Oxime sulfonate photoacid generator, resist composition, patterning method and application

Abstract

The invention provides an oxime sulfonate photoacid generator. The oxime sulfonate photoacid generator has the following general formula (I). The sulfonate group is directly connected with an imine structure, and the structure has a photosensitive cracking characteristic and can generate N-O bond rupture under the irradiation of active energy rays to generate different types of sulfonic acids. The active energy ray is an active energy ray having a wavelength of 300-450 nm in a near ultraviolet light region and a visible light region, particularly an active energy ray having a wavelength of 365 nm (i-ray). Meanwhile, C = N double bonds and S atoms further exist in the structure shown in the general formula (I), and under the combined action of the S element, sulfonate groups connected with the carbon-nitrogen double bonds and the imine structure, the oxime sulfonate photoacid generator with the structure shown in the general formula (I) has high absorption and higher sensitivity and solubility on the active energy rays and is easy to synthesize. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to the technical field of photosensitive materials, and in particular to an oxime sulfonate photoacid generator, a resist composition, a patterning method and applications. Background Art

[0002] Photoacid generator is one of the key components of chemically amplified photoresists, and its structure and performance have a great influence on the photolithographic image. With the development of the semiconductor industry, people's demand for high-precision patterns is growing, and at the same time, higher requirements are put forward for the expansion of the applicable types of photoacid generators and the performance of photoacid generators, especially low diffusivity, high solubility, high acid production rate and other characteristics. Although sulfonic acid ester compounds of naphthalene anhydride are widely known as photoinitiators in the semiconductor field, most of the current resist formulations require the addition of additives to inhibit acid migration or enhance pattern robustness.

[0003] CN114114839 provides a photosensitive resin composition, comprising a resin component and an acid generator, wherein the acid generator is a sulfonimide photoacid generator, and the sulfonimide photoacid generator has the following structure: The above acid generator contains a sulfonate group in its molecule, which is directly connected to the imide structure. The structure has photosensitive decomposition and can be photolyzed to produce strong sulfonic acid under the irradiation of active energy rays. However, the above structure has the disadvantages of poor solubility, yellowish color (not suitable for use in colorless or white systems), and is very difficult to synthesize. Summary of the invention

[0004] The main purpose of the present invention is to provide an oxime sulfonate photoacid generator, a resist composition, a patterning method and application, so as to solve the problem that the existing sulfonate photoacid generator has unsatisfactory sensitivity and poor solubility in photoresist.

[0005] In order to achieve the above object, the present invention provides an oxime sulfonate photoacid generator, which has the following general formula (I):

[0006]

[0007] Among them, R 1 Selected from substituted or unsubstituted C1~C 25 One of a straight chain or branched alkyl, cycloalkyl or aryl group; and when R 1 When it is a straight chain or branched chain alkyl or cycloalkyl, -CH2- therein may be optionally replaced by -NH-, -O-, -S-, -CO-, -O-CO- or -COO-, and -CH3 therein may be optionally replaced by -SiMe3, -NH2, -OH or -COOH; when R 1When it is an aryl group, it is selected from substituted or unsubstituted phenyl, thienyl or furyl, and the aromatic ring is directly connected to -X-, or connected to -X- via one or more groups;

[0008] R 2 ~R 6 Each independently selected from substituted or unsubstituted C1 to C 20 One of a straight chain or branched chain alkyl, a halogen atom, and a hydrogen atom, R 2 or R 3 , R 4 , R 5 , R 6 When it is a straight chain or branched alkyl group, the -CH2- therein may be optionally replaced by -NH-, -O-, -S-, -CO-, -O-CO- or -COO-, and the -CH3 therein may be optionally replaced by -SiMe3, -NH2, -OH, -COOH; when R 2 or R 3 , R 4 , R 5 , R 6 When it is a halogen atom, it is selected from F, Cl, Br or I;

[0009] R 7 is selected from one of C1-C5 substituted or unsubstituted straight-chain or branched alkyl, cyano or halogen atoms, when R 7 When used as a straight-chain or branched alkyl group, the H atom attached to the C atom is optionally replaced by a F atom.

[0010] X is an S atom.

[0011] Furthermore, R 1 Selected from substituted or unsubstituted C1~C 10 One of the linear or branched alkyl, cycloalkyl or aryl groups, R 1 When it is a straight chain or branched alkyl or cycloalkyl group, the -CH2- therein is replaced by -NH-, -O-, -S- or -CO-, and the -CH3 therein is replaced by -SiMe3 or -OH; R 1 When used as an aryl group, it is selected from substituted or unsubstituted phenyl or thienyl, and the position of the aromatic ring is preferably directly connected to -X-;

[0012] Preferably, when R 1 When it is a straight chain or branched alkyl or cycloalkyl group, -CH2- therein is replaced by -O- or -S-, and -CH3 therein is replaced by -SiMe3 or -OH.

[0013] Furthermore, R 2 ~R 6 Each independently selected from substituted or unsubstituted C1 to C 20One of a straight chain or branched chain alkyl, a halogen atom, and a hydrogen atom, R 2 or R 3 , R 4 , R 5 , R 6 When it is a straight chain or branched alkyl group, -CH2- therein may be optionally replaced by -NH-, -O-, -S-, -CO-, -O-CO- or -COO-, -CH3 therein may be optionally replaced by -SiMe3, -NH2, -OH, -COOH, and the H atom connected to the C atom may be optionally replaced by a F atom;

[0014] Preferably, R 2 ~R 6 Each is independently preferably a substituted or unsubstituted C1-C8 straight chain or branched alkyl, a halogen atom and a hydrogen atom. 2 R 3 , R 4 , R 5 or R 6 When it is a straight chain or branched alkyl group, one or more -CH2- are replaced by -O- or -S-, and one or more -CH3 are replaced by -SiMe3 or -OH; when R 2 , R 3 , R 4 , R 5 or R 6 The halogen atom is any one selected from F, Cl, Br, and I, and a F atom is more preferable.

[0015] Furthermore, R 7 is selected from one of C1-C5 substituted or unsubstituted straight-chain or branched alkyl, cyano or halogen atoms, when R 7 When it is a straight chain or branched chain alkyl group, R 7 is selected from a C1-C5 straight-chain perfluoroalkyl group; when R 7 When it is cyano, R 7 is a -C≡N group; when R 7 When it is a halogen atom, R 7 is the F atom.

[0016] Furthermore, R 1 C1-C 10 A straight chain or branched alkyl group, X is S, R 2 ~R 6 Each is independently selected from a F atom, a hydrogen atom or a C1-C5 straight or branched alkyl group, R 7 is cyano; or R 1 C1-C 10 A straight chain or branched alkyl group, X is S, R 2 ~R 6are each independently selected from a F atom or a hydrogen atom, R 7 is a F atom or a C1-C 10 unsubstituted or substituted by F atom straight chain or branched alkyl; or R 1 C1-C 10 A straight chain or branched alkyl group, X is S, R 2 ~R 6 are each independently selected from a F atom or R'Si(Me)3, and R' is selected from a C1-C5 straight or branched alkyl group, R 7 is cyano; or

[0017] R 1 C1-C 10 A straight chain or branched alkyl group, X is S, R 2 ~R 6 are each independently selected from a F atom or OR', and R' is selected from a C1-C5 straight chain or branched alkyl group, R 7 is cyano; or

[0018] R 1 is R'Si(Me)3, and R' is selected from a C1-C5 straight chain or branched alkyl group, X is S, R 2 ~R 6 are each independently selected from a F atom or a hydrogen atom, R 7 is cyano; or

[0019] R 1 is HOR', and R' is selected from a C1-C5 straight chain or branched alkyl group, X is S, R 2 ~R 6 are each independently selected from a F atom or a hydrogen atom, R 7 It is cyano.

[0020] Furthermore, the oxime sulfonate photoacid generator is selected from one or more of the following compounds:

[0021]

[0022]

[0023] The second aspect of the present application also provides a resist composition, comprising a resin component and an acid generator, wherein the acid generator is the above-mentioned oxime sulfonate photoacid generator.

[0024] Further, the resin component has an acid-labile group protected by a protecting group, and the acid-labile group is selected from at least one of a carboxyl group, a phenolic hydroxyl group or a sulfonic acid group;

[0025] Preferably, the content of the acid-labile groups accounts for 1 to 80 wt % of the resin component, preferably 3 to 70 wt %;

[0026] Preferably, the protecting group comprises at least one of the groups represented by formula (a) and formula (b):

[0027]

[0028] Among them, in formula (a), R 8 Selected from substituted or unsubstituted C1~C 20 Straight chain alkyl, substituted or unsubstituted C3~C 20 Branched alkyl, substituted or unsubstituted C3~C 20 One or more of the cycloalkyl groups,

[0029] Preferred R 8 Selected from substituted or unsubstituted C1~C 10 Straight chain alkyl, substituted or unsubstituted C3~C 10 Branched alkyl, substituted or unsubstituted C3~C 10 Any one or more of the cycloalkyl groups of

[0030] Further preferred R 8 Any one or more selected from substituted or unsubstituted C1-C6 straight-chain alkyl, substituted or unsubstituted C3-C6 branched-chain alkyl, substituted or unsubstituted C3-C6 cycloalkyl, preferably R 8 When there is a substituent, the substituent is selected from any one or more of halogen, hydroxyl, cyano, C1-C4 straight-chain alkyl, C3-C5 branched alkyl, preferably any one or more of fluorine atom, methyl, ethyl, preferably R 8 One or more C atoms in may be substituted by any heteroatom of O, S, N or Si; further, preferably R 8 is selected from methoxy, ethoxy, n-propoxy, n-butoxy, tert-butoxy, benzyloxy, 1-methoxyethoxy, 1-ethoxyethoxy or One or more of

[0031] In formula (b), R 9 Selected from substituted or unsubstituted C1~C 20 Straight chain alkyl, substituted or unsubstituted C3~C 20 Branched alkyl, substituted or unsubstituted C3~C 20 Any one or more of the cycloalkyl groups of 9 Selected from substituted or unsubstituted C1~C 10 Straight chain alkyl, substituted or unsubstituted C3~C 10 Branched alkyl, substituted or unsubstituted C3~C 10 Any one or more of the cycloalkyl groups of 9Any one or more selected from substituted or unsubstituted C1-C6 straight-chain alkyl, substituted or unsubstituted C3-C6 branched-chain alkyl, substituted or unsubstituted C3-C6 cycloalkyl; further, preferably R 9 Any one or more selected from tert-butoxycarbonyl, propoxycarbonyl, adamantyloxycarbonyl and tert-butoxycarbonylmethyl.

[0032] Furthermore, the weight content of the acid generator is 0.01 to 5%, preferably 0.1 to 3%, relative to the weight of the solid content of the resist composition. Preferably, the resist composition further includes a solvent.

[0033] The third aspect of the present application also provides a patterning method, comprising mixing, film forming and patterning a resist composition, wherein the resist composition is the above-mentioned resist composition.

[0034] The fourth aspect of the present application also provides an application of the above-mentioned resist composition, which includes applying the resist composition to the preparation of a protective film, an interlayer insulating material or a pattern transfer material of an electronic component.

[0035] By applying the technical solution of the present invention, the oxime sulfonate photoacid generator of the general formula I in the present application contains a sulfonate group in the molecule, and the sulfonate group is directly connected to the imine structure. The structure has a photosensitive decomposition property, and can break the NO bond under the irradiation of active energy rays to produce different types of sulfonic acids. The above-mentioned active energy rays are active energy rays with a wavelength between 300 and 450nm in the near-ultraviolet light region and the visible light region, especially active energy rays with a wavelength of 365nm (i line). At the same time, there are C=N double bonds and S atoms in the structure shown in the general formula (I). Under the joint action of the S element and the carbon-nitrogen double bond and the connected sulfonate group and the imine structure, the oxime sulfonate photoacid generator having the structure shown in the general formula (I) has strong absorption and higher sensitivity and solubility to the above-mentioned active energy rays, and is easy to synthesize. When the resist composition including the oxime sulfonate photoacid generator and the resin component is used to dissolve the exposed photosensitive composition in an alkaline developer, due to the improvement of the photosensitivity of the oxime sulfonate photoacid generator, a pattern with excellent sensitivity and good contrast can be formed, and even a fine pattern can have sufficiently high resolution and sensitivity. At the same time, the oxime sulfonate photoacid generator of the present invention is improved in ultraviolet absorption intensity, sensitivity, solubility and acidity at 365nm compared with the traditional oxime sulfonate photoacid based on p-methoxyphenylacetonitrile. DETAILED DESCRIPTION

[0036] It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application can be combined with each other. The present invention will be described in detail below in conjunction with the embodiments.

[0037] As described in the background art, existing sulfonate photoacid generators have problems of unsatisfactory sensitivity and poor solubility in photoresists. In order to solve the above technical problems, the present application provides an oxime sulfonate photoacid generator, which has the following general formula (I):

[0038]

[0039] Among them, R 1 Selected from substituted or unsubstituted C1~C 25 One of a straight chain or branched alkyl, cycloalkyl or aryl group; and when R 1 When it is a straight chain or branched chain alkyl or cycloalkyl, -CH2- therein may be optionally replaced by -NH-, -O-, -S-, -CO-, -O-CO- or -COO-, and -CH3 therein may be optionally replaced by -SiMe3, -NH2, -OH or -COOH; when R 1 When it is an aryl group, it is selected from substituted or unsubstituted phenyl, thienyl or furyl, and the aromatic ring is directly connected to -X-, or connected to -X- via one or more groups;

[0040] R 2 ~R 6 Each independently selected from substituted or unsubstituted C1 to C 20 A straight chain or branched chain alkyl group, a halogen atom, R 2 or R 3 , R 4 , R 5 , R 6 When it is a straight chain or branched alkyl group, the -CH2- therein may be optionally replaced by -NH-, -O-, -S-, -CO-, -O-CO- or -COO-, and the -CH3 therein may be optionally replaced by -SiMe3, -NH2, -OH, -COOH; when R 2 or R 3 , R 4 , R 5 , R 6 When it is a halogen atom, it is selected from F, Cl, Br or I;

[0041] R 7 is selected from one of C1-C5 substituted or unsubstituted straight-chain or branched alkyl, cyano or halogen atoms, when R 7 When it is a straight chain or branched alkyl group, the H atom connected to the C atom is optionally replaced by a F atom; and X is a S atom.

[0042] The oxime sulfonate photoacid generator of the general formula I in the present application contains a sulfonate group in the molecule, and the sulfonate group is directly connected to the imine structure. The structure has a photosensitive decomposition property, and the NO bond can be broken under the irradiation of active energy rays to produce different types of sulfonic acids. The above-mentioned active energy rays are active energy rays with a wavelength between 300 and 450nm in the near-ultraviolet light region and the visible light region, especially active energy rays with a wavelength of 365nm (i line). At the same time, there are C=N double bonds and S atoms in the structure shown in the general formula (I). Under the joint action of the S element and the sulfonate group connected to the carbon-nitrogen double bond and the imine structure, the oxime sulfonate photoacid generator having the structure shown in the general formula (I) has strong absorption and higher sensitivity and solubility to the above-mentioned active energy rays, and is easy to synthesize. When the resist composition including the oxime sulfonate photoacid generator and the resin component is used to dissolve the exposed photosensitive composition in an alkaline developer, due to the improvement of the photosensitivity of the oxime sulfonate photoacid generator, a pattern with excellent sensitivity and good contrast can be formed, and even a fine pattern can have sufficiently high resolution and sensitivity. At the same time, the oxime sulfonate photoacid generator of the present invention is improved in ultraviolet absorption intensity, sensitivity, solubility and acidity at 365nm compared with the traditional oxime sulfonate photoacid based on p-methoxyphenylacetonitrile.

[0043] In order to reduce the difficulty of synthesis, preferably, R 1 Selected from substituted or unsubstituted C1~C 10 One of the linear or branched alkyl, cycloalkyl or aryl groups, R 1 When it is a straight chain or branched alkyl or cycloalkyl group, -CH2- is replaced by -NH-, -O-, -S- or -CO-, and -CH3 is replaced by -SiMe3 or -OH; R 1 When it is an aryl group, it is selected from substituted or unsubstituted phenyl or thienyl, and preferably the position of the aromatic ring is directly connected to -X-; more preferably, when R 1 When it is a straight chain or branched alkyl or cycloalkyl group, -CH2- therein is replaced by -O- or -S-, and -CH3 therein is replaced by -SiMe3 or -OH. Furthermore, R 1 Preferred is methyl, isopropyl, n-butyl, tert-butyl, propanol, trimethylsilylpropyl or 4-butylphenyl.

[0044] In order to further improve the sensitivity and solubility of the oxime sulfonate photoacid generator, preferably, R 2 ~R 6 Each independently selected from substituted or unsubstituted C1 to C 20 A straight chain or branched chain alkyl group, a halogen atom, R 2 or R 3 , R 4 , R 5, R 6 When it is a straight chain or branched alkyl group, -CH2- therein may be optionally replaced by -NH-, -O-, -S-, -CO-, -O-CO- or -COO-, -CH3 therein may be optionally replaced by -SiMe3, -NH2, -OH, -COOH, and the H atom connected to the C atom may be optionally replaced by a F atom. More preferably, R 2 ~R 6 Each is independently preferably a substituted or unsubstituted C1-C8 straight chain or branched alkyl, a halogen atom and a hydrogen atom. 2 R 3 , R 4 , R 5 or R 6 When it is a straight chain or branched alkyl group, one or more -CH2- are replaced by -O- or -S-, and one or more -CH3 are replaced by -SiMe3 or -OH; when R 2 , R 3 , R 4 , R 5 or R 6 When the halogen atom is selected from any one of F, Cl, Br, and I, the F atom is preferred. More preferably, R 2 ~R 6 Each independently is a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, a butyl group, a butoxy group, a trimethylsilylpropyl group, a propanol group or a tert-butyl group. In order to further improve the comprehensive performance of Qi, it is further preferred that R 2 ~R 6 At least one of them is a fluorine atom.

[0045] In order to further improve the comprehensive performance of the oxime sulfonate photoacid generator, the combination of the groups in the general formula (I) can be optimized.

[0046] In a preferred embodiment, R 7 is selected from one of C1-C5 substituted or unsubstituted straight-chain or branched alkyl, cyano or halogen atoms, when R 7 When it is a straight chain or branched chain alkyl group, R 7 is selected from a C1-C5 straight-chain perfluoroalkyl group; when R 7 When it is cyano, R 7 is a -C≡N group; when R 7 When it is a halogen atom, R 7 is the F atom.

[0047] In a preferred embodiment, R 1 C1-C 10 A straight chain or branched alkyl group, X is S, R 2 ~R 6Each is independently selected from a F atom, a hydrogen atom or a C1-C5 straight or branched alkyl group, R 7 It is cyano.

[0048] In a preferred embodiment, R 1 C1-C 10 A straight chain or branched alkyl group, X is S, R 2 ~R 6 are each independently selected from a F atom or a hydrogen atom, R 7 is a F atom or a C1-C 10 unsubstituted or substituted by F atom straight chain or branched alkyl.

[0049] In a preferred embodiment, R 1 C1-C 10 A straight chain or branched alkyl group, X is S, R 2 ~R 6 are each independently selected from a F atom or R'Si(Me)3, and R' is selected from a C1-C5 straight or branched alkyl group, R 7 It is cyano.

[0050] In a preferred embodiment, R 1 C1-C 10 A straight chain or branched alkyl group, X is S, R 2 ~R 6 are each independently selected from a F atom or OR', and R' is selected from a C1-C5 straight chain or branched alkyl group, R 7 It is cyano.

[0051] In a preferred embodiment, R 1 is R'Si(Me)3, and R' is selected from a C1-C5 straight chain or branched alkyl group, X is S, R 2 ~R 6 are each independently selected from a F atom or a hydrogen atom, R 7 It is cyano.

[0052] In a preferred embodiment, R 1 is HOR', and R' is selected from a C1-C5 straight chain or branched alkyl group, X is S, R 2 ~R 6 are each independently selected from a F atom or a hydrogen atom, R 7 It is cyano.

[0053] More preferably, the oxime sulfonate photoacid generator is selected from one or more of the following compounds:

[0054]

[0055]

[0056] In another typical embodiment of the present application, a method for preparing the aforementioned oxime sulfonate photoacid generator is provided, the preparation method comprising: step S1, reacting compound 1 with isoamyl nitrite to generate compound 2; step S2, esterifying compound 2 with compound 3 to generate a target product; the structural formulas of compound 1, compound 2 and compound 3 are as follows:

[0057]

[0058]

[0059] Among them, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , -X- has the same definition as above.

[0060] In the above step S1, compound 1 can be subjected to an oximation reaction with isoamyl nitrite to obtain an oximide (compound 2), wherein compound 1 can be purchased, or prepared from alcohols, thiols and aromatic halogenated hydrocarbons, or prepared from cyanide and aromatic halogenated hydrocarbons; wherein isoamyl nitrite can be purchased; in step S2, compound 2 is subjected to an esterification reaction with compound 3 under alkaline conditions to finally obtain the target product, and the oximation reaction temperature is preferably controlled between 25 and 100° C., and more preferably between 25 and 50° C., which is more conducive to improving the efficiency of the hydroxylation reaction;

[0061] In the above step S2, the oxime product and the acylating agent undergo esterification reaction in an inert solvent under alkaline conditions to generate oxime sulfonate compounds. The temperature of the esterification reaction is preferably controlled between -10 and 60°C, and more preferably between 0 and 25°C, so as to be more conducive to improving the efficiency of the esterification reaction.

[0062] In addition, the raw materials and reagents used in the above preparation method are all known compounds in the prior art, which can be obtained commercially or easily prepared by known processes, and will not be described in detail here.

[0063] The oxime sulfonate photoacid generator of the present invention can be used for any known use of photoacid generators, such as resist films, liquid resists, negative resists, positive resists, resists for MEMS, materials for stereolithography and microstereolithography, etc. Among them, as a photoacid generator in a resist composition, it can be used together with a resin having an acid dissociable group to prepare a resist for semiconductor lithography.

[0064] In another typical embodiment of the present application, a resist composition is provided, comprising a resin component and an acid generator, wherein the acid generator is an oxime sulfonate photoacid generator provided in the present application.

[0065] The resist composition of the present invention can be divided into a positive composition and a negative composition according to the application. In addition to the oxime sulfonate photoacid generator, the positive composition generally contains a resin component (B1) that increases the solubility in the alkaline developer through the action of an acid. During the composition pattern formation process, after selective exposure, the acid-labile group protected by the protecting group in the positive resin in the exposed area will be deprotected under the action of the acid generated by the photoacid generator, making it soluble in the alkaline developer. Therefore, when the alkaline development operation is performed, the pattern of the unexposed area remains to form a positive pattern. Unlike the positive composition, the negative composition uses a resin-crosslinking agent component (B2) that is cross-linked under the action of an acid and is insoluble in an organic developer. Under the catalysis of the acid generated by the photoacid generator, the resin and the cross-linker react in the exposed area to form a polymer insoluble in the organic developer and remain, while the unexposed area is dissolved and removed by the organic developer, finally forming a negative pattern. Among them, the specific resin component (B1) and the resin-cross-linker component (B2) can refer to the specific contents disclosed in paragraphs

[0046] to

[0076] of the specification of the Chinese patent application with application number 202011299973.1, which will not be repeated here.

[0066] In the positive / negative resist composition of the present invention, the oxime sulfonate photoacid generator can generate sulfonic acid by breaking the NO bond under the irradiation of active energy rays, and the difference in solubility of the developer between the exposed area and the unexposed area is achieved through the PEB process. The oxime sulfonate photoacid generator product can be used alone or in combination of two or more.

[0067] Thanks to the performance of the oxime sulfonate photoacid generator having the general formula I in the present application, when the resist composition including the oxime sulfonate photoacid generator and the resin component is used to dissolve the exposed photosensitive composition in an alkaline developer, even if a fine pattern is formed, it can have sufficiently high resolution and sensitivity. At the same time, due to the improvement in sensitivity, the amount of photoinitiator in the resist can be reduced.

[0068] In a preferred embodiment, the resin component has an acid-labile group protected by a protecting group, and the acid-labile group is selected from at least one of a carboxyl group, a phenolic hydroxyl group or a sulfonic acid group; preferably, the content of the acid-labile group accounts for 1 to 80 wt %, preferably 3 to 70 wt % of the content of the resin component; preferably, the protecting group includes at least one of the groups represented by formula (a) and formula (b):

[0069]

[0070] Among them, in formula (a), R8 Selected from substituted or unsubstituted C1~C 20 Straight chain alkyl, substituted or unsubstituted C3~C 20 Branched alkyl, substituted or unsubstituted C3~C 20 One or more of the cycloalkyl groups,

[0071] Preferred R 8 Selected from substituted or unsubstituted C1~C 10 Straight chain alkyl, substituted or unsubstituted C3~C 10 Branched alkyl, substituted or unsubstituted C3~C 10 Any one or more of the cycloalkyl groups of

[0072] Further preferred R 8 Any one or more selected from substituted or unsubstituted C1-C6 straight-chain alkyl, substituted or unsubstituted C3-C6 branched-chain alkyl, substituted or unsubstituted C3-C6 cycloalkyl, preferably R 8 When there is a substituent, the substituent is selected from any one or more of halogen, hydroxyl, cyano, C1-C4 straight-chain alkyl, C3-C5 branched alkyl, preferably any one or more of fluorine atom, methyl, ethyl, preferably R 8 One or more C atoms in may be substituted by any heteroatom of O, S, N or Si; further, preferably R 8 is selected from methoxy, ethoxy, n-propoxy, n-butoxy, tert-butoxy, benzyloxy, 1-methoxyethoxy, 1-ethoxyethoxy or One or more of

[0073] In formula (b), R 9 Selected from substituted or unsubstituted C1~C 20 Straight chain alkyl, substituted or unsubstituted C3~C 20 Branched alkyl, substituted or unsubstituted C3~C 20 Any one or more of the cycloalkyl groups of 9 Selected from substituted or unsubstituted C1~C 10 Straight chain alkyl, substituted or unsubstituted C3~C 10 Branched alkyl, substituted or unsubstituted C3~C 10 Any one or more of the cycloalkyl groups of 9 Any one or more selected from substituted or unsubstituted C1-C6 straight-chain alkyl, substituted or unsubstituted C3-C6 branched-chain alkyl, substituted or unsubstituted C3-C6 cycloalkyl; further, preferably R 9Any one or more selected from tert-butoxycarbonyl, propoxycarbonyl, adamantyloxycarbonyl, tert-butoxycarbonylmethyl. The above-mentioned resin components are preferred to facilitate the synergistic effect with the oxime sulfonate photoacid generator to obtain a good photolithography pattern.

[0074] The amount of the acid generator can refer to the amount of conventional acid generators in the prior art. The weight content of the acid generator is 0.01-5%, preferably 0.1-3%, relative to the weight of the solid component of the resist composition, so as to exert good sensitivity and improve the development effect. Preferably, the resist composition also includes a solvent.

[0075] The solvent is used to dissolve the various components in the anti-etching composition to form a uniform solution, which is used to adjust its viscosity and coating properties to facilitate film formation. The specific solvent can refer to the Chinese patent application with application number 202011299973.1. Optionally, the anti-etching composition may also include conventional additives in this field, which will not be repeated here.

[0076] The fourth aspect of the present application also provides a patterning method, including mixing, film forming and patterning the resist composition, wherein the resist composition is the resist composition provided in the present application.

[0077] When applying the resist composition of the present invention, first, a resin solution dissolved or dispersed in an organic solvent can be applied to a substrate using a method such as spin coating, and then heated to volatilize the solvent to form a resist film on the substrate, and then light irradiation (i.e., exposure) in the shape of a wiring pattern is performed, followed by post-exposure heat treatment (PEB) and alkaline development to form a wiring pattern.

[0078] Drying conditions of the applied resin solution vary depending on the solvent used, but are preferably carried out at 50 to 150° C. for 1 to 30 minutes, and are appropriately determined by the amount of residual solvent (mass percentage) after drying and the like.

[0079] After forming the resist film on the substrate, the wiring pattern shape is irradiated with light. Light irradiation can use a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a metal halide lamp, an electron beam irradiation device, an X-ray irradiation device, a laser (such as an argon laser, a dye laser, a nitrogen laser, an LED, a helium cadmium laser), etc., preferably a high-pressure mercury lamp and an LED lamp.

[0080] The temperature of the post-exposure heat treatment (PEB) is usually 40 to 200°C, preferably 60 to 150°C. If the temperature is lower than 40°C, the deprotection reaction or cross-linking reaction cannot be fully carried out, so the difference in solubility between the exposed part and the unexposed part is insufficient and a pattern cannot be formed; if the temperature is higher than 200°C, there is a problem of reduced productivity. The above-mentioned heating time is usually 0.5 to 30 minutes.

[0081] The alkaline developer is used for development, and the alkaline development method includes using an alkaline developer. The alkaline developer can be selected from 0.1-10% (mass percentage) of tetramethylammonium hydroxide, sodium hydroxide, potassium hydroxide, and sodium bicarbonate aqueous solutions. The alkaline developer can also contain water-soluble organic solvents, such as methanol, ethanol, isopropanol, tetrahydrofuran, N-methylpyrrolidone, etc. The developing method can be selected from immersion method, spray method and spray method, preferably spray method. The temperature of the developer is preferably used at 25-40°C, and the developing time is appropriately determined according to the thickness of the resist film, and finally a pattern corresponding to the mask is obtained.

[0082] The fifth aspect of the present application also provides an application of the above-mentioned resist composition, including applying the resist composition to the preparation of a protective film, an interlayer insulating material or a pattern transfer material of an electronic component.

[0083] The above applications can specifically include forming the resist composition into an interlayer insulating film for use in TFT and panels of liquid crystal display devices; it can also be used as a protective film for color filters and spacers, and as a PS photoresist or BCS photoresist for pattern transfer.

[0084] The present application is further described in detail below in conjunction with specific embodiments. These embodiments should not be construed as limiting the scope of protection claimed in the present application.

[0085] Preparation Example of Oxime Sulfonate Photoacid Generator

[0086] Example 1

[0087]

[0088] At room temperature, 600g toluene and 60g methanol were added to a four-necked flask, stirring was started, 200g p-methylthiophenylacetonitrile (S1) and 120g NaOH were added to the reactor at 25°C, the temperature was raised to 40°C, 172g of isoamyl nitrite was added dropwise, the temperature was controlled not to be higher than 45°C during the addition, and the reaction was maintained at 40°C for 3 hours after the addition was completed. The reaction system was cooled to room temperature, and the filter cake was rinsed twice with toluene. The obtained solid was added to 2L water to dissolve, the ice bath was cooled to 5°C, hydrochloric acid was added to adjust the pH to 4-5, the precipitated solid was filtered and collected, the filter cake was washed twice with pure water, and 183g of off-white to light yellow solid (T1) was obtained after drying.

[0089] At room temperature, add 1L of dichloromethane to a four-necked flask, start stirring, add 183g of oxime (T1) and 184.7g of p-toluenesulfonyl chloride to the reactor, stir evenly, cool to about 5°C in an ice bath, add 136g of triethylamine dropwise, control the temperature not to exceed 10°C during the addition, slowly warm up to 25°C after the addition is complete, and react for 2 hours. Add 1L of pure water, separate the liquids, first wash the organic phase with sodium carbonate aqueous solution once, and then wash it with water once. Wash the organic phase with 1N hydrochloric acid until it is acidic, then wash it with water three times, and collect the organic phase. Concentrate the organic phase until solid precipitates, add 500mL of methanol for crystallization, filter, wash the filter cake twice with methanol, and dry to obtain 285g of off-white to light yellow solid (1).

[0090] Referring to the reaction steps similar to those in Example 1, the substrates in Examples 2 to 24 were replaced and the reaction conditions were appropriately adjusted to obtain other corresponding oxime sulfonate photoacid generators 2, 3, 4, 5, 6, 7, 11, 12, 10, 13, 15, 19, 20, 18, 22, 24, 21, 26, 27, 31, 32, 33, and 34.

[0091] The serial numbers and 1H NMR characterization results of the oxime sulfonate photoacid generators prepared in all the examples are listed in Table 1.

[0092] Table 1

[0093]

[0094]

[0095]

[0096] Performance Evaluation

[0097] The performance of the sulfonate photoacid generators synthesized in Examples 1 to 24 and the oxime sulfonate photoacid generator of Comparative Example 1 was evaluated, respectively, and the evaluation indicators included molar absorption coefficient, solubility and chemical stability.

[0098] (1) Molar absorptivity

[0099] The compound was diluted to 0.25 mmol / L with acetonitrile, and the absorbance of the cuvette length of 1 cm was measured in the range of 200 to 600 nm using a UV-visible spectrophotometer (UPG-752). The molar absorption coefficient ε at each wavelength was calculated by the following formula, i.e., ε (L·mol -1 cm -1 )=A / (0.00025mol / L×1cm), where A represents the absorbance at each wavelength.

[0100] (2) Solubility

[0101] High solubility not only makes it easier to purify the photoacid generator compound, but also enables the photoacid generator compound to expand its concentration range in photoresist and different solvent systems. Take 1.0000g of the photoacid generator compound product, gradually add solvent at 25°C until all the solids in each test tube are dissolved, and record the mass of the solvent used. Solubility = (1g / solvent mass) × 100%. The evaluation results are shown in Table 2.

[0102] Table 2

[0103]

[0104]

[0105] The nonionic photoacid generator of Comparative Example 1 is Denoted as A*1; the nonionic photoacid generator of Comparative Example 2 is Denoted as A*2.

[0106] The test results in Table 2 show that the photoacid generator of the present invention has a high molar absorption coefficient at 365 nm, has a strong light absorption capacity, can fully utilize light energy, can ensure a high utilization rate in resist applications, and exhibits good solubility.

[0107] Examples of Resist Compositions

[0108] Referring to the formulations of resist composition examples 1 to 31 and resist composition comparative examples 1 to 6 in Table 3, each raw material was uniformly dissolved in PGMEA (propylene glycol methyl ether acetate) to obtain a resist composition having a solid content concentration of about 20% (mass percentage). Among them, the component types and contents of the sulfonate photoacid generator (A), the resin component (B), and the sensitizer (C) are as shown in Table 3.

[0109] Composition Example 1

[0110] The resin component (B) is a B1 type resin having the formula 11 , Formula B 12 Japanese style B 13 The repeating unit composition is shown in FIG. 1 , and the value at the lower right of each repeating unit represents the content (mass percentage) of the repeating unit in the resin. The weight average molecular weight of B1 resin is about 10,000.

[0111]

[0112] The oxime sulfonate photoacid generator (A) is the oxime sulfonate photoacid generator of Example 1.

[0113] Composition Examples 2 to 24

[0114] The difference from composition example 1 is that the sulfonate photoacid generator (A) is the sulfonate photoacid generator of examples 2 to 24, respectively.

[0115] The types and contents of the remaining components are shown in Table 3.

[0116] Composition Example 25

[0117] The difference from composition example 18 is that the resin component (B) uses a B2 type resin, which is represented by formula B 21 , Formula B 22 Japanese style B 23 The numerical value at the lower right of each repeating unit indicates the content (mass %) of the repeating unit in the resin. The weight average molecular weight of B2 resin is about 10,000.

[0118]

[0119] Composition Example 26

[0120] The difference from composition example 18 is that the resin component (B) uses a B3 type resin, which is represented by formula B 31 Japanese style B 32 The numerical value at the lower right of each repeating unit indicates the content (mass %) of the repeating unit in the resin. The weight average molecular weight of B3 resin is about 10,000.

[0121]

[0122] Composition Examples 27-28

[0123] The difference from composition example 18 is that the content of the oxime sulfonate photoacid generator is different.

[0124] Composition Example 29

[0125] The difference from Composition Example 18 is that no sensitizer is added.

[0126] Composition Example 30

[0127] The difference from Composition Example 25 is that no sensitizer is added.

[0128] Composition Example 31

[0129] The difference from Composition Example 26 is that no sensitizer is added.

[0130] Composition Comparative Example 1

[0131] The difference from composition example 18 is that the oxime sulfonate photoacid generator A*1 of comparative example 1 is used.

[0132] Composition Comparative Example 2

[0133] The difference from composition example 25 is that the oxime sulfonate photoacid generator A*1 of comparative example 1 is used.

[0134] Composition Comparative Example 3

[0135] The difference from composition example 26 is that the oxime sulfonate photoacid generator A*1 of comparative example 1 is used.

[0136] Composition Comparative Example 4

[0137] The difference from the composition comparative example 1 is that no sensitizer is added.

[0138] Composition Comparative Example 5

[0139] The difference from the composition comparative example 2 is that no sensitizer is added.

[0140] Composition Comparative Example 6

[0141] The difference from the composition comparative example 3 is that no sensitizer is added.

[0142] The resist compositions prepared in Composition Examples 1 to 31 and Composition Comparative Examples 1 to 6 were evaluated for sensitivity and resolution by the following methods. The results are recorded in Table 3.

[0143] (1) Sensitivity evaluation

[0144] On each silicon wafer, the resist composition of each embodiment and comparative example was applied in a film thickness of 1 μm capable of forming a pattern to form a coating film. The formed coating film was pre-baked at 90°C for 100 seconds. After pre-baking, the coating film was exposed through a mask for forming a hole pattern with a diameter of 10 μm while gradually changing the exposure amount (exposure wavelength 365 nm), and then developed for 30 seconds at 25°C with a 2.0% tetramethylammonium hydroxide aqueous solution. The minimum exposure required to form a hole pattern with a diameter of 10 μm was determined by the above method. From the minimum exposure value obtained, the sensitivity was evaluated according to the following standard: "○" indicates a sensitivity of -50 mJ / cm 2 In the following, “×” indicates that the sensitivity is -300mJ / cm 2 above.

[0145] (2) Resolution evaluation

[0146] A mask for forming a hole pattern with a diameter of 5 μm was used, except that the irradiation rate was 100 mJ / cm 2The coating film formation, coating film exposure and development were performed in the same manner as the sensitivity evaluation, except that the exposure was performed with an exposure amount of 100%. The coating film after development was observed, and the resolution was evaluated according to the following criteria: "○" means that a pattern with a diameter of 5 μm can be formed, and "×" means that a pattern with a diameter of 5 μm cannot be formed.

[0147] Table 3

[0148]

[0149]

[0150]

[0151] From the results in Table 3, it can be seen that the resist compositions of the present invention as shown in Composition Examples 1 to 28 have very good sensitivity and resolution, which are significantly better than those of Comparative Examples 1 to 3. Composition Examples 29 to 31 show that the sensitivity is still very good without a sensitizer, but Comparative Examples 4 to 6, which also do not add a sensitizer, show average sensitivity. Comparative Examples 7 to 12 are generally yellowish in color, and the initiator solubility is low and the resolution is poor.

[0152] From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects: the oxime sulfonate photoacid generator having the general formula I in the present application contains a sulfonate group in the molecule, and the sulfonate group is directly connected to the imine structure, and the structure has a photosensitive decomposition property, and the NO bond can be broken under the irradiation of active energy rays to produce different types of sulfonic acids. The above-mentioned active energy rays are active energy rays with a wavelength between 300 and 450nm in the near-ultraviolet region and the visible light region, and in particular, have high sensitivity and strong absorption to active energy rays with a wavelength of 365nm (i line). When the resist composition including the oxime sulfonate photoacid generator and the resin component is used for dissolving the exposed photosensitive composition in an alkaline developer, due to the improvement of the photosensitivity of the oxime sulfonate photoacid generator, a pattern with excellent sensitivity and good contrast can be formed, and even a fine pattern can have a sufficiently high resolution and sensitivity. At the same time, compared with the traditional p-methoxyphenylacetonitrile-type oxime sulfonate photoacid generator, the oxime sulfonate photoacid generator of the present invention has a significant improvement in solubility and a very obvious improvement in ultraviolet absorption at 365nm, which can reduce the dependence of traditional photoresists on sensitizers when working under a 365nm light source.

[0153] It should be noted that the terms "first", "second", etc. in the specification and claims of the present application are used to distinguish similar objects, and are not necessarily used to describe a specific order or sequence. It should be understood that the terms used in this way can be interchangeable where appropriate, so that the embodiments of the present application described herein can be implemented in an order other than those described herein, for example.

[0154] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. An oxime sulfonate photoacid generator, characterized in that: The oxime sulfonate photoacid generator has the following general formula (I): Among them, R 1 Selected from substituted or unsubstituted C1~C 25 One of a straight chain or branched alkyl, cycloalkyl or aryl group; and when R 1 When it is a straight chain or branched chain alkyl or cycloalkyl, -CH2- therein may be optionally replaced by -NH-, -O-, -S-, -CO-, -O-CO- or -COO-, and -CH3 therein may be optionally replaced by -SiMe3, -NH2, -OH or -COOH; when R 1 When it is an aryl group, it is selected from substituted or unsubstituted phenyl, thienyl or furyl, and the aromatic ring is directly connected to -X-, or connected to -X- via one or more groups; R 2 ~R 6 Each independently selected from substituted or unsubstituted C1 to C 20 One of a straight chain or branched chain alkyl, a halogen atom, and a hydrogen atom, R 2 or R 3 , R 4 , R 5 , R 6 When it is a straight chain or branched alkyl group, the -CH2- therein may be optionally replaced by -NH-, -O-, -S-, -CO-, -O-CO- or -COO-, and the -CH3 therein may be optionally replaced by -SiMe3, -NH2, -OH, -COOH; when R 2 or R 3 , R 4 , R 5 , R 6 When it is a halogen atom, it is selected from F, Cl, Br or I; R 7 is selected from one of C1-C5 substituted or unsubstituted straight-chain or branched alkyl, cyano or halogen atoms, when R 7 When used as a straight-chain or branched alkyl group, the H atom attached to the C atom is optionally replaced by a F atom. X is an S atom.

2. The oxime sulfonate photoacid generator according to claim 1, characterized in that: The R 1 Selected from substituted or unsubstituted C1~C 10 One of the linear or branched alkyl, cycloalkyl or aryl groups, R 1 When it is a straight chain or branched alkyl or cycloalkyl group, -CH2- is replaced by -NH-, -O-, -S- or -CO-, and -CH3 is replaced by -SiMe3 or -OH; R 1 When used as an aryl group, it is selected from substituted or unsubstituted phenyl or thienyl, and the position of the aromatic ring is preferably directly connected to -X-; Preferably, when R 1 When it is a straight chain or branched alkyl or cycloalkyl group, -CH2- therein is replaced by -O- or -S-, and -CH3 therein is replaced by -SiMe3 or -OH.

3. The oxime sulfonate photoacid generator according to claim 2, characterized in that: The R 2 ~R 6 Each independently selected from substituted or unsubstituted C1 to C 20 One of a straight chain or branched chain alkyl, a halogen atom, and a hydrogen atom, R 2 or R 3 , R 4 , R 5 , R 6 When it is a straight chain or branched alkyl group, -CH2- therein may be optionally replaced by -NH-, -O-, -S-, -CO-, -O-CO- or -COO-, -CH3 therein may be optionally replaced by -SiMe3, -NH2, -OH, -COOH, and the H atom connected to the C atom may be optionally replaced by a F atom; Preferably, the R 2 ~R 6 Each is independently preferably a substituted or unsubstituted C1-C8 straight or branched alkyl, a halogen atom and a hydrogen atom. 2 R 3 , R 4 , R 5 or R 6 When it is a straight chain or branched alkyl group, one or more -CH2- are replaced by -O- or -S-, and one or more -CH3 are replaced by -SiMe3 or -OH; when R 2 , R 3 , R 4 , R 5 or R 6 The halogen atom is any one selected from F, Cl, Br, and I, and a F atom is more preferable.

4. The oxime sulfonate photoacid generator according to any one of claims 1 to 3, characterized in that: The R 7 is selected from one of C1-C5 substituted or unsubstituted straight-chain or branched alkyl, cyano or halogen atoms, when R 7 When it is a straight chain or branched chain alkyl group, R 7 is selected from a C1-C5 straight-chain perfluoroalkyl group; when R 7 When it is cyano, R 7 is a -C≡N group; when R 7 When it is a halogen atom, R 7 is the F atom.

5. The oxime sulfonate photoacid generator according to claim 4, characterized in that: The R 1 C1-C 10 A straight chain or branched alkyl group, wherein X is S, and R 2 ~R 6 Each independently selected from a F atom, a hydrogen atom or a C1-C5 straight or branched alkyl group, wherein R 7 is cyano; or The R 1 C1-C 10 A straight chain or branched alkyl group, wherein X is S, and R 2 ~R 6 are each independently selected from a F atom or a hydrogen atom, said R 7 is a F atom or a C1-C 10 unsubstituted or substituted by F atom straight chain or branched alkyl; or The R 1 C1-C 10 A straight chain or branched alkyl group, wherein X is S, and R 2 ~R 6 Each is independently selected from F atom or R'Si(Me)3, and the R' is selected from C1-C5 straight chain or branched alkyl, the R 7 is cyano; or The R 1 C1-C 10 A straight chain or branched alkyl group, wherein X is S, and R 2 ~R 6 are each independently selected from a F atom or OR', and the R' is selected from a C1-C5 straight or branched alkyl group, the R 7 is cyano; or The R 1 is R'Si(Me)3, and R' is selected from a C1-C5 straight chain or branched alkyl group, X is S, and R 2 ~R 6 are each independently selected from a F atom or a hydrogen atom, said R 7 is cyano; or The R 1 is HOR', and R' is selected from a C1-C5 straight chain or branched alkyl group, X is S, and R 2 ~R 6 are each independently selected from a F atom or a hydrogen atom, said R 7 It is cyano.

6. The oxime sulfonate photoacid generator according to claim 1, characterized in that: The oxime sulfonate photoacid generator is selected from one or more of the following compounds:

7. A resist composition comprising a resin component and an acid generator, characterized in that: The acid generator is the oxime sulfonate photoacid generator according to any one of claims 1 to 6.

8. The resist composition according to claim 7, characterized in that The resin component has an acid-labile group protected by a protecting group, and the acid-labile group is selected from at least one of a carboxyl group, a phenolic hydroxyl group, or a sulfonic acid group; Preferably, the content of the acid-labile groups accounts for 1 to 80 wt % of the content of the resin component, preferably 3 to 70 wt %; Preferably, the protecting group comprises at least one of the groups represented by formula (a) and formula (b): Wherein, in the formula (a), R 8 Selected from substituted or unsubstituted C1~C 20 Straight chain alkyl, substituted or unsubstituted C3~C 20 Branched alkyl, substituted or unsubstituted C3~C 20 One or more of the cycloalkyl groups of Preferably, the R 8 Selected from substituted or unsubstituted C1~C 10 Straight chain alkyl, substituted or unsubstituted C3~C 10 Branched alkyl, substituted or unsubstituted C3~C 10 Any one or more of the cycloalkyl groups of It is further preferred that the R 8 Any one or more selected from substituted or unsubstituted C1-C6 straight-chain alkyl, substituted or unsubstituted C3-C6 branched-chain alkyl, substituted or unsubstituted C3-C6 cycloalkyl, preferably R 8 When there is a substituent, the substituent is selected from any one or more of halogen, hydroxyl, cyano, C1-C4 straight-chain alkyl, C3-C5 branched alkyl, preferably the substituent is selected from any one or more of fluorine atom, methyl, ethyl, preferably R 8 One or more C atoms in may be substituted by any heteroatom of O, S, N or Si; further, preferably, R 8 is selected from methoxy, ethoxy, n-propoxy, n-butoxy, tert-butoxy, benzyloxy, 1-methoxyethoxy, 1-ethoxyethoxy or One or more of In the formula (b), R 9 Selected from substituted or unsubstituted C1~C 20 Straight chain alkyl, substituted or unsubstituted C3~C 20 Branched alkyl, substituted or unsubstituted C3~C 20 Any one or more of the cycloalkyl groups of 9 Selected from substituted or unsubstituted C1~C 10 Straight chain alkyl, substituted or unsubstituted C3~C 10 Branched alkyl, substituted or unsubstituted C3~C 10 Any one or more of the cycloalkyl groups of 9 Any one or more selected from substituted or unsubstituted C1-C6 straight-chain alkyl, substituted or unsubstituted C3-C6 branched-chain alkyl, substituted or unsubstituted C3-C6 cycloalkyl; further, preferably, R 9 Any one or more selected from tert-butoxycarbonyl, propoxycarbonyl, adamantyloxycarbonyl and tert-butoxycarbonylmethyl.

9. The resist composition according to claim 7 or 8, characterized in that The weight content of the acid generator is 0.01 to 5%, preferably 0.1 to 3%, relative to the weight of the solid content of the resist composition. Preferably, the resist composition further includes a solvent.

10. A patterning method comprising mixing, film forming and patterning a resist composition, characterized in that: The resist composition is the resist composition according to any one of claims 7 to 9.

11. Use of the resist composition according to any one of claims 7 to 9, comprising applying the resist composition to the preparation of a protective film, an interlayer insulating material or a pattern transfer material of an electronic component.

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