blocked C ₂ -C ₄ alkenyl group; a C ₂ -C ₆ linear or branched alkynyl group; a C ₁ -C ₆ alkylsulfonyloxy group, optionally Alternatively, the hydrogen on the alkyl group may be replaced by a fluorine atom; or a C ₆ -C ₁₀ arylsulfonyloxy group.

Furthermore, one of the above-mentioned R ₂ -R _{7 is} selected from any one of methyl, ethyl, propyl, butyl, and pentyl, and the rest is H; or R ₂ and R ₄ -R ₇ are hydrogen, R _{3 is} selected from any one of the following groups: halogen, halomethyl, and haloethyl; or R ₂ , R ₄ -R ₇ are hydrogen, and R _{3 is} selected from any one of the following groups: Methyl, ethyl, propyl, butyl, pentyl, and one of -CH ₂ -is replaced by -O-; or R ₂ , R ₄ -R ₇ are hydrogen, and R _{3 is} selected from the following groups Any one of: C ₇ -C ₁₀ phenylalkyl group, optionally, one hydrogen atom on the phenyl group can be replaced by a methyl group, and/or one -CH ₂ -in the alkyl group can be- O- or -S- group; or R _2, R ₄ -R ₇ are hydrogen, R ₃ is selected from any one of the following radicals: R ₁ '-CO-, wherein R _1' represents a methyl group, b Group, propyl group, cyclohexyl group, phenyl group, methyl phenyl group, ethyl phenyl group, tert-butyl phenyl group, alkoxymethyl phenyl group or alkoxy ethyl phenyl group; or R ₂ , R ₄ -R ₇ is hydrogen, R ₃ is selected from any one of the following _{radicals: R 2 '-CO-oR 3} ' -, wherein R ₂ 'represents methyl, ethyl, propyl or phenyl group, a phenyl group of hydrogen atoms may be substituted by methyl, R ₃ 'represents a blank or a propynyl group; or R _2, R ₄ -R ₇ are hydrogen, R ₃ is selected from any one of the following radicals: R _4' -O-CO -R ₅ '-, wherein R _4' represents methyl, ethyl, propyl, butyl, pentyl or hexyl group, R ₅ 'represents a methylene group or an ethylene group, and R _4' and R ₅ 'is One -CH ₂ -may be substituted by -O-; or R ₂ , R ₄ -R ₇ are hydrogen, and R _{3 is} selected from any of the following groups: linear butenyl, branched butenyl, Phenyl-terminated propenyl or cyclohexyl-terminated propenyl; or R ₂ , R ₄ -R ₇ are hydrogen, and R _{3 is} selected from any of the following groups: ethynyl, propynyl, butynyl or Pentynyl; or R ₂ , R ₄ -R ₇ are hydrogen, and R _{3 is} selected from any one of the following groups: C ₁ -C ₆ methylsulfonyloxy, trifluoromethylsulfonyloxy , Butylsulfonyloxy, phenylsulfonyloxy or p-methylphenylsulfonyloxy.

Illustratively, the photoacid generator having the structure represented by the general formula (A) of the present invention can be selected from the following structures:

The present invention also relates to a preparation method of the above-mentioned sulfonimide photoacid generator, which comprises the following steps:

(1) The coupling reaction between 4-bromo-1,8 naphthalenedicarboxylic acid anhydride and indole derivatives produces intermediate 1, the reaction formula is as follows:

(2) Intermediate 1 undergoes a hydroxylamination reaction with hydroxylamine hydrochloride to produce Intermediate 2. The reaction formula is as follows:

(3) Intermediate 2 reacts with sulfonic anhydride (R ₁ -SO ₂ ) ₂ O or sulfonyl chloride R ₁ -SO ₂ -Cl to produce compound A, the reaction formula is as follows:

The reactions involved in steps (1)-(3) are all conventional reactions in the field of organic synthesis. Based on the knowledge of the synthetic route disclosed in the present invention, specific reaction conditions are easily determined by those skilled in the art.

Without limitation, the reaction of step (1) is carried out in an organic solvent. The organic solvent used is not particularly limited, as long as it can dissolve the raw materials without adversely affecting the reaction, such as dioxane, dichloroethane, tert-butanol, toluene, xylene, DMF, and DMSO.

The hydroxylamination reaction in step (2) and the esterification reaction in step (3) are also carried out in an organic solvent. The organic solvent used is not particularly limited, as long as it can dissolve the raw materials without adversely affecting the reaction, such as dichloromethane, dichloroethane, benzene, toluene, xylene and the like.

The raw materials used in the above preparation methods are all known compounds in the prior art, and they can be purchased commercially or conveniently prepared by known synthetic methods such as coupling and FuK.

The compound of the general formula (A) of the present invention 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, and has a wavelength of 300-450nm, especially 365nm (I line ) And 405nm (H line) active energy rays have high sensitivity and strong absorption, and can produce acid quickly under short-time irradiation. At the same time, it also has good solubility.

In view of this, the present invention also provides an acid generation method characterized by irradiating the above-mentioned photoacid generator, that is, the compound of general formula (A) with active energy rays.

The molecule of the compound of general formula (A) contains a sulfonic acid ester group, which is directly connected to the imide structure. The structure has the characteristics of photo-decomposition and can be photodegraded to produce strong sulfonic acid under the irradiation of active energy rays. The active energy rays are active energy rays with a wavelength between 300-450 nm in the near-ultraviolet light region and visible light region, and active energy rays with wavelengths of 365 nm (I line) and 405 nm (H line) are particularly preferred.

The photoacid generator of the present invention can be used for any known application of the photoacid generator, such as paints, coating agents, inks, inkjet inks, resist films, liquid resists, negative resists, and positive resists. Etchants, resists for MEMS, negative photosensitive materials, materials for stereo lithography and micro stereo lithography, etc. It is most suitable as a photoacid generator in a resist, and a resist is prepared together with a resin having acid dissociation properties for use in semiconductor photolithography.

In a typical embodiment of the present application, a photosensitive resin composition is provided, the photosensitive resin composition includes a resin component and an acid generator, and the acid generator is a sulfonimide photoacid generator .

The sulfonimide photoacid generator with the general formula (A) of the present application contains a sulfonate group in its molecule and is directly connected to the imide structure. This structure has the characteristics of photosensitive cleavage and can be irradiated by active energy rays. Photolysis produces stronger sulfonic acids. When the photosensitive resin composition including the sulfonimide photoacid generator and the resin component is used for the positive photosensitive composition exposed by the dissolution of an alkali developer, during the patterning process, due to the sulfonimide The sensitivity of the photoacid generator is increased, so that patterns with excellent sensitivity and good contrast can be formed, and even fine patterns can be formed with sufficiently high sensitivity. The above-mentioned active energy rays are active energy rays with a wavelength between 300-450 nm in the near ultraviolet region and visible light region, and active energy rays with wavelengths of 365 nm (I line) and 405 nm (H line) are particularly preferred, so as to further improve the resolution and Sensitivity.

The resin component used in the present application may be a resin commonly used in photosensitive resin compositions. In the present application, it is preferable that the above-mentioned resin component has an acid labile group protected by a protective group.

The acid labile group includes at least one of a carboxyl group and a phenolic hydroxyl group, which can be derived from (meth)acrylic acid (acrylic resin), a polymer with hydroxystyrene (polyhydroxystyrene resin) and a phenolic resin polymer; The content of the acid labile group accounts for 1 to 80% of the resin component content, preferably 3 to 70%, optionally 26%, 45%, within this range, the photosensitive composition can be obtained with Better developability.

Optionally, the above-mentioned hydroxystyrene resin is a polymer containing monomers of styrene compounds, which may be selected from p-hydroxystyrene, α-methylhydroxystyrene, α-ethylhydroxystyrene, and the like.

In addition, the hydroxystyrene resin is preferably a copolymer of a hydroxystyrene compound and a styrene compound, and may be selected from styrene, chlorostyrene, chloromethylstyrene, vinyl toluene, α-methylstyrene, and the like. And the molecular weight of the hydroxystyrene resin is preferably 1,000 to 50,000. In the resin component, a resin in which at least a part of the hydroxyl groups of the hydroxystyrene resin is protected by a protective group is used. As described above, the polyhydroxystyrene resin may incorporate crosslinking groups as needed. The cross-linking group is a functional group that can be thermally cross-linked when the patterned film to be formed is post-baked. Groups suitable for crosslinking can be selected from epoxy groups, oxetanyl groups, and groups containing unsaturated double bonds (for example, (meth)acryloyl groups. In the resin component, the content of crosslinking groups is preferably It is 20 to 70% (w/w). Within this range, a film with excellent mechanical properties and chemical resistance can be formed by thermal crosslinking between crosslinking groups during PEB (heating after exposure).

Optionally, the acrylic resin is preferably a resin obtained by copolymerizing (meth)acrylic acid and other monomers having unsaturated bonds. The monomer copolymerized with (meth)acrylic acid can be selected from unsaturated carboxylic acids other than (meth)acrylic acid, (meth)acrylate, (meth)acrylamide, allyl compound, vinyl ether, etc. . Among them, the unsaturated carboxylic acid is preferably a monocarboxylic acid of (meth)acrylic acid and a dicarboxylic acid of maleic acid. The linear or branched (meth)acrylate can be selected from methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, pentyl (meth)acrylate, (meth) ) Tert-octyl acrylate, etc. Among (meth)acrylates having no epoxy group, (meth)acrylates having an alicyclic skeleton are preferred, and in (meth)acrylates having an alicyclic skeleton, the alicyclic group may be Monocyclic or polycyclic, the monocyclic alicyclic group can be selected from cyclopentyl and cyclohexyl, and the polycyclic alicyclic group can be selected from norbornyl, isobornyl, tricyclononyl and the like.

The above-mentioned (meth)acrylamide includes (meth)acrylamide, (meth)N-alkyl(meth)acrylamide, (meth)N-aryl(meth)acrylamide, N-methyl- N-phenyl(meth)acrylamide, N-hydroxyethyl-N-methyl(meth)acrylamide, etc. Allyl compounds include allyl acetate, allyl hexanoate, allyl octoate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate Esters, allyl lactate, etc. Vinyl ethers include hexyl vinyl ether, octyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl Base-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, Diethylaminoethyl vinyl ether and benzyl vinyl ether, etc.

Optionally, the novolak resin can be obtained by addition condensation of an aromatic compound having a phenolic hydroxyl group (hereinafter referred to as "phenol") with an aldehyde under an acid catalyst. The phenol can be selected from phenol, o-cresol, m-cresol, p-cresol, o-ethyl phenol, m-ethyl phenol, p-ethyl phenol, o-butyl phenol, m-butyl phenol, p-butyl phenol, 2. 3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3, 5-trimethylphenol, 3,4,5-trimethylphenol, p-phenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, phloroglucinol, hydroxyl Diphenyl, bisphenol A, gallic acid, α-naphthol, β-naphthol, etc. The aldehyde can be selected from formaldehyde, acetaldehyde, furfural, benzaldehyde, nitrobenzaldehyde and the like. The acid catalyst can be selected from hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid and the like. The molecular weight of the novolak resin is preferably 1,000 to 50,000, and a resin in which at least a part of the hydroxyl groups of the novolak resin is protected by a protective group can be used as the resin component. As described above, a crosslinking group such as a carboxyl group bonded to an aromatic group, an alcoholic hydroxyl group, and a cyclic ether group can be introduced into the novolak resin as needed to react.

In addition, it is preferable that the above-mentioned protective group includes at least one of the following groups:

Wherein R ₈ , R ₉ , and R ₁₀ each independently represent any one of a C ₁ -C ₆ alkyl group or a C ₁ -C ₁₀ fluorinated alkyl group, wherein the alkyl group is a straight chain alkyl group or a branched alkyl group. Alkyl group, and _{any two of R 8} , R ₉ , and R ₁₀ are suitable for bonding to each other to form a ring; R ₁₁ , R ₁₂ and R ₁₃ each independently represent a C ₁ -C ₂₀ hydrocarbon group, and R ₁₁ , R ₁₂ , _{Any two of R 13} are suitable for bonding to each other to form a ring; R ₁₄ represents a C ₁ -C ₆ straight chain alkyl group, a C ₁ -C ₆ branched chain alkyl group, a C ₁ -C ₆ cyclic alkyl group Base, and n is 0 or 1.

Specifically, in formula (a), when R ₈ , R ₉ and R ₁₀ are alkyl groups, exemplary can be selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl Base, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethyl n-hexyl, n-nonyl, n-decyl, etc.; When _{any two groups of R 3} , R ₄ and R ₅ are bonded to each other to form a ring, it is preferably a C ₅ -C ₂₀ monocyclic or polycyclic aliphatic hydrocarbon, and exemplary can be selected from cyclopentane , Cyclohexane, cycloheptane, cyclooctane, adamantane, norbornane, tricyclodecane, tetracyclodecane, etc.; formed by combining any two groups of _{R 3} , R ₄ and R ₅ The ring may have substituents such as a hydroxyl group, a cyano group, and an oxygen atom (=O), and a linear or branched alkyl group _{having C 1} -C _4. Preferably, the formula (a) can be selected from the following molecular formula (formula a ₁ -formula a ₆ );

Specifically, in formula (b), R ₁₁ , R ₁₂ and R ₁₃ are aliphatic or/and aromatic hydrocarbon groups having C ₁ -C _20. When R ₁₁ , R ₁₂ and R ₁₃ are aliphatic hydrocarbon groups, they can be linear and cyclic. The linear structure can be selected from methyl, ethyl, n-propyl, isopropyl, n-butyl and isopropyl. Butyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethyl-n-hexyl, n-nonyl, n-decyl And n-undecyl, etc.; the ring structure can be selected from cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecane Group, and a polycyclic group of the following molecular formula (formula b ₁ -formula b ₈ );

And, in formula (b), when R ₁₁ , R ₁₂ and R ₁₃ are aromatic hydrocarbon groups, they can be selected from phenyl, naphthyl, anthracenyl, biphenyl, phenanthryl, and fluorenyl. When R ₁₁ , R ₁₂ and R ₁₃ contain both aliphatic and aromatic groups, they can be selected from benzyl, phenethyl, 3-phenyl-n-propyl, 4-phenyl-n-butyl, α- Naphthylmethyl, β-naphthylmethyl, 2-(α-naphthyl)ethyl, 2-(β-naphthyl)ethyl and the like. The aromatic ring may be substituted or partially substituted, and the substituents are selected from halogen atoms, hydroxyl groups, C ₁ -C ₁₀ alkyl groups or alkoxy groups, C ₂ -C ₁₀ alkanoyl groups and alkanoyloxy groups. In formula (b), R ₁₁ is preferably a hydrogen atom, R ₁₂ is preferably a methyl group, and R ₁₃ is preferably an ethyl, isobutyl, cyclohexyl, 2-ethyl-n-hexyl or octadecyl group; when R ₁₂ and When R _{13 is} bonded to each other to form a ring, a C ₄ -C ₆ heterocyclic ring containing O, S or N atoms is preferred; when R ₁₁ and R ₁₂ are bonded to each other to form a ring, a C ₃ -C _12- membered saturated aliphatic hydrocarbon is preferred ring.

Preferably, the formula (b) may preferably be a group of the following molecular formula (formula b ₉ -formula b ₁₄ ):

Specifically, the formula (c) can be selected from t-butoxycarbonyl and t-butoxycarbonylmethyl.

The amount of the above acid generator can refer to the amount of conventional acid generators in the prior art. In one embodiment, the weight content of the acid generator is 0.5 to 5% relative to the mass of the solid content of the photosensitive resin composition. , Preferably 1 to 3%, preferably the resin component is selected from any one of (meth)acrylic resin, polyhydroxystyrene resin and phenolic resin polymer.

In another embodiment of the present application, the above-mentioned resin composition further includes an aromatic carboxylic acid compound, that is, at least one carboxyl group is bonded to an aromatic group, and the aromatic group can be an aromatic hydrocarbon group and an aromatic heterocyclic group. . The aromatic carboxylic acid compound can promote the deprotection reaction of the acid labile group protected by the protecting group in the resin component of the composition after exposure. When the aromatic carboxylic acid compound is used in combination with the above-mentioned resin component and acid generator of the present application, the resolution of the pattern can be further improved. It is preferable that the weight content of the aromatic carboxylic acid compound is 3 to 35% with respect to the mass of the solid content of the photosensitive resin composition.

The above-mentioned aromatic carboxylic acid compound can be selected from at least one of a low-molecular-weight aromatic carboxylic acid compound or a high-molecular-weight aromatic carboxylic acid compound; wherein the low-molecular-weight aromatic carboxylic acid compound includes at least two carboxyl groups and/or monocarboxylates with substituents. Acid compounds, polycarboxylic acid compounds; Macromolecular aromatic carboxylic acid compounds include macromolecular compounds containing carboxyl groups bonded to aromatic groups and unsaturated double bonds.

In the aromatic carboxylic acid compound, in addition to the carboxyl group, it can also have one or more substituents, which can be selected from halogens, hydroxyl groups, mercapto groups, sulfide groups, silyl groups, silanol groups, nitro groups, and nitroso groups. Group, sulfonate group, phosphonyl group and phosphonate group; when the substituent on the aromatic group is an organic group, it can be selected from alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl And aralkyl groups; the organic group may contain bonds or substituents other than hydrocarbyl groups, such as O, Si, N and other heteroatoms. The heteroatom bonds may include ether bonds, thioether bonds, carbonyl bonds, and thiocarbonyl bonds , Ester bond, amide bond, urethane bond and imino bond, carbonate bond, sulfonyl bond, sulfinyl bond and azo bond, etc. The organic group can be linear, branched or cyclic. As the substituent on the aromatic group, a C ₁ -C ₁₂ alkyl group, an aryl group, an alkoxy group and a halogen are preferable.

The above-mentioned aromatic carboxylic acid compound may be a low-molecular compound, such as benzoic acid or naphthoic acid, or a high-molecular compound having a carboxyl group bonded to an aromatic group, as follows:

The low molecular weight aromatic carboxylic acid compound may be a monocarboxylic acid compound or a multivalent carboxylic acid compound having two or more carboxyl groups. The aromatic group contained in the low-molecular-weight aromatic carboxylic acid compound may have a substituent other than the carboxyl group. The low molecular weight aromatic carboxylic acid compound can be selected from the following carboxylic acids: benzoic acid; hydroxybenzoic acid such as salicylic acid, m-hydroxybenzoic acid and p-hydroxybenzoic acid, etc.; alkyl benzoic acid such as o-toluic acid, m-toluic acid, etc. Formic acid and p-toluic acid; halogenated benzoic acid such as o-chlorobenzoic acid, m-chlorobenzoic acid, p-chlorobenzoic acid, o-bromobenzoic acid, m-bromobenzoic acid and p-bromobenzoic acid; alkoxy benzoic acid such as o Methoxy benzoic acid, m-methoxy benzoic acid, p-methoxy benzoic acid, o-ethoxy benzoic acid, m-ethoxy benzoic acid and p-ethoxy benzoic acid; amino benzoic acid such as anthoxy benzoic acid, M-aminobenzoic acid and p-aminobenzoic acid; acyloxy benzoic acid such as o-acetoxy benzoic acid, m-acetoxy benzoic acid and p-acetoxy benzoic acid; naphthoic acid such as 1-naphthoic acid and 2-naphthoic acid; Hydroxynaphthoic acid such as 1-hydroxy-2-naphthoic acid, 1-hydroxy-3-naphthoic acid, 1-hydroxy-4-naphthoic acid, 1-hydroxy-5-naphthoic acid, 1-hydroxy-6-naphthoic acid, 1 -Hydroxy-7-naphthoic acid, 1-hydroxy-8-naphthoic acid, 2-hydroxy-1-naphthoic acid, 2-hydroxy-3-naphthoic acid, 2-hydroxy-4-naphthoic acid, 2-hydroxy-5-naphthalene Formic acid, 2-hydroxy-6-naphthoic acid, 2-hydroxy-7-naphthoic acid and 2-hydroxy-8-naphthoic acid; amino naphthoic acid such as 1-amino-2-naphthoic acid, 1-amino-3-naphthoic acid , 1-amino-4-naphthoic acid, 1-amino-5-naphthoic acid, 1-amino-6 naphthoic acid, 1-amino-7-naphthoic acid, 1-amino-8-naphthoic acid, 2-amino-1 -Naphthoic acid, 2-amino-3-naphthoic acid, 2-amino-4-naphthoic acid, 2-amino-5-naphthoic acid, 2-amino-6-naphthoic acid, 2-amino-7-naphthoic acid and 2 -Amino-8-naphthoic acid; Alkoxynaphthoic acid such as 1-methoxy-2-naphthoic acid, 1-methoxy-3-naphthoic acid, 1-methoxy-4-naphthoic acid, 1-methyl Oxy-5-naphthoic acid, 1-methoxy-6 naphthoic acid, 1-methoxy-7-naphthoic acid, 1-methoxy-8 naphthoic acid, 2-methoxy-1-naphthoic acid, 2-methoxy-3-naphthoic acid, 2-methoxy-4-naphthoic acid, 2-methoxy-5-naphthoic acid, 2-methoxy-6-naphthoic acid, 2-methoxy- 7-naphthoic acid, 2-methoxy-8-naphthoic acid, 1-ethoxy-2-naphthoic acid, 1-ethoxy-3-naphthoic acid, 1-ethoxy-4-naphthoic acid, 1 -Ethoxy-5-naphthoic acid, 1-ethoxy-6-naphthoic acid, 1-ethoxy-7-naphthoic acid, 1-ethoxy-8-naphthoic acid, 2-ethoxy-1 -Naphthoic acid, 2-ethoxy-3-naphthoic acid, 2-ethoxy-4-naphthoic acid, 2-ethoxy-5-naphthoic acid, 2-ethoxy-6-naphthoic acid, 2- Ethoxy-7-naphthoic acid and 2-ethoxy-8-naphthoic acid, etc.; phthalic acid such as phthalic acid, terephthalic acid and isophthalic acid; naphthalene dicarboxylic acid such as 1,2-naphthalene dicarboxylic acid Formic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalene Dicarboxylic acid, 2,6-naphthalenedicarboxylic acid and 2,7-naphthalenedicarboxylic acid; biphenyl carboxylic acid such as 1,1'-biphenyl-4-carboxylic acid, 1,1'-biphenyl-3-carboxylic acid and 1,1'-biphenyl-2-carboxylic acid; biphenyl dicarboxylic acid such as 1,1'-biphenyl-4,4'-dicarboxylic acid, 1,1'-biphenyl-3,3'-di Carboxylic acid, 1,1′-biphenyl-2,2′-dicarboxylic acid, 1,1′-biphenyl-3,4′-dicarboxylic acid, 1,1′-biphenyl-2,4′- Dicarboxylic acids and 1,1'-biphenyl-2,3'-dicarboxylic acids; trivalent or higher aromatic polycarboxylic acids such as pyromellitic acid, trimellitic acid and trimellitic acid; hydroxybenzene Dicarboxylic acids such as 5-hydroxyisophthalic acid, 4-hydroxyisophthalic acid and 2-hydroxyisophthalic acid; dihydroxybenzene dicarboxylic acids such as 2,5-dihydroxyterephthalic acid, 2,6- Dihydroxyisophthalic acid, 4,6-dihydroxyisophthalic acid, 2,3-dihydroxyphthalic acid, 2,4-dihydroxyphthalic acid and 3,4-dihydroxyphthalic acid Etc.; pyridine carboxylic acid such as pyridine-2-carboxylic acid, pyridine-3-carboxylic acid and pyridine-4-carboxylic acid, etc.; pyridine dicarboxylic acid such as pyridine-2,5-dicarboxylic acid, pyridine-3,5-di Carboxylic acid, pyridine-2,6-dicarboxylic acid and pyridine-2,4-dicarboxylic acid, etc.; pyrimidine carboxylic acid such as pyrimidine-2-carboxylic acid, pyrimidine-4-carboxylic acid, pyrimidine-5-carboxylic acid and pyrimidine -6-carboxylic acid; and pyrimidine dicarboxylic acid such as 2,6-pyrimidine dicarboxylic acid and 2,5-pyrimidine dicarboxylic acid. These low-molecular-weight aromatic carboxylic acid compounds can be used singly or in combination of two or more.

The high molecular weight aromatic carboxylic acid compound may be a polymer compound having a carboxyl group bonded to an aromatic group. The monomer has a carboxyl group and an unsaturated double bond bonded to an aromatic group, and does not include an acid labile group protected by a protecting group. The polymer can be used as a polymer aromatic carboxylic acid compound. As a preferred copolymerization component, it is used together with a monomer having a carboxyl group bound to an aromatic group and an unsaturated double bond. The above-mentioned (meth)acrylic acid as a monomer for preparing acrylic resins can be used, such as (meth) ) Unsaturated carboxylic acids other than acrylic acid, (meth)acrylates, (meth)acrylamides, allyl compounds, vinyl ethers, vinyl esters and styrene.

In another embodiment of the present application, the above-mentioned resin composition further includes a cross-linking compound. Preferably, the weight content of the cross-linking compound is 10-50% relative to the mass of the solid content of the photosensitive resin composition.

As the name implies, the bridging compound contains at least one cross-linking group, which is thermally cross-linked in the case of PEB. Preferably, the above-mentioned crosslinking group includes an epoxy group, an oxetanyl group, and a group containing an unsaturated double bond (such as a vinyl group). The bridging compounds include: bridging low molecular compounds and bridging high molecular compounds.

The bridging group low-molecular compound includes: at least one of a bifunctional or higher-functional polyfunctional epoxy compound, a polyoxetane compound, and a polymerizable monomer containing a vinyl group.

Optionally, the multifunctional epoxy compound can be selected from bifunctional epoxy resins, such as bisaldehyde A type epoxy resin and bisphenol S type epoxy resin; glycidyl ester type epoxy resin, such as dimer acid glycidol Esters and triglycidyl esters, etc.; glycidylamine epoxy resins, such as tetraglycidylaminodiphenylmethane and tetraglycidyl diaminomethylcyclohexane, etc.; heterocyclic epoxy resins, such as triglycidyl Isocyanurate, etc.; multifunctional epoxy resin, such as phloroglucinol triglycidyl ether, tetrahydroxyphenylethane tetraglycidyl ether, etc. The alicyclic epoxy compound is also preferable as a polyfunctional epoxy compound, and it is easy to form a highly transparent film. Optionally, the polyfunctional oxetane compound can be selected from 3,3'-(oxybismethylene)bis(3-ethyloxetane), 4,4-bis[(3-ethyloxetane) 3-oxetanyl)methyl]biphenyl and 3,7-bis(3-oxetanyl)-5-oxanonane, etc.

Optionally, the polymerizable monomer includes a monofunctional monomer and a multifunctional monomer. Monofunctional monomers can be selected from (meth)acrylamide, methylol (meth)acrylamide, methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, propoxy Methyl(meth)acrylamide, N-methylol(meth)acrylamide, (meth)acrylic acid, maleic acid, crotonic acid, 2-acrylamide-2-methylpropanesulfonic acid, tert-butyl Acrylamide sulfonic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate , 2-hydroxypropyl (meth)acrylate and glycerol mono(meth)acrylate, these monofunctional monomers can be used alone or in combination of two or more. The multifunctional monomer can be selected from propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth) Acrylate, glycerol di(meth)acrylate, pentaerythritol triacrylate, pentaerythritol di(meth)acrylate, 2,2-bis(4-(meth)acryloyloxydiethoxyphenyl)propane , 2-Hydroxy-3-(meth)acryloxypropyl (meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether two (meth) Base) acrylate, diglycidyl phthalate di(meth)acrylate, glycerol triacrylate, glycerol polyglycidyl ether poly(meth)acrylate, urethane (meth)acrylate (ie toluene) Diisocyanate), trimethylhexamethylene diisocyanate and hexamethylene ester diisocyanate with 2-hydroxyethyl (meth)acrylate, methylene bis(meth)acrylamide, (meth)acrylamide Methylene ether, etc., these polyfunctional monomers can be used singly or in combination of two or more.

The above-mentioned bridging group polymer compound includes at least one of epoxy group-containing resin and unsaturated double bond-containing resin. Epoxy-containing resins can be formed by polymerization of epoxy-containing monomers or monomer mixtures, and can be selected from novolac epoxy resins, such as phenol novolac type epoxy resins, brominated phenol novolac type epoxy resins, etc. ; Alicyclic epoxy resins, such as epoxidized products of dicyclopentadiene-type phenolic resins; and aromatic epoxy resins, such as epoxidized products of naphthalene-type phenolic resins.

Among epoxy group-containing resins, aliphatic (meth)acrylates having a chain aliphatic epoxy group and aliphatic (meth)acrylates having an alicyclic epoxy group are preferred, and an alicyclic group is particularly preferred. Aliphatic (meth)acrylate of formula epoxy. In the polymer having an epoxy group, the content of the unit derived from the (meth)acrylate having an epoxy group is preferably 100% (w/w).

When the epoxy-containing polymer is a copolymer of an epoxy-containing (meth)acrylate and another monomer, the other monomer has an unsaturated carboxylic acid, such as but not limited to maleic acid, Citraconic acid; or (meth)acrylates without epoxy groups, such as but not limited to methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate; (meth)acrylamide, such as but not limited to Not limited to N-alkyl(meth)acrylamide, N-hydroxyethyl-N-methyl(meth)acrylamide; propyl compounds (such as but not limited to allyl acetate, allyl laurate), Vinyl ether (such as but not limited to hexyl vinyl ether, chloroethyl vinyl ether), vinyl ester (such as but not limited to vinyl butyrate, vinyl chloroacetate), styrene (such as but not limited to benzene Ethylene, chloromethyl styrene) and so on. These compounds can be used alone or in combination of two or more. From the chemical viewpoints of the storage stability of the positive composition and the alkali resistance of the film formed using the positive composition, the copolymer of (meth)acrylate having an epoxy group and other monomers preferably does not contain derivative Units from unsaturated carboxylic acids. The molecular weight of the epoxy group-containing resin is preferably 5,000 to 15,000.

The resin containing unsaturated double bonds can be selected from (meth)acrylic acid, maleic acid, 2-hydroxyethyl (meth)acrylate, ethylene glycol monomethyl ether (meth) acrylate, ethylene glycol monoethyl ether (Meth)acrylate, glycerol (meth)acrylate, meth)acrylamide, acrylonitrile, methacrylonitrile, methyl (meth)acrylate, ethyl (meth)acrylate, propylene glycol bis(methyl) ) Acrylate, pentaerythritol tri(meth)acrylate and 1,6-hexanediol di(meth)acrylate polymerized oligomers, di-membered epoxy diacrylate, etc.; polyhydric alcohol and monobasic acid or by making A polyester (meth)acrylate obtained by reacting (meth)acrylic acid with a polyester prepolymer obtained by condensing a polybasic acid.

In addition, the ethylenically unsaturated group-containing resin is a resin obtained by reacting a reaction product of an epoxy compound and an unsaturated group-containing carboxylic acid compound with a polybasic acid anhydride or an unsaturated carboxylic acid. It is by reacting at least a part of the carboxyl group contained in the polymer containing the unit derived from the (meth)acrylate and/or the epoxyalkyl (meth)acrylate having the alicyclic epoxy group acquired. Resins (hereinafter collectively referred to as "resin containing a structural unit having an ethylenically unsaturated group") can be appropriately used. The ethylenically unsaturated group in the structural unit having an ethylenically unsaturated group is preferably a (meth)acryloyloxy group.

The mass average molecular weight of the ethylenically unsaturated group-containing resin is preferably 2,000 to 30,000, and good heat resistance, film strength, and good developability can be obtained.

In addition, it is preferable that the above-mentioned photosensitive composition further includes a solvent to facilitate film formation. The solvent is used in the photosensitive composition to adjust coating performance and viscosity. The solvent preferably contains an aprotic organic solvent, and a photosensitive composition excellent in sensitivity and resolution can be obtained. Can be selected from lactones, such as γ-butyrolactone; ketones, such as acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentyl ketone, methyl isoamyl ketone and 2-heptanone; polyols, such as ethyl Glycol, diethylene glycol, propylene glycol and dipropylene glycol; compounds with ester linkages, such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, dipropylene glycol monoacetate, ethylene Glycol monopropionate, diethylene glycol monopropionate, propylene glycol monopropionate or dipropylene glycol monopropionate; monoalkyl ethers or monophenyl ethers of compounds with ester bonds, such as methyl ether and ethyl ether , Propyl ether, butyl ether, etc.; aromatic organic solvents, such as anisole, ethyl benzyl ether, cresol methyl ether, diphenyl ether, dibenzyl ether, phenol, butyl phenyl ether, ethyl benzene, Diethylbenzene, pentylbenzene, cumene, toluene, xylene, cumene and mesitylene; polar solvents containing nitrogen, such as N,N,N',N'-tetramethylurea, N- Methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, hexamethylphosphoramide, etc., these organic solvents can be used alone or as a mixed solvent of two or more. The content of the aprotic organic solvent in the solvent is preferably 100% (w/w).

Furthermore, the above-mentioned solvent is preferably one or a mixture of two or more of propylene glycol monomethyl ether acetate (PGMEA), cyclohexanone, γ-butyrolactone and N,N-dimethylacetamide. Usually, the solvent amount is selected so that the solid content concentration of the photosensitive composition is preferably 5-30% (w/w).

In addition, according to functional requirements, the photosensitive resin composition of the present application may also include the following auxiliary materials: dissolution control agents, dissolution inhibitors, basic compounds, surfactants, dyes, pigments, plasticizers, photosensitizers, light Any one or more of absorbents, anti-halation agents, storage stabilizers, defoamers, adhesion promoters, phosphors, and magnetic materials.

Optionally, the content of the photosensitizer is 0.1-100% of the content of the sulfonate photoacid generator, and can be selected from at least one of an alkoxy group, a substituted carbonyloxy group, an oxo group (=O) and a thiophene ring A compound as a substituent, preferably a condensed polycyclic aromatic hydrocarbon compound or a condensed polycyclic aromatic heterocyclic compound (ie anthracene ring, naphthacene ring), and the substituent preferably has C ₁ -C ₆ The alkoxy group has a C ₆ -C ₁₀ aryloxy group, a C ₂ -C ₇ alkanoyl group, a C ₇ -C ₁₁ aroyl group, a cyano group, a nitro group, a nitroso group, a halogen, a hydroxyl group and Sulfhydryl.

Anthracene ring-containing compounds suitable for use as photosensitizers include but are not limited to: 9,10-bis(acetoxy)anthracene, 9,10-bis(propionyloxy)anthracene, 9,10-bis(n-propyl) Carbonyloxy)anthracene, 9,10-bis(n-butylcarbonyloxy)anthracene, 9,10-bis(n-pentylcarbonyloxy)anthracene, 9,10-bis(n-hexylcarbonyloxy)anthracene, 9,10-bis(benzoyloxy)anthracene, 9,10-bis(4-methylbenzoyloxy)anthracene, 9,10-bis(2-naphthyloxy)anthracene, 2-methyl Base-9,10-bis(acetoxy)anthracene, 2-methyl-9,10-bis(propionyloxy)anthracene, 2-methyl-9,10-bis(n-propylcarbonyloxy) Anthracene, 2-methyl-9,10-bis(n-butylcarbonyloxy)anthracene, 2-methyl-9,10-bis(n-pentylcarbonyloxy)anthracene, 2-methyl-9,10 -Bis(n-hexylcarbonyloxy)anthracene, 2-methyl-9,10-bis(benzoyloxy)anthracene, 1-methyl-9,10-bis(acetoxy)anthracene, 1-methyl Group-9,10-bis(propionyloxy)anthracene, 1-methyl-9,10-bis(n-propylcarbonyloxy)anthracene, 1-methyl-9,10-bis(n-butylcarbonyl) Oxy)anthracene, 1-methyl-9,10-bis(n-pentylcarbonyloxy)anthracene, 1-methyl-9,10-bis(n-hexylcarbonyloxy)anthracene, 1-methyl-9 , 10-bis(benzoyloxy)anthracene, 1-methyl-9,10-bis(2-naphthylmethoxy)anthracene, 2-ethyl-9,10-bis(acetoxy)anthracene, 2-Ethane-9,10-bis(propionyloxy)anthracene, 2-ethyl-9,10-bis(n-propylcarbonyloxy)anthracene, 2-ethyl-9,10-bis(n Butylcarbonyloxy)anthracene, 2-ethyl-9,10-bis(benzoyloxy)anthracene, 1-ethyl-9,10-bis(acetoxy)anthracene, 1-ethyl-9 ,10-bis(propionyloxy)anthracene, 1-ethyl-9,10-bis(n-propylcarbonyloxy)anthracene, 1-ethyl-9,10-bis(n-butylcarbonyloxy) Anthracene, 1-ethyl-9,10-bis(n-pentylcarbonyloxy)anthracene, 1-ethyl9,10-bis(benzoyloxy)anthracene, 1-ethyl-9,10-bis (2-Naphthoyloxy)anthracene, 1-(tert-butyl)-9,10-bis(n-propylcarbonyloxy)anthracene, 1-(tert-butyl)-9,10-bis(n-butyl) Carbonyloxy)anthracene, 1-(tert-butyl)-9,10-bis(n-pentylcarbonyloxy)anthracene, -(tert-butyl)-9,10-bis(n-hexylcarbonyl)xanthene, 1-(tert-butyl)-9,10-bis(benzoyloxy)anthracene, 1-(tert-butyl)-9,10-bis(4-(tert-butyl)-benzoyloxy) Anthracene, 1-(tert-butyl)-9,10-bis(2-naphthyloxy)anthracene, 2-(tert-butyl)-9,10-bis(n-propylcarbonyloxy)anthracene, 2-( Tert-butyl)-9,10-bis(n-butylcarbonyloxy)anthracene, 2-(tert-butyl)-9,10-bis(n-pentylcarbonyloxy)anthracene, 2-(tert-butyl) -9,10-bis(n-hexylcarbonyloxy)anthracene, 2-(tert-butyl)-9,10-bis(2-naphthalene Methoxy)anthracene, 2-pentyl-9,10-bis(n-propylcarbonyloxy)anthracene, 2-pentyl-9,10-bis(n-butylcarbonyl)xanthene, 2-pentyl -9,10-bis(n-pentylcarbonyloxy)anthracene, 2-pentyl-9,10-bis(benzoyloxy)anthracene and 2-pentyl-9,10-bis(2-naphthyl) Acyloxy) anthracene and the like.

Compounds that contain naphthacene rings and are suitable for use as photosensitizers include, but are not limited to: alkylcarbonyloxy substituted naphthacene compounds, such as 2-methyl-5,11-dioxo-6,12-bis( Acetoxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(n-hexylcarbonyloxy)naphthalene, etc.; aryloxy substituted naphthacene compounds, such as 2-methyl -5,11-Dioxy-6,12-bis(benzoyloxy)naphthacene, 2-methyl-5,11-diox-6,12-bis(o-toluyloxy)naphthacene Benzene, etc.; aryloxycarbonyloxy substituted tetranaphthalene compounds, such as 2-methyl-5,11-dioxo-6,12-bis(phenoxycarbonyloxy)tetracene and 2-ethyl -5,11-Dioxy-6,12-bis(α-naphthyloxycarbonyloxy)naphthalene, etc.

For other types of auxiliary agents, those skilled in the art can choose from commonly used substances in the photosensitive resin composition, which will not be repeated here.

In another exemplary embodiment of the present application, a patterning method is also provided, including mixing, filming and patterning a photosensitive resin composition, the photosensitive resin composition being any of the above Photosensitive resin composition.

The above-mentioned patterning method may specifically include: coating the photosensitive composition on the carrier, pre-baking to form a coating film; selectively exposing the coating film; heating after exposure; and developing the exposed coating film with an alkaline developer. The specific operations are as follows:

The photosensitive composition is mixed and coated on a substrate (silicon substrate, metal substrate, glass substrate, inorganic and/or organic film), preferably using a spinner to coat; the formed coating film is at 80 to 120°C as required Perform pre-bake for 40 to 120 seconds.

After the resist is formed on the substrate, the shape of the wiring pattern is irradiated with light. Actinic rays include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, metal halide lamps, electron beam irradiation devices, X-ray irradiation devices, lasers (argon laser, dye laser, nitrogen) Laser, LED, helium cadmium laser), preferably high-pressure mercury lamp and LED lamp.

The post-exposure heating (PEB) temperature is 80-150°C, preferably 95-110°C, and the heating time is preferably 0.5-30 min. The deprotection reaction or the crosslinking reaction cannot sufficiently proceed at a temperature lower than 40°C, so there is not a sufficient difference in solubility between the ultraviolet irradiated portion and the ultraviolet non-irradiated portion, and the pattern cannot be formed.

The development is performed with an alkaline developer, and the alkaline development method includes the use of an alkaline developer to dissolve and remove the wiring pattern shape. The alkaline developer may be selected from 0.1-10% (w/w) aqueous solutions of tetramethylammonium hydroxide, sodium hydroxide, potassium hydroxide, and sodium bicarbonate. These alkaline developers may contain water-soluble organic solvents, Such as methanol, ethanol, isopropanol, tetrahydrofuran, N-methylpyrrolidone and so on. The development method can be selected from the dipping method, spray method and spray method, preferably the spray method; the temperature of the developer is preferably used at 25-40 ℃, the development time is appropriately determined according to the thickness of the resist, and finally the mask is faithful to the mask Patterned resist pattern.

Among them, the wavelength used for exposure can be selected from g, h, i lines, ArF excimer laser (wavelength 193nm), KrF excimer laser (wavelength 248nm), F2 excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet) ), EB (electron beam), X-ray, soft X-ray etc. can be used for exposure. Among them, g, h, i lines, ArF excimer laser, KrF excimer laser, EUV and EB are preferred. In addition, even if a photosensitive composition that does not contain a compound that generates acid or free radicals by the action of light is used, a good pattern can be formed, so ArF excimer laser (wavelength 193nm) can be used, and EB (electron beam) is preferred of.

In another exemplary embodiment of the present application, an application of any one of the above-mentioned photosensitive resin compositions is provided. The application includes applying the photosensitive composition to the protective film, interlayer insulating material, and image of electronic components. Type transfer material.

The above-mentioned applications can specifically include forming the photosensitive composition into an interlayer insulating film for use in TFTs and panels of liquid crystal display devices; it can also be used as a protective film for color filters and spacers, as well as PS photoresist and BCS photolithography. Glue is used for pattern transfer.

The above-mentioned electronic components include, but are not limited to, liquid crystal display devices, organic EL display devices, electronic components such as Micro-LED, Mini-LED, and quantum dot LED display devices.

In order to facilitate the synthesis of the above-mentioned sulfonimide photoacid generator by those skilled in the art, the preparation method of the sulfonimide photoacid generator of the present application will be briefly described as follows:

The preparation method includes the following steps:

(1) The coupling reaction between 4-bromo-1,8 naphthalenedicarboxylic acid anhydride and indole derivatives produces intermediate 1, the reaction formula is as follows:

(2) Intermediate 1 undergoes a hydroxylamination reaction with hydroxylamine hydrochloride to produce Intermediate 2. The reaction formula is as follows:

(3) Intermediate 2 reacts with sulfonic anhydride (R ₁ -SO ₂ ) ₂ O or sulfonyl chloride R ₁ -SO ₂ -Cl to produce compound A, the reaction formula is as follows:

The reactions involved in steps (1)-(3) are all conventional reactions in the field of organic synthesis. Based on the knowledge of the synthetic route disclosed in the present invention, specific reaction conditions are easily determined by those skilled in the art.

Without limitation, the reaction of step (1) is carried out in an organic solvent. The organic solvent used is not particularly limited, as long as it can dissolve the raw materials without adversely affecting the reaction, such as dioxane, dichloroethane, tert-butanol, toluene, xylene, DMF, and DMSO.

The hydroxylamination reaction in step (2) and the esterification reaction in step (3) are also carried out in an organic solvent. The organic solvent used is not particularly limited, as long as it can dissolve the raw materials without adversely affecting the reaction, such as dichloromethane, dichloroethane, benzene, toluene, xylene and the like.

The raw materials used in the above preparation methods are all known compounds in the prior art, and they can be purchased commercially or conveniently prepared by known synthetic methods such as coupling and FuK.

Hereinafter, the above-mentioned preparation method of the present application will be exemplified by the preparation of specific compounds.

Preparation examples

Preparation Example 1

Synthesis of photoacid generator (A1-1)

Put 5.27g of 2-methylindole into a four-necked flask, dissolve it with 200.19g of toluene, add 13.90g of 4-bromo-1,8-naphthalene anhydride under stirring, and then add 0.58g of tetra( Triphenylphosphine) palladium, 1 mL (1 mol/L) tri-tert-butyl phosphine, and 13.56 g potassium carbonate were heated to 110° C. to reflux, and stirring was continued for 18 h, controlled by HPLC, and then cooled to room temperature. The solution was brown. Water was added and stirred, insoluble matter was filtered off, liquid separation, the organic layer was washed 3 times with water, and then toluene was distilled off under reduced pressure at 60° C. to obtain 11.02 g of light yellow solid.

Dissolve 6.58g of the obtained light yellow solid in 100.2g methanol, add 3.50g hydroxylamine hydrochloride and 4.05g triethylamine, stir at 25°C for 0.5h, then heat up to 70°C, after 8h, wash with water 3 times after cooling, and steam out Methanol and toluene were added to crystallize to obtain 4.85 g of solid.

Put 3.02g of the obtained solid into 60.00g of dichloromethane, then add 0.88g of pyridine and 2.72g of trifluoromethanesulfonic anhydride, react at 0-5°C for 1h, then warm to room temperature, add 1.0g activated carbon for decolorization, room temperature Wash twice with water, adjust pH=2 with hydrochloric acid (35.0%), wash twice with water at room temperature, adjust pH=8 with ammonia water, wash to pH=7, distill at 60°C under normal pressure until dichloromethane remains about 10g, and cool to 40°C Next, add 20.0 g of methanol, then lower the temperature to 5-10° C., stir for 0.5 h, and filter with suction. It was put into a blast oven and dried at 40°C to obtain 1.62 g of a white solid, which is the compound shown in (A1-1).

The ^{structure of the product was characterized by 1} H NMR, and the results are as follows:

¹ H NMR (400MHz, CDCl ₃ ): 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).

Preparation Example 2

Synthesis of photoacid generator (A1-2)

It was synthesized in a similar manner in a 58% yield by following the same procedure as A1-1, in which 3-methylindole was substituted for 2-methylindole. That is, the compound represented by (A1-2).

The ^{structure of the product was characterized by 1} H NMR, and the results are as follows:

¹ H NMR (400MHz, CDCl ₃ ): 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 = 7.5 Hz, 1H), 7.49 (d, J = 7.5 Hz, 1H), 7.28 (t, J = 7.5 Hz, 1H), 7.09 (td, J = 7.5, 1.5Hz, 1H), 2.45 (s, 3H).

Preparation Example 3

Synthesis of photoacid generator (A1-3)

It was synthesized in a similar manner in a 44% yield by following the same procedure as A1-1, in which 4-methylindole was substituted for 2-methylindole. That is, the compound represented by (A1-3).

The ^{structure of the product was characterized by 1} H NMR, and the results are as follows:

¹ H NMR (400MHz, CDCl ₃ ): 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 = 7.5 Hz, 1H), 7.10-7.04 (m, 2H), 2.48 (d, J = 0.7 Hz, 3H).

Preparation Example 4

Synthesis of photoacid generator (A1-4)

It was synthesized in a similar manner in a 40% yield by following the same procedure as A1-1, in which 5-methylindole was substituted for 2-methylindole. That is, the compound represented by (A1-4).

The ^{structure of the product was characterized by 1} H NMR, and the results are as follows:

¹ H NMR (400MHz, CDCl ₃ ): 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, 1.7 Hz, 1H), 2.48 (s, 3H).

Preparation Example 5

Synthesis of photoacid generator (A1-5)

It was synthesized in a similar manner in a 36% yield by following the same procedure as A1-1, in which 6-methylindole was substituted for 2-methylindole. That is, the compound represented by (A1-5).

The ^{structure of the product was characterized by 1} H NMR, and the results are as follows:

¹ H NMR (400MHz, CDCl ₃ ): 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 = 0.8 Hz, 3H).

Preparation Example 6

Synthesis of photoacid generator (A1-6)

It was synthesized in a similar manner in a 46% yield by following the same procedure as A1-1, in which 7-methylindole was substituted for 2-methylindole. That is, the compound represented by (A1-6).

The ^{structure of the product was characterized by 1} H NMR, and the results are as follows:

¹ H NMR(400MHz, CDCl ₃ ): 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) .

Preparation Example 7

Synthesis of photoacid generator (A2-2)

Add 6.51g of 3-methoxymethylindole to a four-necked flask, dissolve it with 200.10g of toluene, add 13.87g of 4-bromo-1,8-naphthalene anhydride while stirring, and then add 0.12 g palladium acetate, 1 mL (1 mol/L) of tri-tert-butyl phosphine, and 18.54 g of potassium phosphate were heated to 110° C. and refluxed, stirring was continued for 12 h, controlled by HPLC, and then cooled to room temperature. The solution was brown. Water was added and stirred, insoluble matter was filtered off, liquid separation, the organic layer was washed 3 times with water, and then toluene was distilled off under reduced pressure at 60° C. to obtain 12.02 g of light yellow solid.

Dissolve 7.02g of the obtained light yellow solid in 100.20g methanol, add 3.42g hydroxylamine hydrochloride and 3.67g triethylamine, stir at 20°C for 0.5h, then warm up to 80°C, after 6h, wash with water 3 times after cooling, and steam out Methanol and toluene were added to crystallize to obtain 5.07 g of solid.

Put 4.05g of the obtained solid into 100.10g of dichloromethane, then add 1.11g of pyridine and 3.62g of perfluoro-1-butanesulfonic acid, react at 5-10℃ for 2h, warm up to room temperature, add 0.95g of activated carbon to decolorize , Wash twice with water at room temperature, adjust pH=2 with hydrochloric acid (35.0%), wash twice with water at room temperature, adjust pH=8 with ammonia water, wash to pH=7, distill at 60°C under normal pressure until dichloromethane remains about 10g, and cool to Below 40°C, add 20.00g of methanol, then lower the temperature to 5-10°C, stir for 0.5h, and filter with suction. Put it into a blast oven and dry at 40°C to obtain 3.55 g of a white solid, which is the compound shown in (A2-2).

The ^{structure of the product was characterized by 1} H NMR, and the results are as follows:

¹ H NMR(400MHz, CDCl ₃ ): δ8.40-8.26(m,3H), 8.06-771(m,2H), 7.69-7.58(m,3H), 7.27(t,J=7.4Hz,1H) , 7.19 (t, J = 7.5 Hz, 1H), 4.54 (s, 2H), 3.41 (s, 3H).

Preparation Example 8

Synthesis of photoacid generator (A3-1)

In a four-necked flask were added 3.65 g of white-like powder 3-indole formaldehyde, 3.11 g of benzyl triphenylphosphonium chloride, 3.12 g of potassium tert-butoxide and 100 mL of absolute ethanol, and the reaction was refluxed for 10 hours under stirring. After evaporation of part of the ethanol, it was purified by silica gel column chromatography and recrystallized from ethanol to obtain 3.05 g of an off-white solid.

The ^{structure of the solid product was characterized by 1} H NMR, and the results are as follows:

¹ H NMR (400MHz, CDCl ₃ ): δ9.93 (d, J = 8.4Hz, 1H), 7.71-7.64 (m, 2H), 7.56 (d, J = 11.0 Hz, 1H), 7.51-7.26 (m , 6H), 7.22 (t, J = 7.5 Hz, 1H), 7.11 (t, J = 7.5 Hz, 1H), 6.54-6.50 (m, 1H).

In a four-necked flask, 8.80g of off-white solid was added, dissolved in 200.30g of toluene, 13.92g of 4-bromo-1,8-naphthalene anhydride was added under stirring, and then 0.56g of tetrakis(triphenylphosphine)palladium, 11.21g potassium tert-butoxide and 0.26g triphenylphosphine, heated to 110°C under reflux, continued stirring for 22h, controlled by HPLC, and then cooled to room temperature, the solution was brown. Water was added and stirred, the insoluble matter was filtered off, the liquid was separated, the organic layer was washed 3 times with water, and then toluene was distilled off under reduced pressure at 60° C. to obtain 13.56 g of light yellow solid.

The obtained light yellow solid 8.35 was dissolved in 200.52g methanol, and 3.51g hydroxylamine hydrochloride and 2.85g diethylamine were added dropwise. After the addition, the temperature was kept at 35°C and stirred for 1h, then the temperature was raised to 80°C, after 10h, cooled After washing 3 times with water, distilling out methanol, adding toluene to crystallize to obtain 6.04 g of solid.

Put 5.01g of the obtained solid into 80.20g of dichloromethane, then add 1.35g of pyridine and 3.63g of trifluoromethanesulfonic anhydride, react at 0-5°C for 1h, warm up to room temperature, add 1.05g of activated carbon for decolorization, wash with water at room temperature Twice, adjust pH=2 with hydrochloric acid (35.0%), wash twice with water at room temperature, adjust pH=8 with ammonia water, wash to pH=7, distill at 60°C under normal pressure to about 10g of dichloromethane residue, and cool to below 40°C , Add 20.00g of methanol, then lower the temperature to 5-10°C, stir for 0.5h, and filter with suction. It was put into a blast oven and dried at 40°C to obtain 4.28 g, which is the compound shown in (A3-1).

The ^{structure of the product was characterized by 1} H NMR, and the results are as follows:

¹ H NMR (400MHz, CDCl ₃ ): δ 8.39-8.35 (m, 2H), 8.21 (s, 1H), 7.86 (d, J = 7.3 Hz, 1H), 7.73-7.64 (m, 3H), 7.58 (dd, J=7.5, 1.6 Hz, 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).

Preparation Example 9

Synthesis of photoacid generator (A4-4)

Add 100.10g of 3-methoxybutanol and 20.01g of indole-3-acetic acid to a four-necked flask, then add dropwise 20.05g of sulfuric acid at room temperature, raise the temperature to 150°C, stir and react for 3h, then cool to room temperature, and wash with water three times. The organic layer was added with dichloromethane and pure water, washed 2-3 times to neutrality, 1.02 g of anhydrous sodium sulfate was added for suction filtration, and then distilled under reduced pressure to obtain 27.25 g of solid.

The ^{structure of the solid product was characterized by 1} H NMR, and the results are as follows:

¹ H NMR (400MHz, CDCl ₃ ): 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 = 6.9 Hz, 1H), 3.36 (s, 3H), 1.90–1.76 (m, 2H), 1.23 (d, J = 6.8 Hz, 3H).

Put 10.80g of the obtained solid into a four-necked flask, dissolve it with 206.30g of toluene, add 13.88g of 4-bromo-1,8-naphthalene anhydride under stirring, and then add 0.29g of bis(dibenzylidene Acetone) palladium, 13.27g potassium carbonate and 1 mL (2mol/L) of tri-tert-butyl phosphine, heated to 110°C under reflux, continued stirring for 18h, controlled by HPLC, and then cooled to room temperature, the solution was brown. Water was added and stirred, the insoluble matter was filtered off, liquid separation, the organic layer was washed 3 times with water, and then toluene was distilled off under reduced pressure at 60° C. to obtain 14.59 g of solid.

The obtained solid 9.39 was dissolved in 201.56g methanol, and 3.50g hydroxylamine hydrochloride and 4.06g triethylamine were added dropwise. After the addition, the temperature was kept at 35°C and stirred for 1h, and then the temperature was raised to 80°C. After 10h, it was cooled and washed with water 3. Next, the methanol was distilled off, and toluene was added to crystallize to obtain 6.24g of solid.

Put 5.02g of the obtained solid into 100.05g of dichloromethane, then add 1.15g of pyridine and 3.23g of trifluoromethanesulfonic anhydride, react at 0-5°C for 1h, warm up to room temperature, add 1.10g of activated carbon for decolorization, wash with water at room temperature Twice, adjust pH=2 with hydrochloric acid (35.0%), wash twice with water at room temperature, adjust pH=8 with ammonia water, wash to pH=7, distill at 60°C under normal pressure to about 10g of dichloromethane residue, and cool to below 40°C , Add 20.10g of methanol, then lower the temperature to 5-10°C, stir for 0.5h, and filter with suction. Put it into a blast oven and dry at 40°C to obtain 4.17 g of off-white solid, which is the compound shown in (A4-4).

The ^{structure of the product was characterized by 1} H NMR, and the results are as follows:

¹ H NMR (400MHz, CDCl ₃ ): 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=6.8 Hz, 3H).

Preparation Example 10

Synthesis of photoacid generator (A5-3)

In a four-necked flask, 8.82 g of 3-bromoindole, 0.27 g of triphenylphosphine, 10.12 g of triethylamine, and 200 mL of THF were added, and nitrogen gas was added, and then 0.48 g of CuI and 0.35 g of Pd(PPh ₃ ) ₂ Cl _{2 were added} . The mixture was heated to reflux, and a THF solution containing 9.81 g of propargyl acetate was added dropwise, controlled by HPLC, stirred and refluxed for 15 hours and then cooled to room temperature. After washing with water, the organic phase was evaporated to remove the solvent to obtain a brown solid; the dichloromethane was dissolved, washed with water and then dichloromethane was evaporated, and acetonitrile was recrystallized to obtain 6.73 g of solid.

The ^{structure of the solid product was characterized by 1} H NMR, and the results are as follows:

¹ H NMR (400MHz, CDCl ₃ ): 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).

Add 8.60g of the obtained solid into a four-neck flask, dissolve it with 201.95g of xylene, add 13.92g of 4-bromo-1,8-naphthalene anhydride under stirring, and then add 0.29g of bis(dibenzylidene Base acetone) palladium, 13.53g potassium carbonate and 1 mL (2mol/L) of tri-tert-butyl phosphine, heat to 140°C and reflux, continue stirring for 20h, HPLC control, then cool to room temperature, add water to stir, filter, separate liquid, organic The layer was washed three times with water, and then xylene was distilled off under reduced pressure at 60° C. to obtain 14.00 g of solid.

Dissolve 8.20g of the obtained solid in 150.18g methanol, add dropwise 2.35g hydroxylamine hydrochloride and 2.77g triethylamine, after the dropwise addition, heat and stir at 25℃ for 1h, then heat up to 80℃, after 12h, wash with water after cooling Three times, methanol was distilled off, and toluene was recrystallized to obtain 5.59 g of solid.

Put 5.01g of the obtained solid into 100.20g of dichloromethane, then add 1.21g of pyridine and 3.66g of trifluoromethanesulfonic anhydride, react at 0-5°C for 1h, then warm to room temperature, add 0.98g of activated carbon for decolorization, room temperature Wash twice with water, adjust pH=2 with hydrochloric acid (35.0%), wash twice with water at room temperature, adjust pH=8 with ammonia water, wash to pH=7, distill at 60°C under normal pressure until dichloromethane remains about 10g, and cool to 40°C Next, add 20.25g of methanol, then lower the temperature to 5-10°C, stir for 0.5h, and filter with suction. Put it in a blast oven and dry at 40°C to obtain 4.92 g of off-white solid, which is the compound shown in (A5-3).

The ^{structure of the product was characterized by 1} H NMR, and the results are as follows:

¹ H NMR (400MHz, CDCl ₃ ): 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, 1.7 Hz, 1H), 7.31-7.25 (m, 2H), 4.84 (s, 2H), 2.10 (s, 3H).

Preparation Example 11

Synthesis of photoacid generator (A6-3)

Add 100.33g of dioxane and 6.67g of 3-hydroxyindole to a four-necked flask, stir at room temperature and add 5.08g of dihydropyran dropwise, then add 0.20g of p-toluenesulfonic acid, and wash with water until neutral after 2h reaction. After extraction with dichloromethane, the dichloromethane was distilled off, and 9.73 g of solid was precipitated.

The ^{structure of the solid product was characterized by 1} H NMR and the results are as follows:

¹ H NMR (400MHz, CDCl ₃ ): 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, add 8.71g of off-white solid, dissolve it with 200.36g of toluene, add 13.92g of 4-bromo-1,8-naphthalene anhydride under stirring, and then add 0.59g of tetrakis(triphenylphosphine) ) Palladium, 11.26g potassium tert-butoxide and 0.28g triphenylphosphine, heated to 110°C and refluxed, continued stirring for 25h, controlled by HPLC, then cooled to room temperature, stirred with water, filtered and separated, and the organic layer was washed 3 times with water. Then, toluene was distilled off under reduced pressure at 60°C to obtain 13.29 g of light yellow solid.

The obtained solid 15.69 was dissolved in 300.21 g of dichloromethane, and 2.28 g of hydroxylamine hydrochloride was added dropwise, stirred at room temperature for 6 hours, filtered, rinsed with methanol, and dried in a blast oven at 40° C. to obtain 10.56 g of solid.

The ^{structure of the solid product was characterized by 1} H NMR, and the results are as follows:

¹ H NMR (400MHz, CDCl ₃ ): 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).

Dissolve 13.9g of the above solid in 203.29g methanol, add 6.95g of methanesulfonyl chloride and 7.54g of triethylamine, react at 65°C for 12h, then add dropwise 2.28g of hydroxylamine hydrochloride and 2.35g of triethylamine, then add 100.76g of methanol Incubate at 15°C and stir for 0.5h, then heat up to 80°C. After 10h, filter after cooling, wash 2-3 times with dilute hydrochloric acid and water, and dry in a blast oven at 40°C to obtain 5.89g of solid.

The ^{structure of the solid product was characterized by 1} H NMR and the results are as follows:

¹ H NMR(400MHz, CDCl ₃ ): 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, 1.6 Hz, 2H), 7.29 (t, J = 7.4 Hz, 1H), 7.11 (t, J = 7.5 Hz, 1H), 3.22 (s, 3H).

Put 8.45 g of the obtained solid into 60.09 g of dichloromethane, then add 2.76 g of pyridine, and then add dropwise a solution of camphorsulfonyl chloride in dichloromethane (camphorsulfonyl chloride 5.91 g, dichloromethane 60.19 g) at room temperature, and add dropwise After the completion, keep stirring at 40℃ for 5h, then add 1.00g activated carbon to decolorize, wash twice with water at room temperature, adjust pH=2 with hydrochloric acid (35.0%), wash twice with water at room temperature, adjust pH=8 with ammonia water, wash with water to pH=7,60 Distill at normal pressure to about 10g of dichloromethane residue, reduce the temperature to below 40°C, add 20.50g of methanol, and then lower the temperature to 5-10°C, stir for 0.5h, and filter with suction. It was put into a blast oven and dried at 40°C to obtain 4.27 g of solid, which is the compound shown in (A6-3).

The ^{structure of the product was characterized by 1} H NMR, and the results are as follows:

¹ H NMR (400MHz, CDCl ₃ ): 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 = 8.5 Hz, 1H), 1.88-1.60 (m, 4H), 1.04 (d, J = 1.6 Hz, 3H), 0.99 (d, J = 1.4 Hz, 3H).

Preparation Example 12

Synthesis of photoacid generator (A7-1)

Add 7.9g of 3-bromoindole into a four-necked flask, dissolve it with 201.72g of xylene, add 13.95g of 4-bromo-1,8-naphthalene anhydride under stirring, and then add 0.32g of bis(two) Benzylidene acetone) palladium, 1 mL (1 mol/L) of tri-tert-butyl phosphine, and 21.39 g potassium phosphate were heated to 140° C. to reflux, stirring was continued for 12 h, controlled by HPLC, and then cooled to room temperature. The solution was brown. Water was added and stirred, the insoluble matter was filtered off, liquid separation, the organic layer was washed 3 times with water, and then toluene was distilled off under reduced pressure at 60° C. to obtain 13.12 g of solid.

Dissolve 7.88g of the obtained solid in 100.88g methanol, add 2.11g hydroxylamine hydrochloride and 2.23g triethylamine, stir at 20°C for 0.5h, then warm up to 80°C, after 6h, wash with water 3 times after cooling, and distill out the methanol. Toluene was added for crystallization to obtain 5.37 g of solid.

Put 5.01g of the obtained solid into 101.02g of dichloromethane, then add 1.30g of pyridine and 3.49g of trifluoromethanesulfonic anhydride, react at 0-5℃ for 1h, then warm to room temperature, add 1.29g of activated carbon for decolorization, room temperature Wash twice with water, adjust pH=2 with hydrochloric acid (35.0%), wash twice with water at room temperature, adjust pH=8 with ammonia water, wash to pH=7, distill at 60°C under normal pressure until dichloromethane remains about 10g, and cool to 40°C Next, add 20.12g of methanol, then cool to 5-10°C, stir for 0.5h, and filter with suction. It was put into a blast oven and dried at 40°C to obtain 4.36 g of a white solid, which is the compound shown in (A7-1).

The ^{structure of the product was characterized by 1} H NMR, and the results are as follows:

¹ H NMR (400MHz, CDCl ₃ ): δ8.39-8.24 (m, 3H), 7.94 (dd, J = 7.4, 1.5 Hz, 1H), 7.71 (d, J = 7.5 Hz, 1H), 7.64-7.59 (m, 3H), 7.34 (t, J=7.4 Hz, 1H), 7.27 (t, J=7.5 Hz, 1H).

Preparation Example 13

Synthesis of photoacid generator (A8-1)

Add p-methylbenzyl chloride 15.11, indole 11.72g, 14.70g aluminum trichloride and 155.06g benzene into a four-necked flask. After stirring at 0-4℃ for 8h, the temperature is raised to 30℃ and stirred for 1h, and then washed with water at about 25℃. Three times to pH5-6; concentrated under reduced pressure, then methanol was added, the temperature was lowered by 2-6°C, and a solid was precipitated. Wash with water until it is neutral, then add methanol to crystallize to obtain solid 15.95g.

The ^{structure of the solid product was characterized by 1} H NMR, and the results are as follows:

¹ H NMR(400MHz, CDCl ₃ ): 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 = 1.0 Hz, 3H).

Add 8.89g of the obtained solid into a four-neck flask, dissolve it with 207.80g of xylene, add 13.95g of 4-bromo-1,8-naphthalene anhydride under stirring, and then add 0.29g of bis(dibenzylidene Base acetone) palladium, 21.25g potassium phosphate and 0.62g triphenylphosphine, heated to 140°C and refluxed, continued stirring for 18h, controlled by HPLC, and then cooled to room temperature; add water and stir, filter out insoluble materials, separate the liquid, and wash the organic layer with water After 3 times, xylene was distilled off under reduced pressure to obtain 16.92 g of solid.

Dissolve 8.35g of the obtained solid in 204.29g methanol, add dropwise 2.24g hydroxylamine hydrochloride and 2.56g triethylamine, after the addition, stir at 25°C for 1h, then warm to 80°C, after 10h, wash with water after cooling for 3 Next, the methanol was distilled off, and toluene was added to crystallize to obtain 5.83 g of solid.

Put 5.00 g of the obtained solid into 60.53 g of dichloromethane, then add 1.16 g of pyridine, and add dropwise the methylene chloride solution of p-toluenesulfonyl chloride (p-toluenesulfonyl chloride 2.41g, dichloromethane 61.27g), and the addition is complete. Incubate at 40°C and stir for 6 hours. After cooling, add 1.06g activated carbon to decolorize, wash twice with water at room temperature, adjust pH=2 with hydrochloric acid (35.0%), wash twice with water at room temperature, adjust pH=8 with ammonia water, wash with water to pH=7,60 Distill under normal pressure at ℃ until dichloromethane remains about 10g, cool to below 40°C, add 20.43g of methanol, then cool to 5-10°C, stir for 0.5h, and filter with suction. Put it into a blast oven and dry at 40°C to obtain 4.02 g of off-white solid, which is the compound shown in (A8-1).

The ^{structure of the product was characterized by 1} H NMR, and the results are as follows:

¹ H NMR (400MHz, CDCl ₃ ): 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 = 0.8 Hz, 3H), 2.34 (d, J = 0.9 Hz, 3H).

Preparation Example 14

Synthesis of photoacid generator (A9-1)

Add 6.82g of anhydrous zinc chloride, 100mL of dichloroethane, and 14.13g of acetyl chloride to a four-necked flask, stir at room temperature for 30min, and slowly add dropwise 5.83g of indole solution dissolved in 50mL of dichloroethane; reaction at room temperature for 1 hour , The temperature was raised to 50°C to continue the reaction. During the reaction, 13.58g of anhydrous zinc chloride powder was added in 3 times, controlled by TLC, and the raw material was completely transformed after the reaction for 3 hours. Dichloroethane was distilled out, and 50% potassium hydroxide was added. 150 mL of the aqueous solution was extracted 3 times with anhydrous ether. The organic layers were combined and dried overnight with anhydrous magnesium sulfate. The ether solvent was removed and recrystallized with dichloromethane/petroleum ether to obtain 5.81 g of light yellow needle-like crystals.

The ^{structure of the crystal product was characterized by 1} H NMR, and the results are as follows:

¹ H NMR(400MHz, CDCl ₃ ): 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).

Add 6.93g of the obtained light yellow solid into a four-necked flask, dissolve it with 202.25g of toluene, add 13.90g of 4-bromo-1,8-naphthalene anhydride under stirring, and then add 0.29g of bis(diethylene) Benzylacetone) palladium, 10.23g triethylamine and 1mL (2mol/L) tri-tert-butylphosphine, heated to 110°C and refluxed, continued stirring for 12h, controlled by HPLC, then cooled to room temperature, added water, stirred, filtered, and separated , The organic layer was washed 3 times with water, and then toluene was distilled off under reduced pressure at 60° C. to obtain 12.68 g of solid.

The obtained solid 7.32 was dissolved in 201.53g methanol, and 2.45g hydroxylamine hydrochloride and 3.23g triethylamine were added dropwise. After the addition, the mixture was stirred at 25°C for 1h, and then heated to 70°C. After 6h, it was cooled and washed 3 times with water. , Distill off methanol, add toluene to crystallize, obtain 5.17g solid.

Put 3.82g of the obtained solid into 60.21g of dichloromethane, then add 0.95g of pyridine, and then add dropwise the dichloromethane solution of pentafluorobenzenesulfonyl chloride (pentafluorobenzenesulfonyl chloride 3.07g, dichloromethane 61.65g), After dripping, keep stirring at 40℃ for 4h. After cooling, add 1.09g activated carbon to decolorize, wash twice with water at room temperature, adjust pH=2 with hydrochloric acid (35.0%), wash twice at room temperature, adjust pH=8 with ammonia water, wash with water to pH= 7. Distill at 60°C under normal pressure until the residual dichloromethane is about 10g, cool to below 40°C, add 20.46g of methanol, then cool to 5-10°C, stir for 0.5h, and filter with suction. Put it in a blast oven and dry at 40°C to obtain 3.22 g of off-white solid, which is the compound shown in (A9-1).

The ^{structure of the product was characterized by 1} H NMR, and the results are as follows:

¹ H NMR(400MHz, CDCl ₃ ): 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, 1.6 Hz, 1H), 7.34-7.25 (m, 2H), 2.63 (s, 3H).

Comparative Example Compound

Compound Comparative Example 1

Non-ionic photoacid generator (B-1)

Compound Comparative Example 2

Non-ionic photoacid generator (B-2)

Performance evaluation

The performance evaluation of the photoacid generator compound synthesized in the preparation example and the compound of the comparative example was performed respectively, and the evaluation indicators included molar absorption coefficient, acid production, solubility, and resist curability.

(1) Molar absorption coefficient

The compound was diluted to 0.25 mmol/L with acetonitrile, and the absorbance of a cuvette length of 1 cm was measured in the range of 200-500 nm using an ultraviolet-visible spectrophotometer (Universal UPG-752). _{The molar absorption coefficients (ε 365} ) and (ε ₄₀₅ ) of the I line (365 nm) and the H line (405 nm) were calculated from the following formula.

ε ₃₆₅ (L·mol ^-1 ·cm ^-1 )=A ₃₆₅ /(0.00025mol/L*1cm)

In the formula, A ₃₆₅ represents the absorbance at 365 nm.

ε ₄₀₅ (L·mol ^-1 ·cm ^-1 )=A ₄₀₅ /(0.00025mol/L*1cm)

In the formula, A ₄₀₅ represents the absorbance at 405 nm.

The results are shown in Table 1.

Table 1

(2) Acid production

Each of 10 mg of the compound was weighed on a glass dish, and 100 mg of dichloromethane was added to prepare a solution. Monochromatic light at 365nm (I line) and 405nm (H line) is selected as the exposure light source, which is irradiated by an ultraviolet light source device (IWATA UV-100D) with a specific exposure intensity through 365nm and 405nm bandpass filters (103Mw/ cm ² ) Obtained. To the irradiated solution, a 0.04w/v% thymol blue solution was added dropwise to confirm whether there was acid generation. When the color of the solution is red, the solution shows sufficient acidity below pH 1.2 through the generation of acid, so it is evaluated as "○"; when the color of the solution is yellow, the pH is 2.8-8.0, which does not show sufficient acidity, and it is evaluated as "×".

(3) Solubility

The high solubility not only makes the purification of the photoacid generator compound easy, but also enables the photoacid generator compound to expand the concentration range used in photoresist and different solvent systems. Take 1.0000g of the light acid generator compound product, and gradually add solvents (PGMEA, butyl acetate and cyclohexanone) at 25°C until the solids in each test tube are completely dissolved. Record the quality of the solvent used. The solubility is expressed by the following formula .

(4) Hardening of resist

Use a spin coater to mix 75 parts of p-hydroxystyrene resin (Maruka LINKER S-2P), 25 parts of melamine curing agent (Benok Biotech), 1 part of photoacid generator and 1 part of photoacid generator at 100rpm/10s. A resin solution of 200 parts of propylene glycol monomethyl ether acetate (PGMEA) was coated on a glass substrate (diameter 10 cm). Next, vacuum drying was performed at 25° C. for 5 minutes, and then drying was performed on a hot plate at 80° C. for 3 minutes, thereby forming a resist film with a thickness of about 3 μm. The resist film was exposed using an ultraviolet irradiation device (IWATA UV-100D) equipped with a filter. The cumulative exposure is measured at a wavelength of 365nm. Next, post-exposure heating (PEB) was performed for 10 minutes in a dryer at 120°C, and then immersed in 0.5% potassium hydroxide for 30 seconds to develop, and immediately washed with water and dried. The film thickness of the resist was measured using a shape measuring microscope (Keyence VK-8500). The resist curability was evaluated based on the following criteria based on the minimum exposure amount in which the film thickness change of the resist before and after development was within 10%.

⊙: The minimum exposure is less than 200mJ/cm ² ;

○: The minimum exposure is greater than 200mJ/cm ² and less than 250mJ/cm ^2;

×: The minimum exposure is greater than 250mJ/cm ² .

The evaluation results are listed in Table 2.

Table 2

The test results in Table 1 and Table 2 show that, compared with the compound of the comparative example, the photoacid generator of the present invention has a significantly higher molar absorption coefficient at both the I line and the H line, and the light absorption capacity is much higher than that of the comparative example. . At the same time, the photoacid generator compound of the present invention is excellent in acid production, and also has obvious advantages in solubility and resist hardenability.

Further, the difference between the acid generator compounds shown in Preparation Examples 1-6 is only the difference in the positions of the substituents on the indole group, which are the 2-position, 3-position, 4-position, 5-position, 6-position and 7-position respectively. . The test results in Table 1 and Table 2 show that, compared to other sites, the compound of Preparation Example 2 (that is, the indole group contains a 3-position substituent) has significantly higher molar absorption at both the I line and the H line. Coefficient, and the solubility and resist hardenability are more excellent.

Furthermore, other example compounds containing the 3-position substituent on the indole group were characterized, and the results are listed in Table 3.

table 3

It can be seen from Table 3 that the molar absorption coefficients in Preparation Examples 7-14 are high, and the solubility is all above 30%, which provides a sufficient possibility for the photoresist.

Industrial availability

The photoacid generator with the structure represented by the general formula (A) of the present invention has high sensitivity to I line and H line, and can be used for coatings, coating agents, inks, and inkjet inks in the wavelength range of 300nm-450nm , Resist films, liquid resists, negative resists, positive resists, resists for MEMS, negative photosensitive materials, materials for stereo lithography and micro stereo lithography, etc.

The industrial applicability of the above-mentioned industry will be described below in conjunction with the composition examples and comparative examples.

Examples of photosensitive compositions

Each raw material of the photosensitive composition was uniformly dissolved in 100% PGMEA (propylene glycol methyl ether acetate) to obtain a photosensitive composition having a solid content concentration of 20% (w/w). The types and contents of resin component (A), aromatic carboxylic acid compound (B), and sulfonimide photoacid generator (C) are shown in Table 4.

Composition Example 1

Among them, the resin component (A) adopts A ₁ type resin, and the structural formula of each component is shown in formula A ₁₁ -formula A _15. The value at the bottom right of each repeating unit represents the content of the repeating unit in the resin (mass %).

The sulfonimide photoacid generator (C) adopts _{the sulfonimide photoacid generator of type C 11} (that is, A1-9 above), and its molecular formula structure is:

The other component types and contents are shown in Table 4.

Composition Example 2

The difference between composition example 2 and composition example 1 is that:

The resin component (A) using a mixture of resin and A ₃ types of resins of the type A _1, A ₁ mass ratio of resin and the type of resin of the type A ₃ is 7: 3, A ₁ type resins such as Formula A ₁₁ - of formula a _15, lower right value of each repeating unit represented by the repeating units in the resin content (% by mass).

A ₃ type resin is represented by formula A ₃₁ -formula A ₃₂ , and the value at the lower right of each structural unit represents the content (mass %) of the repeating unit in the resin.

The other component types and contents are shown in Table 4.

Composition Example 3

Among them, the resin component (A) adopts A ₁ type resin, and the structural formula of each component is shown in formula A ₁₁ -formula A _15. The value at the bottom right of each repeating unit represents the content of the repeating unit in the resin (mass %).

The aromatic carboxylic acid compound (B ₁ ) is obtained by reacting an aromatic diol (B′) with a molar ratio of 1:1 with 2,3,3′,4′-biphenyltetracarboxylic dianhydride.

The sulfonimide photoacid generator (C) adopts _{the sulfonimide photoacid generator of type C 11} (that is, A1-9 above), and its molecular formula structure is:

Composition Example 4

The difference between composition example 4 and composition example 3 is that:

Resin component (A) adopts A ₂ type resin, and the structural formula of each component is as shown in formula A ₂₁ -formula A _24. The value at the bottom right of each repeating unit represents the content of the repeating unit in the resin (mass %).

The other component types and contents are shown in Table 4.

Composition Example 5

The difference between composition example 5 and composition example 3 is that:

Resin component (A) adopts A ₃ type resin, and the structural formula of each component is shown in formula A ₃₁ -formula A ₃₂ respectively. The value at the bottom right of each structural unit represents the content of the repeating unit in the resin (mass %).

The other component types and contents are shown in Table 4.

Composition Example 6

The difference between composition example 6 and composition example 3 is that:

(1) Sulfonimide photoacid generator (C) adopts C ₁₂ (that is, A2-4 above) type sulfonimide photoacid generator, and its molecular formula structure is:

(2) The types and contents of other components are shown in Table 4.

Composition Example 7

The difference between composition example 7 and composition example 3 is that:

(1) Sulfonimide photoacid generator (C) adopts C ₁₃ (ie A3-2 above) type sulfonimide photoacid generator, and its molecular formula structure is:

(2) The types and contents of other components are shown in Table 4.

The difference between composition example 8 and composition example 3 is that:

(1) Sulfonimide photoacid generator (C) adopts C ₁₄ (that is, A5-4 above) type sulfonimide photoacid generator, and its molecular formula structure is:

(2) The types and contents of other components are shown in Table 4.

The difference between composition example 9 and composition example 3 is that:

(1) Sulfonimide photoacid generator (C) adopts C ₁₅ (that is, A9-2 above) type sulfonimide photoacid generator, and its molecular formula structure is:

(2) The types and contents of other components are shown in Table 4.

Composition Example 10

The difference between composition example 10 and composition example 3 is that:

_{(1) A non-aromatic carboxylic acid compound B 2} obtained by reacting an aromatic diol (B′) and tetrahydrophthalic anhydride at a molar ratio of 1:1 is used.

(2) The types and contents of other components are shown in Table 4.

Composition Example 11

The difference between composition example 11 and composition example 3 is that:

(1) Use non-aromatic carboxylic acid compound polymethacrylic acid (B ₃ ).

(2) Add 1 part by mass of 2-isopropylthioxanthone as a photosensitizer.

(3) The types and contents of other components are shown in Table 4.

Composition Example 12

The difference between composition example 12 and composition example 3 is that:

(1) The content of C ₁₁ type sulfonate photoacid generator is different.

(2) Add 1 part by mass of 9,10-bis(n-butoxy)anthracene as a photosensitizer.

(3) The types and contents of other components are shown in Table 4.

Composition Example 13

The difference between composition example 13 and composition example 3 is that:

The content of C ₁₁ type sulfonimide photoacid generator is different.

The other component types and contents are shown in Table 4.

Composition Comparative Example 1

Compositions distinction Comparative Example 1 Example 1 of the embodiment wherein the composition, imide photoacid class (C) C ₂ using the sulfonimide type photoacid class, the structure having the formula:

The other component types and contents are shown in Table 4.

Composition Comparative Example 2

The difference between composition comparative example 2 and composition example 2 is that:

(1) Sulfonimide photoacid generator (C) adopts C ₂ type sulfonimide photoacid generator, and its molecular structure is:

(2) The types and contents of other components are shown in Table 4.

Composition Comparative Example 3

The difference between composition comparative example 3 and composition example 3 is that:

(1) Sulfonimide photoacid generator (C) adopts C ₂ type sulfonimide photoacid generator, and its molecular structure is:

(2) The types and contents of other components are shown in Table 4.

The photosensitive compositions prepared in Composition Examples 1-13 and Composition Comparative Examples 1-3 were evaluated for sensitivity and resolution by the following methods, and the results are recorded in Table 4.

(1) Sensitivity evaluation method

On each silicon wafer, the photosensitive composition of each of the examples and the comparative example was coated with a film thickness of 3 μm that can form a pattern to form a coating film. The formed coating film was prebaked at 90°C for 100 seconds. After pre-baking, while gradually changing the exposure amount, the coating film was exposed through a mask for forming a hole pattern with a diameter of 10 μm, and then developed at 25° C. with a 2.0% tetramethylammonium hydroxide aqueous solution for 30 seconds. The minimum exposure required to form a hole pattern with a diameter of 10 μm is determined by the above method. From the obtained minimum exposure value, the sensitivity is evaluated according to the following criteria. (○-50mJ/cm ² or less, X-300mJ/cm ² or more)

(2) Resolution evaluation

Using a mask for forming a hole pattern with a diameter of 5 μm, coating film formation, coating film exposure, and development were performed in the same manner as the sensitivity evaluation, except for exposure at an exposure amount of ^{100 mJ/cm 2.} The coating film after development was observed, and the resolution was evaluated according to the following criteria. (○-Can form a pattern with a diameter of 5μm, X-Cannot form a pattern with a diameter of 5μm)

Table 4

As can be seen from Table 4, the resin component (A) having an acid group protected by a protective group, an aromatic carboxylic acid compound (B) having a carboxyl group bonded to an aryl group, and a naphthalimide sulfonate having a predetermined structure (C) Mixing and forming a photosensitive composition containing a derivative can form a pattern excellent in sensitivity and resolution. If there is no resin protected by a protecting group, patterns cannot be formed.

It can be seen from Composition Example 1 and Composition Comparative Example 1 that when the photosensitive composition contains the sulfonimide-based photoacid generator of the present invention, the photosensitive composition can obtain the desired sensitivity. It can be seen from Composition Example 3, Composition Example 10, and Composition Example 11 that even if the photosensitive composition contains a compound having a carboxyl group, when the compound does not have a carboxyl group bonded to an aromatic group, the photosensitive composition The resolution of the sexual composition can not meet the requirements. Comparing composition example 2 and composition comparison example 2, it is found that the naphthalimide sulfonate substituted with indole derivatives has better sensitivity and resolution. It can be seen from Composition Example 3 and Composition Comparative Example 3 that when the photosensitive composition contains the sulfonimide photoacid generator of the present invention, the photosensitive composition can obtain the required sensitivity and resolution.

In summary, the photosensitive composition of the present invention can be used as a positive photosensitive composition. The difference between the width of the opening of the pattern mask and the width of the pattern is small, and it can form a fine pattern and suppress the pattern generation after development. Undercut, and excellent sensitivity. It can be used as a photosensitive composition in protective films or interlayer insulating materials or pattern transfer materials for electronic components such as liquid crystal display devices, organic EL display devices, Micro-LED, Mini-LED, and quantum dot LED display devices.

The above descriptions are only preferred embodiments of the present invention and are not used to limit the present invention. For those skilled in the art, the present invention can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (18)

1. A sulfonimide photoacid generator capable of producing high acid in the I line and H line, and has the structure shown in the following general formula (A):

   

   among them,

   R ₁ represents a C ₁ -C ₂₀ linear or branched alkyl or fluoroalkyl group, a C ₆ -C ₁₈ substituted or unsubstituted aryl group, or a camphor group;

   R ₂ -R ₇ each independently represent the following groups:

   hydrogen;

   halogen;

   C ₁ -C ₂₀ linear or branched alkyl or haloalkyl, optionally, -CH ₂ -can be substituted by -O-;

   In the phenyl group, optionally, at least one of its hydrogen atoms may be substituted by a C ₁ -C ₈ alkyl group or an alkoxy group;

   A C ₇ -C ₂₀ phenyl alkyl group, optionally, at least one hydrogen atom on the phenyl group may be substituted by a C ₁ -C ₈ alkyl group or an alkoxy group, and -CH ₂ -in the alkyl group may be Replaced by -O- or -S-;

   R ₁ 'CO-, wherein R _1' represents a C ₁ -C ₁₀ alkyl, C ₃ -C ₁₀ cycloalkyl, phenyl, and optionally, a phenyl group at least one hydrogen atom may be C ₁ -C ₈ substituted by alkyl or alkoxy;

   _{R 2 '-CO-OR 3'} -, wherein R ₂ 'represents C ₁ -C ₁₀ alkyl group, a phenyl group, R _3' represents a blank, C ₁ -C ₈ alkoxy or C ₃ -C ₈ Optionally, at least one hydrogen atom in the phenyl group may be _{substituted by a C 1} -C ₈ alkyl group;

   _{R 4 '-O-CO-R} 5' -, wherein R ₄ 'represents a C ₁ -C ₁₀ alkyl, R _5' represents a C ₁ -C ₁₀ alkylene group, and optionally, R ₄ 'and -CH ₂ -in R ₅ 'can be replaced by -O-;

   C ₂ -C ₁₀ linear or branched alkenyl;

   C ₃ -C ₁₀ cycloalkyl group or C ₆ -C ₂₀ aryl group as end-capped C ₂ -C ₈ alkenyl group;

   C ₂ -C ₁₀ linear or branched alkynyl group;

   A C ₁ -C ₁₀ alkylsulfonyloxy group, optionally, the hydrogen on the alkyl group may be replaced by a fluorine atom;

   Or a C ₆ -C ₂₀ arylsulfonyloxy group;

   The premise is that R ₂ -R _{7 are} not hydrogen at the same time.
2. The sulfonimide photoacid generator according to claim 1, wherein R ₁ is a C ₁ -C ₆ linear or branched perfluoroalkyl, perfluorophenyl, at least one The hydrogen atom is substituted by a C ₁ -C ₆ alkyl group or a fluoroalkyl group or a camphor group. Preferably, the R ₁ is perfluoromethyl, perfluoroethyl, perfluoropropyl, Perfluorobutyl, perfluoropentyl, perfluorophenyl, camphor, p-methylphenyl or perfluoromethylphenyl.
3. The sulfonimide photoacid generator according to claim 1 or 2, wherein R ₂ , R ₄ -R ₇ are hydrogen, and R _{3 is} selected from the following groups:

   halogen;

   C ₁ -C ₁₀ linear or branched alkyl or haloalkyl, optionally, -CH ₂ -may be substituted by -O-;

   In the phenyl group, optionally, at least one of its hydrogen atoms may be substituted by a C ₁ -C ₄ alkyl group or an alkoxy group;

   A C ₇ -C ₁₀ phenyl alkyl group, optionally, at least one hydrogen atom on the phenyl group may be substituted by a C ₁ -C ₄ alkyl group or alkoxy group, and -CH ₂ -in the alkyl group may be Replaced by -O- or -S-;

   R ₁ 'CO-, wherein R _1' represents a C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, phenyl, and optionally, a phenyl group at least one hydrogen atom may be C ₁ -C ₄ substituted by alkyl or alkoxy;

   _{R 2 '-CO-OR 3'} -, wherein R ₂ 'represents C ₁ -C ₈ alkyl group, a phenyl group, R _3' represents a blank, C ₁ -C ₄ alkoxy or C ₃ -C ₄ Optionally, at least one hydrogen atom in the phenyl group may be _{substituted by a C 1} -C ₄ alkyl group;

   _{R 4 '-O-CO-R} 5' -, wherein R ₄ 'represents a C ₁ -C ₆ alkyl group, R _5' represents a C ₁ -C ₆ alkyl is alkylene, and optionally, R ₄ 'and -CH ₂ -in R ₅ 'can be replaced by -O-;

   C ₂ -C ₆ linear or branched alkenyl;

   A C ₃ -C ₆ cycloalkyl group or a C ₆ -C ₁₀ aryl group as a capped C ₂ -C ₄ alkenyl group;

   C ₂ -C ₆ linear or branched alkynyl group;

   A C ₁ -C ₆ alkylsulfonyloxy group, optionally, the hydrogen on the alkyl group may be replaced by a fluorine atom;

   Or a C ₆ -C ₁₀ arylsulfonyloxy group.
4. The sulfonimide photoacid generator according to any one of claims 1 to 3, wherein one of R ₂ -R _{7 is} selected from the group consisting of methyl, ethyl, propyl, butyl, Any one of the pentyl groups, and the rest are H;

   Or said R ₂ , R ₄ -R ₇ are hydrogen, and said R _{3 is} selected from any one of the following groups: halogen, halomethyl, and haloethyl;

   Or the R ₂ , R ₄ -R ₇ are hydrogen, and the R _{3 is} selected from any one of the following groups: methyl, ethyl, propyl, butyl, pentyl, and one of- CH ₂ -is replaced by -O-;

   Or said R ₂ , R ₄ -R ₇ are hydrogen, and said R _{3 is} selected from any one of the following groups: C ₇ -C ₁₀ phenylalkyl group, optionally, one hydrogen on the phenyl group Atoms may be substituted by methyl groups, and/or one -CH ₂ -in the alkyl group may be substituted by -O- or -S-;

   Or said R _2, R ₄ -R ₇ are hydrogen, R ₃ is selected from any one of the following groups A: R ₁ '-CO-, wherein R _1' represents methyl, ethyl, propyl, Cyclohexyl, phenyl, methylphenyl, ethylphenyl, tert-butylphenyl, alkoxymethylphenyl or alkoxyethylphenyl;

   Or said R _2, R ₄ -R ₇ is any one of hydrogen, R ₃ is selected from the group consisting _{of: R 2 '-CO-OR 3} ' -, wherein R ₂ 'represents methyl, ethyl, , a propyl group or a phenyl group, a hydrogen atom in the phenyl group may be substituted with methyl group, R ₃ 'represents a blank or a propynyl group;

   Or said R _2, R ₄ -R ₇ are hydrogen, R ₃ is selected from any one of the following _{radicals: R 4 '-O-CO-} R 5' -, wherein R ₄ 'represents a methyl group, Ethyl, propyl, butyl, pentyl or hexyl, R ₅ 'represents methylene or ethylene, and one of R ₄ ' and R ₅ '-CH ₂ -may be substituted by -O-;

   Or said R ₂ , R ₄ -R ₇ are hydrogen, and said R _{3 is} selected from any one of the following groups: linear butenyl, branched butenyl, phenyl-terminated propenyl or cyclohexyl Blocked propylene group;

   Or said R ₂ , R ₄ -R ₇ are hydrogen, and said R _{3 is} selected from any one of the following groups: ethynyl, propynyl, butynyl or pentynyl;

   Or the R ₂ and R ₄ -R ₇ are hydrogen, and the R _{3 is} selected from any one of the following groups: C ₁ -C ₆ methylsulfonyloxy, trifluoromethylsulfonyloxy , Butylsulfonyloxy, phenylsulfonyloxy or p-methylphenylsulfonyloxy.
5. The sulfonimide photoacid generator according to claim 1, wherein the sulfonimide photoacid generator is selected from any one of the following structural formulas:

   

   

   

   

   
6. The preparation method of the sulfonimide photoacid generator according to any one of claims 1 to 5, comprising the following steps:

   (1) The coupling reaction between 4-bromo-1,8 naphthalenedicarboxylic acid anhydride and indole derivatives produces intermediate 1, the reaction formula is as follows:

   

   (2) Intermediate 1 undergoes a hydroxylamination reaction with hydroxylamine hydrochloride to produce Intermediate 2. The reaction formula is as follows:

   

   (3) Intermediate 2 reacts with sulfonic anhydride (R ₁ -SO ₂ ) ₂ O or sulfonyl chloride R ₁ -SO ₂ -Cl to produce compound A, the reaction formula is as follows:

   
7. An acid generation method, characterized in that the sulfonimide photoacid generator according to any one of claims 1 to 5 is irradiated with active energy rays.
8. The acid generation method according to claim 7, wherein the active energy rays are active energy rays with a wavelength between 300-450 nm in the near ultraviolet and visible light regions, preferably the active energy rays have a wavelength of 365 nm (I line) and 405nm (H line) active energy rays.
9. A photosensitive resin composition comprising a resin component and an acid generator, characterized in that the acid generator is the sulfonimide photoacid generator according to any one of claims 1 to 5
10. The photosensitive resin composition according to claim 9, wherein the resin component has an acid labile group protected by a protecting group; the acid labile group includes at least one of a carboxyl group and a phenolic hydroxyl group. One; and the content of the acid-labile group accounts for 1 to 80% of the resin component content, preferably 3 to 70%.
11. The photosensitive resin composition according to claim 10, wherein the protective group includes at least one of the following groups:

    

    Wherein R ₈ , R ₉ , and R ₁₀ each independently represent any one of a C ₁ -C ₆ alkyl group or a C ₁ -C ₁₀ fluorinated alkyl group, wherein the alkyl group is a straight chain alkyl group or a branched alkyl group. Alkyl group, and _{any two of R 8} , R ₉ , and R ₁₀ are suitable for bonding to each other to form a ring; R ₁₁ , R ₁₂ and R ₁₃ each independently represent a C ₁ -C ₂₀ hydrocarbon group, and R ₁₁ , R ₁₂ , _{Any two of R 13} are suitable for bonding to each other to form a ring; R ₁₄ represents a C ₁ -C ₆ straight chain alkyl group, a C ₁ -C ₆ branched chain alkyl group, a C ₁ -C ₆ cyclic alkyl group Base, and n is 0 or 1.
12. The photosensitive resin composition according to claim 10, wherein the weight content of the acid generator is 0.5 to 5%, preferably 1 to 3, relative to the mass of the solid content of the photosensitive resin composition %, preferably the resin component is selected from any one of (meth)acrylic resin, polyhydroxystyrene resin and phenolic resin polymer.
13. The photosensitive resin composition according to claim 9, wherein the resin composition further comprises an aromatic carboxylic acid compound, preferably relative to the mass of the solid content of the photosensitive resin composition, the aromatic carboxylic acid compound The weight content of the acid compound is 3 to 35%.
14. The photosensitive resin composition according to claim 9, wherein the resin composition further comprises a cross-linking compound, preferably relative to the mass of the solid content of the photosensitive resin composition, the cross-linking compound The weight content is 10-50%.
15. The photosensitive resin composition according to claim 9, wherein the photosensitive resin composition further includes a solvent.
16. A patterning method, comprising mixing, forming a film and patterning a photosensitive resin composition, wherein the photosensitive resin composition is the photosensitive resin according to any one of claims 9 to 15 combination.
17. An application of the photosensitive resin composition according to any one of claims 9 to 15, the application comprising applying the photosensitive composition to protective films, interlayer insulating materials, and pattern transfer materials of electronic components In preparation.
18. The sulfonimide photoacid generator according to any one of claims 1 to 5 or the photosensitive resin composition according to any one of claims 9 to 15 is used in the preparation of coatings, coating agents, inks, sprays Application in ink, resist film, liquid resist, negative resist, positive resist, MEMS resist, negative photosensitive material, stereolithography and micro stereolithography materials.