WO2021057862A1 - Sulfimide photo acid generator capable of efficiently generating acid at i-ray, photosensitive composition and preparation method therefor, pattern forming method, and applications of sulfimide photo acid generator and photosensitive composition - Google Patents

Abstract

A sulfimide photo acid generator capable of efficiently generating an acid at an I-ray, a photosensitive composition and a preparation method therefor, a pattern forming method, and applications of a sulfimide photo acid generator and a photosensitive composition. The sulfimide photo acid generator has a structure shown in the following general formula (A). The photo acid generator has high sensitivity, high solubility, and excellent heat resistance to an active energy ray having the wavelength of 300-450 nm, particularly 365 nm. The photosensitive composition comprises the following raw materials: a resin component and a sulfonate photo acid generator. A positive photosensitive composition can be used for the dissolution and exposure of an alkali developing liquid, and a pattern having an excellent resolution ratio, excellent sensitivity, and a good contrast ratio is formed.

Description

Sulfonimide photoacid generator capable of producing high acid in the I line, photosensitive composition and preparation method thereof, pattern formation method, and application of both Technical field

The present invention relates to the technical field of organic chemistry, in particular to a sulfonimide photoacid generator capable of producing high acid in the I line, a photosensitive composition and a preparation method thereof, a pattern formation method, and applications of both.

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 type, and the resist material in which the exposed part is changed to be insoluble in the developer is called a negative type.

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 in terms of miniaturization technology to adjust the 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 generate carboxylic acid Or phenol. After 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.

As a resist for I-line lithography with a wavelength of 365 nm, a diazonaphthoquinone (DNQ) resist is usually used, but chemically amplified resists can have high sensitivity that DNQ resists cannot achieve, and are advantageous for making thick Film resist, therefore, the use of chemically amplified I-line lithography has attracted attention. Currently, many types of photoacid generators used in chemically amplified resists for I line are known, such as naphthylsulfimide derivatives, heteroanthrone derivatives, coumarin derivatives, acyl Phosphorus oxide derivatives, oxime ester derivatives, etc., can be roughly classified into two types: non-ionic and ionic.

Among them, ionic photoacid generators often have insufficient compatibility with solvents, resulting in their inability to fully play their role in resists; non-ionic photoacid generators have good compatibility with hydrophobic materials, but the existing non-ionic photoacid generators have good compatibility with hydrophobic materials. Ionic photoacid generators have low sensitivity to line I (resulting in poor acid generation efficiency), and due to insufficient heat resistance, they are easily decomposed in the heating (PEB) process after exposure, and there are also narrow margins. problem.

Summary of the invention

In view of the shortcomings of the prior art, the main purpose of the present invention is to provide a photoacid generator with high sensitivity to active energy rays of wavelength 300-450nm, especially 365nm (I line), high solubility and excellent heat resistance.

For the above purpose, a sulfonimide photoacid generator capable of producing high acid in line I is specifically provided, which has the structure shown in the following general formula (A):

among them,

R ₁ is 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;

L is a C ₄ -C ₁₈ heterocyclic group containing N, S or O, optionally (optionally), at least one hydrogen atom on L may be _{substituted by R 2} ; wherein,

R _{2 is} selected from the following groups:

halogen;

A C ₁ -C ₂₀ linear or branched (halo) alkyl group, optionally, -CH ₂ -can be substituted by -O- or -S-;

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

A C ₇ -C ₁₀ phenylalkyl group, optionally, -CH ₂ -may be substituted by -O-;

R ₁ 'CO-, wherein R _1' represents C ₁ -C ₆ alkyl, a phenyl group, and optionally, at least one hydrogen atom in the phenyl group may be alkyl or C ₁ -C ₄ alkoxy is Substituted by

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

C ₂ -C ₆ linear or branched alkenyl, optionally, -CH ₂ -can be substituted by -O-;

A C ₂ -C ₄ alkenyl group terminated by a C ₆ -C _{10 aryl group;}

C ₂ -C ₆ linear or branched alkynyl group;

A C ₂ -C ₄ alkynyl group terminated by a C ₆ -C _{10 aryl 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;

And when _{the number of R 2} is greater than 1, they may be the same or different from each other.

In the present invention, the halogen means fluorine, chlorine, bromine or iodine atom.

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 ) Active energy rays have high sensitivity and strong absorption, and can quickly produce acid under short-term irradiation. At the same time, it also exhibits good solubility and heat resistance during application.

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

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. Without limitation, the active energy rays may be electromagnetic waves with wavelengths in the visible light region (visible rays), electromagnetic waves with wavelengths in the ultraviolet region (ultraviolet rays), electromagnetic waves with wavelengths in the infrared region (infrared rays), and X-rays and other wavelengths in the non- Electromagnetic waves in the visible area, etc. However, preferably, the active energy ray is an active energy ray with a wavelength between 300-450 nm in the near-ultraviolet light region and a visible light region, and particularly preferably an active energy ray with a wavelength of 365 nm (I line).

The photoacid generator of the present invention and the following photosensitive composition can be used for any known applications of photoacid generators, such as paints, coating agents, inks, inkjet inks, resist films, liquid resists, negatives Type resists, positive type resists, MEMS resists, negative photosensitive materials, materials for stereolithography and micro stereolithography, etc. Most suitably, as a photoacid generator in a resist, a resist is prepared together with a resin having acid dissociation properties for use in semiconductor photolithography.

Compared with the prior art, the beneficial effects of the present invention are embodied in:

The photoacid generator can realize long-wave absorption, has high sensitivity to active energy rays with wavelengths of 300-450nm, especially 365nm (I line), and has strong absorption; photolysis can produce strong sulfonic acid; and has good solubility And heat resistance.

In another aspect of the present invention, the present invention also provides a photosensitive composition comprising the following raw materials: a resin component and a sulfonate photoacid generator, and the sulfonate photoacid generator includes benzene imide sulfonate The acid ester and benzimide sulfonate are any one of the above-mentioned sulfonimide photoacid generators, preferably the ratio of the resin component and the sulfonate photoacid generator by mass is 50-80:1 -5. Preferably, the mass content of the sulfonate-based photoacid generator is 1-5% relative to the mass of the solid content of the photosensitive composition.

In a third aspect, the present invention also provides a pattern forming method, including: coating the photosensitive composition on the carrier, pre-baking to form a coating film; selectively exposing the coating film and baking; and using an alkaline developer Develop the exposed coating film.

In the fourth aspect, the present invention also provides an application of the photosensitive composition in the protective film, interlayer insulating material or pattern transfer material of electronic components.

The beneficial effect of the present invention is that the photosensitive composition of the present invention, its preparation method, pattern forming method, and application are mixed with a resin component and a sulfonate photo-acid generator, and can be used for the positive type of the alkali developer solution to dissolve and expose. The photosensitive composition forms a pattern with excellent resolution, sensitivity and good contrast.

Other features and advantages of the present invention will be described in the following description, and part of them will become obvious from the description, or be understood by implementing the present invention. The purpose and other advantages of the present invention are realized and obtained by the structures specifically pointed out in the specification, claims and drawings.

In order to make the above-mentioned objects, features and advantages of the present invention more obvious and understandable, the following is a detailed description of preferred embodiments in conjunction with accompanying drawings.

Description of the drawings

In order to explain the specific embodiments of the present invention or the technical solutions in the prior art more clearly, the following will briefly introduce the drawings that need to be used in the specific embodiments or the description of the prior art. Obviously, the appendix in the following description The drawings are some embodiments of the present invention. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative work.

Fig. 1 is a process flow diagram of the pattern forming method of the present invention.

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 drawings and in conjunction with the embodiments.

As analyzed in the background art of this application, the photoacid generator in the prior art has low sensitivity to line I, resulting in a slower rate of acid production and affecting production efficiency. In order to solve this problem, the present application provides a sulfonimide photoacid generator, a photosensitive composition and a preparation method thereof, a pattern formation method, and applications of both.

In order to improve the sensitivity, some strong electron withdrawing groups containing heteroatoms such as O, N, S, etc. can be introduced on the basis of the sulfonimide structure. The introduction of strong electron withdrawing groups can help increase the longest absorption of the molecule. Wavelength, which can have a strong absorption at the I line. Therefore, in a typical implementation of the present application, a sulfonimide photoacid generator capable of high acid production in line I is provided, which has a structure represented by the general formula (A):

among them,

R ₁ is 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;

L is a C ₄ -C ₁₈ heterocyclic group containing N, S or O. Optionally, at least one hydrogen atom on L may be _{substituted by R 2} ; wherein,

R _{2 is} selected from the following groups:

halogen;

A C ₁ -C ₂₀ linear or branched (halo) alkyl group, optionally, -CH ₂ -can be substituted by -O- or -S-;

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

A C ₇ -C ₁₀ phenylalkyl group, optionally, -CH ₂ -may be substituted by -O-;

R ₁ 'CO-, wherein R _1' represents C ₁ -C ₆ alkyl, a phenyl group, and optionally, at least one hydrogen atom in the phenyl group may be alkyl or C ₁ -C ₄ alkoxy is Substituted by

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

C ₂ -C ₆ linear or branched alkenyl, optionally, -CH ₂ -can be substituted by -O-;

A C ₂ -C ₄ alkenyl group terminated by a C ₆ -C _{10 aryl group;}

C ₂ -C ₆ linear or branched alkynyl group;

A C ₂ -C ₄ alkynyl group terminated by a C ₆ -C _{10 aryl 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;

And when _{the number of R 2} is greater than 1, they may be the same or different from each other.

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 ) Active energy rays have high sensitivity and strong absorption, and can quickly produce acid under short-term irradiation. At the same time, it also exhibits good solubility and heat resistance during application.

Preferably, the above-mentioned halogen is a fluorine, chlorine, bromine or iodine atom.

In order to simplify the structure, it is preferable that the above-mentioned R ₁ is a C ₁ -C ₆ linear or branched perfluoroalkyl group, a perfluorophenyl group, a C ₁ -C ₆ alkyl group or a fluoroalkyl group with at least one hydrogen atom The phenyl group or camphor group substituted by the group, preferably the R ₁ is C ₁ -C ₈ alkyl, perfluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, Perfluoropentyl, perfluorophenyl, camphor, p-methylphenyl or perfluoromethylphenyl.

Those skilled in the art can select a chemically acceptable group as the L group _{from the above-mentioned C 4} -C _{18 N, S or O-containing heterocyclic groups commonly used in the prior art. Preferably, the above L is pyrrole} Group, indolyl, 1,2-dihydroquinolinyl, morpholinyl, thienyl, pyridyl, piperidinyl, pyrrolidinyl, imidazolyl, pyrazolyl, piperazinyl, phenothiazinyl, Thiazolyl, benzothiazolyl or carbazolyl.

In one embodiment, the above L is pyrrolyl, indolyl, 1,2-dihydroquinolinyl, morpholinyl, imidazolyl or carbazolyl attached to the N atom.

In another embodiment, the above-mentioned L group is attached to the 4-position of the phenyl group, that is, the general formula (A) has the following structure:

Specifically, the above-mentioned sulfonimide photoacid generator can be selected from any compound represented by the following structures:

In another typical embodiment of the present application, an acid generation method is provided, which irradiates any one of the above-mentioned sulfonimide photoacid generators with active energy rays.

In order to further improve the efficiency of acid production, it is preferable that the above-mentioned 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 preferably are active energy rays with a wavelength of 365 nm (I line). 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 ) Active energy rays have high sensitivity and strong absorption, and can quickly produce acid under short-term irradiation.

The photosensitive composition and the like of the present application will be described below in conjunction with examples. The test conditions not specified in the examples are usually implemented according to the conventional conditions in the field or according to the conditions recommended by the manufacturer.

Example 1

The photosensitive composition of Example 1 includes the following raw materials: a resin component and a sulfonate photoacid generator.

Optionally, the mass ratio of the resin component and the sulfonate photoacid generator is 50-80:1-5, preferably 65:3.

As an alternative embodiment of the resin component.

The resin component includes a resin having an acidic group protected by a protective group; wherein the acidic group includes at least one of a carboxyl group and a phenolic hydroxyl group, which may be derived from (meth)acrylic acid (acrylic resin), and has Hydroxystyrene polymer (polyhydroxystyrene resin) and phenolic resin polymer; the content of the acidic group accounts for 1-80% of the resin component content, optionally 26%, 45%, within this range In this case, the photosensitive composition can be obtained with good developability.

Optionally, the hydroxystyrene resin is a polymer containing monomers of styrene compounds, which can 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 composition, the content of the cross-linking group is preferably 20-70% (w/w), within this range, the thermal cross-linking between the cross-linking groups during PEB can be formed with excellent mechanical properties and resistance. Chemical membrane.

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.

(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 may 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.

Secondly, the structure and components of the protecting group are described as follows:

The molecular formula of the protecting group includes:

At least one of; wherein R ₃ , R ₄ , and R ₅ all represent a C ₁ -C ₆ linear/branched alkyl group or a C ₁ -C ₁₀ linear/branched fluorinated alkyl group; and Any two of R ₃ , R ₄ , and R ₅ are suitable for bonding to each other to form a ring; R ₆ , R ₇ , and R ₈ all represent a C ₁ -C ₂₀ hydrocarbon group; any two of _{R 6} , R ₇ , and R ₈ R ₉ represents a C ₁ -C ₆ linear/branched/cyclic alkyl group, and n is 0 or 1.

Specifically, in formula (a), when R ₃ , R ₄ and R ₅ 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 ₆ , R ₇ and R ₈ are aliphatic or/and aromatic hydrocarbon groups having C ₁ -C _20. When R ₆ , R ₇ and R ₈ are aliphatic hydrocarbon groups, they can be linear or 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 ₆ , R ₇ and R ₈ are aromatic hydrocarbon groups, they may be selected from phenyl, naphthyl, anthracenyl, biphenyl, phenanthryl, and fluorenyl. When R ₆ , R ₇ and R ₈ 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 ₆ is preferably a hydrogen atom, R ₇ is preferably a methyl group, and R ₈ is preferably an ethyl, isobutyl, cyclohexyl, 2-ethyl-n-hexyl or octadecyl group; when R ₇ and When R _{8 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 ₆ and R ₇ 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.

As an alternative embodiment of the sulfonate photoacid generator.

The sulfonate photoacid generator includes benzimide sulfonate, the structural formula of which is:

Wherein R ₁ represents C ₁ -C ₂₀ linear/branched alkyl or fluoroalkyl, C ₆ -C ₁₈ is substituted or unsubstituted aryl, or camphor; L represents C ₄ -C ₁₈ A heterocyclic group containing N, S or O, optionally, at least one hydrogen atom on L can be replaced by R ₂ ; R ₂ represents any of the following groups: halogen, such as C ₁ -C ₂₀ Straight-chain or branched (halo)alkyl, optionally, where -CH ₂ -can be substituted by -O- or -S-; phenyl, optionally, where at least one hydrogen atom can be C _1- C ₄ alkyl substituted; C ₇ -C ₁₀ phenyl alkyl, optionally, where -CH ₂ -may be substituted by -O-; R ₁ ′-CO-, where R ₁ ′ It represents a C ₁ -C ₆ alkyl group or a phenyl group, and optionally, at least one hydrogen atom in the phenyl group may be taken by a C ₁ -C ₄ alkyl group or alkoxy group; R ₂ ′-CO-OR ₃ '-, wherein R _2' represents C ₁ -C ₈ alkyl group, a phenyl group, R ₃ 'represents a blank or a C ₃ -C ₄ alkynyl group, and the alkyl group is -CH ₂ - optionally Ground is substituted by -O-, at least one hydrogen atom in the phenyl group may be optionally substituted by a C ₁ -C ₄ alkyl group; a C ₂ -C ₆ linear/branched alkenyl group, any Optionally, -CH ₂ -can be substituted by -O-; C ₂ -C _{4 alkenyl group terminated with C 6} -C ₁₀ aryl group; C ₂ -C ₆ linear/branched chain Alkynyl; C ₆ -C ₁₀ aryl is a capped C ₂ -C ₄ alkynyl; C ₁ -C ₆ alkylsulfonyloxy group, optionally, the hydrogen on the alkyl group can be replaced by a fluorine atom Substitution; C ₆ -C ₁₀ arylsulfonyloxy; and when _{the number of R 2} is greater than 1, they may be the same or different from each other.

The sulfonate photoacid generator is preferably a compound of the following molecular formula (formula g ₁ -formula g ₅₀ , corresponding to the aforementioned structural formulas A1 to A50 in sequence), relative to the mass of the solid content of the composition, the sulfonate photoacid generator The content of is preferably 1-5% (w/w).

As an alternative embodiment of the aromatic carboxylic acid compound.

The aromatic carboxylic acid compound includes: 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 substituents The monocarboxylic acid compound, polycarboxylic acid compound; The macromolecular aromatic carboxylic acid compound includes a macromolecular compound containing a carboxyl group bonded to an aromatic group and an unsaturated double bond. It is preferable that the mass content of the aromatic carboxylic acid compound is 3 to 35% with respect to the mass of the solid content of the photosensitive composition.

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 aromatic carboxylic acid compound can 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 acidic 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.

As an alternative embodiment of the bridging compound.

The photosensitive composition further includes a bridging compound; the bridging compound contains at least one crosslinking group; and the crosslinking group includes an epoxy group and an oxetanyl group. The bridging compound includes: bridging low-molecular compound and bridging high-molecular compound. It is preferable that the mass content of the bridging compound is 10-50% with respect to the mass of the solid content of the photosensitive composition.

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 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.

Further, the photosensitive composition further includes the following auxiliary materials: dissolution control agents, dissolution inhibitors, basic compounds, surfactants, dyes, pigments, plasticizers, photosensitizers, light absorbers, antihalation agents, Storage stabilizers, defoamers, adhesion promoters, phosphors, 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.

As an alternative embodiment of the solvent.

The photosensitive composition further includes a solvent; 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).

The solvent is preferably one or a mixture of two or more of propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, γ-butyrolactone, and N,N-dimethylacetamide. Generally, the solid content concentration of the photosensitive composition is preferably 5-30% (w/w).

Example 2

On the basis of Example 1, this Example 2 also provides a method for preparing a photosensitive composition, including: mixing the resin component and the sulfonate photoacid generator, and dissolving them uniformly in a solvent, The photosensitive composition is obtained.

Optionally, the photosensitive composition further includes raw materials: aromatic carboxylic acid compounds and/or bridging compounds.

Regarding the content of the components of the photosensitive composition and the specific implementation process, please refer to the relevant discussion in Example 1, which will not be repeated here.

Example 3

See Figure 1. On the basis of embodiment 1 or 2, this embodiment 3 also provides a pattern forming method, including: coating the photosensitive composition on the carrier, pre-baking to form a coating film; selective exposure Coating film; heating after exposure; and developing the exposed coating film with an alkaline developer. The specific operations are as follows:

The photosensitive composition prepared in Example 1 was coated on the substrate (silicon substrate, metal substrate, glass substrate, inorganic and/or organic film), preferably using a spinner to coat; Perform pre-baking at 120°C 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°C, and the development time is appropriately determined according to the thickness of the resist to obtain a mask 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.

For the content of the components of the photosensitive composition and the specific implementation process, please refer to the relevant discussion in Examples 1 and 2, which will not be repeated here.

Example 4

On the basis of any of Examples 1-3, Example 4 also provides an application of a photosensitive composition in a protective film for electronic components.

Regarding the content of the components of the photosensitive composition and the specific implementation process, please refer to the relevant discussion in Examples 1-3, which will not be repeated here.

Example 5

On the basis of any one of Examples 1 to 3, this Example 5 also provides an application of a photosensitive composition in an interlayer insulating material of an electronic component.

Regarding the content of the components of the photosensitive composition and the specific implementation process, please refer to the relevant discussion in Examples 1-3, which will not be repeated here.

Example 6

On the basis of any of Examples 1-3, Example 6 also provides an application of a photosensitive composition in a pattern transfer material for electronic components.

Regarding the content of the components of the photosensitive composition and the specific implementation process, please refer to the relevant discussion in Examples 1-3, which will not be repeated here.

Optionally, the electronic components in Embodiments 4-6 are, for example, but 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.

To sum up, the photosensitive composition of the present invention, its preparation method, and pattern formation method can be used for dissolving exposure in an alkali developer by mixing a resin component, an aromatic carboxylic acid compound, and a sulfonate photoacid generator. The positive photosensitive composition forms a pattern with excellent resolution, sensitivity and good contrast.

The above-mentioned technical solutions of the present application will be described below in conjunction with examples and test data. The following examples are merely illustrative and should not be understood as limiting the scope of protection of the present application.

Preparation examples

Preparation Example 1

Synthesis of photoacid generator (A1)

Add 10.5g of indole into a four-necked flask, dissolve it with 307.1g of toluene, add 22.9g of 4-bromophthalic anhydride under stirring, then add 0.5g of tetrakis(triphenylphosphine)palladium and 2.7g of triphenylphosphine Phenylphosphine, 31.2g potassium phosphate, nitrogen gas, heated to 110°C under reflux, continued stirring for 4h, and then cooled to room temperature, the solution was brown. 70.3g of 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 17.9g of light yellow solid.

Dissolve 17.9 g of the obtained light yellow solid in 100.2 g of dichloromethane, add dropwise a mixed solution of hydroxylamine hydrochloride and ammonium acetate in dichloromethane (hydroxylamine hydrochloride 4.8 g, ammonium acetate 5.3 g, and dichloromethane 100.1 g). After the completion, heat and stir at 40℃ for 2h, cool and wash 3 times with water to obtain a light yellow mixed solution, and then add the dichloromethane solution of trifluoromethanesulfonic anhydride dropwise (trifluoromethanesulfonic anhydride 14.8g, dichloromethane 100.1g ), after dripping, keep stirring at 40℃ for 1h, wash 3 times with water, distill dichloromethane at 40℃ under reduced pressure to ensure no precipitation, then add 50.3g of methanol to crystallize, keep the temperature below 15℃, and filter to obtain 19.1 g of pale yellow solid is the compound shown in (A1).

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

¹ H NMR (400MHz, CDCl ₃ ): δ8.14–8.02 (m, 2H), 7.98 (dd, J = 8.2, 2.0 Hz, 1H), 7.72–7.60 (m, 2H), 7.38 (d, J = 3.5 Hz, 1H), 7.31 (ddd, J=8.4, 7.1, 1.4 Hz, 1H), 7.27-7.22 (m, 1H), 6.80 (dd, J=3.5, 0.8 Hz, 1H).

Preparation Example 2

Synthesis of photoacid generator (A2)

Put 5.7g pyrrole into a four-neck flask, dissolve it with 300.2g toluene, add 23.1g 4-bromophthalic anhydride under stirring, then add 0.4g palladium acetate, 4.8g Xphos, 20.8g sodium carbonate, and blow nitrogen. , The temperature was raised to 105°C and refluxed, stirring was continued for 18h, and then cooled to room temperature, the solution was brown. Add 70.2 g of water and stir, filter out the insoluble matter, separate the liquid, wash the organic layer 3 times with water, and then distill off toluene under reduced pressure at 60° C. to obtain 10.9 g of light yellow solid.

Dissolve 10.9 g of the obtained light yellow solid in 100.2 g of dichloromethane, add dropwise a mixed solution of hydroxylamine hydrochloride and ammonium acetate in dichloromethane (hydroxylamine hydrochloride 3.7 g, ammonium acetate 4.0 g, and dichloromethane 100.1 g). After the completion, heat and stir at 40℃ for 2h, cool and wash 3 times with water to obtain a light yellow mixed solution, and then add the dichloromethane solution of trifluoromethanesulfonic anhydride dropwise (trifluoromethanesulfonic anhydride 14.8g, dichloromethane 100.1g ), after the dropwise addition, keep stirring at 40°C for 1h, wash 3 times with water, distill dichloromethane at 40°C under reduced pressure to ensure no precipitation, then add 50.2g of methanol to crystallize, keep the temperature below 15°C, and filter to obtain 14.0 g of light yellow solid is the compound shown in (A2).

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

¹ H NMR (400MHz, CDCl ₃ ): δ7.92-7.80 (m, 2H), 7.61 (d, J = 7.5 Hz, 1H), 7.07 (dd, J = 5.5, 3.4 Hz, 2H), 6.22 (dd , J=5.5, 3.4 Hz, 2H).

Preparation Example 3

Synthesis of photoacid generator (A4)

Put 14.3g of carbazole into a four-necked flask, dissolve it with 300.3g of toluene, add 23.0g of 4-bromophthalic anhydride under stirring, then add 0.4g of palladium acetate and 1mL of tri-tert-butylphosphine (1mol/ L) and 20.2 g of potassium carbonate, vented with nitrogen, heated to 110°C under reflux, continued stirring for 24 hours, and then cooled to room temperature, the solution was brown. 70.3 g of 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 10.1 g of light yellow solid.

Dissolve 10.1 g of the obtained light yellow solid in 100.2 g of dichloromethane, add dropwise a mixed solution of hydroxylamine hydrochloride and ammonium acetate in dichloromethane (hydroxylamine hydrochloride 4.6 g, ammonium acetate 5.3 g, and dichloromethane 100.1 g). After the completion, heat and stir at 40℃ for 2h, cool and wash 3 times with water to obtain a light yellow mixed solution, and then add the dichloromethane solution of trifluoromethanesulfonic anhydride dropwise (trifluoromethanesulfonic anhydride 14.8g, dichloromethane 100.1g ), after the dripping, keep stirring at 40℃ for 1 hour, wash 3 times with water, distill dichloromethane at 40℃ under reduced pressure to ensure that there is no precipitation, then add 50.1g methanol to crystallize, control the temperature below 15℃, filter to obtain light 17.9 g of yellow solid is the compound shown in (A4).

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

¹ H NMR (400MHz, CDCl ₃ ): δ8.13–8.06 (m, 2H), 7.97 (d, J = 7.5 Hz, 1H), 7.89 (d, J = 1.5 Hz, 1H), 7.64–7.57 (m ,3H),7.33-7.24(m,4H).

Preparation Example 4

Synthesis of photoacid generator (A8)

Put 6.1g of imidazole into a four-necked flask, dissolve it with 300.1g of toluene, add 22.7g of 4-bromophthalic anhydride under stirring, then add 0.5g of tetrakis(triphenylphosphine)palladium and 2.6g of triphenyl Phosphine, 20.7g potassium carbonate, nitrogen gas, heated to 110 ℃ reflux, continued stirring for 12h, and then cooled to room temperature, the solution was brown. Add 72.9g of water and stir, filter out insoluble materials, separate the liquid, wash the organic layer 3 times with water, then distill off toluene under reduced pressure at 60°C, and separate by column to obtain 16.1g of light yellow solid.

Dissolve 10.7 g of the obtained light yellow solid in 100.2 g of dichloromethane, add dropwise a mixed solution of hydroxylamine hydrochloride and triethylamine in dichloromethane (hydroxyamine hydrochloride 4.4g, triethylamine 6.1g, dichloromethane 100.1g), After the addition, the temperature was kept at 40°C and stirred for 2 hours. After cooling, it was washed with water 3 times to obtain a light yellow mixed solution. Then, the dichloromethane solution of trifluoromethanesulfonic anhydride (trifluoromethanesulfonic anhydride 9.3g, dichloromethane 100.1g) and 3.0g of pyridine. After the dropwise addition, keep at 40°C and stir for 1h. Stop the reaction when the imide peak is ≤1.50%, wash 3 times with water, and distill out dichloromethane under reduced pressure at 40°C (no precipitation). Then 50.3g of methanol was added to crystallize, the temperature was kept below 15°C, and 5.5g of pale yellow solid was obtained after filtration, which was the compound shown in (A8).

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

¹ H NMR (400MHz, CDCl ₃ ): δ 8.37 (s, 1H), 7.93-7.84 (m, 4H), 7.30 (d, J=7.5 Hz, 1H).

Preparation Example 5

Synthesis of photoacid generator (A9)

Put 7.8g of morpholine in a four-necked flask, dissolve it with 300.1g of toluene, add 23.0g of 4-bromophthalic anhydride under stirring, then add 1.1g of Pd(dba) ₂ , 2.5g of triphenylphosphine and 25.4g potassium phosphate, nitrogen gas, heated to 110°C under reflux, continued stirring for 14h, and then cooled to room temperature, the solution was brown. 70.3g of 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 16.2g of light yellow solid.

Dissolve 11.9 g of the obtained light yellow solid in 100.2 g of dichloromethane, add dropwise a mixed solution of hydroxylamine hydrochloride and triethylamine in dichloromethane (4.3 g of hydroxylamine hydrochloride, 6.1 g of triethylamine, and 100.1 g of dichloromethane), After the addition, the temperature was kept at 40°C and stirred for 2 hours. After cooling, it was washed with water three times to obtain a light yellow mixed solution. Then, the dichloromethane solution of trifluoromethanesulfonic anhydride (trifluoromethanesulfonic anhydride 14.8g, dichloromethane) was added dropwise. 100.1g), after the completion of the dropping, keep stirring at 40℃ for 1h, wash with water 3 times, distill dichloromethane at 40℃ under reduced pressure (no precipitation), then add 50.3g of methanol to crystallize, keep the temperature below 15℃, filter Then, 6.1 g of a light yellow solid was obtained, which was the compound represented by (A9).

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

¹ H NMR (400MHz, CDCl ₃ ): δ 7.70 (d, J=7.5 Hz, 1H), 7.36-7.12 (m, 2H), 3.82 (m, 4H), 3.24 (m, 4H).

Preparation Example 6

Synthesis of photoacid generator (A17)

Add 17.3g of 1,2-dihydroquinoline to a four-necked flask, dissolve it with 301.2g of toluene, add 27.3g of 4-bromophthalic anhydride under stirring, then add 0.3g of palladium acetate and 2.6g of triphenyl Phosphine and 15.7g potassium phosphate, nitrogen, heated to 110 ℃ reflux, continued stirring for 4h, and then cooled to room temperature, the solution was brown. 71.2 g of 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 15.4 g of light yellow solid.

Dissolve 15.4 g of the obtained light yellow solid in 150.2 g of dichloromethane, add dropwise a mixed solution of hydroxylamine hydrochloride and ammonium acetate in dichloromethane (3.6 g of hydroxylamine hydrochloride, 3.9 g of ammonium acetate, and 100.1 g of dichloromethane). After the completion, heat and stir at 40℃ for 2h, cool and wash 3 times with water to obtain a light yellow mixed solution, and then add the dichloromethane solution of trifluoromethanesulfonic anhydride dropwise (trifluoromethanesulfonic anhydride 14.8g, dichloromethane 100.1g ), after the dripping, keep stirring at 40℃ for 1h, wash 3 times with water, distill dichloromethane at 40℃ under reduced pressure to ensure no precipitation, then add 50.2g methanol crystal, temperature control below 15℃, filter to obtain light 13.7 g of yellow solid is the compound shown in (A17).

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

¹ H NMR (400MHz, CDCl ₃ ): δ7.88-7.73(m,2H), 7.53-7.44(m,2H), 7.19(t,J=7.5Hz,1H), 7.04(d,J=7.4Hz , 1H), 7.03 (td, J = 7.7, 1.5 Hz, 1H), 5.56 (d, J = 2.0 Hz, 1H), 1.94 (s, 3H), 1.63 (d, J = 1.0 Hz, 6H).

Preparation Example 7

Synthesis of photoacid generator (A18)

Add 11.4g of 3-methylindole into a four-necked flask, dissolve it with 300.7g of toluene, add 23.3g of 4-bromophthalic anhydride under stirring, and then add 0.3g of bis(dibenzylideneacetone) Palladium, 2.5g of triphenylphosphine and 13.1g of cesium carbonate were flushed with nitrogen, heated to reflux, stirred for 4h, cooled to room temperature, and the solution was brown. 70.2 g of 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 17.5 g of light yellow solid.

Dissolve 18.5 g of the obtained light yellow solid in 100.2 g of dichloromethane, add dropwise a mixed solution of hydroxylamine hydrochloride and ammonium acetate in dichloromethane (hydroxylamine hydrochloride 4.8 g, ammonium acetate 5.3 g, and dichloromethane 100.1 g). After the completion, heat and stir at 40°C for 2 hours. After cooling, wash with water 3 times to obtain a light yellow mixed solution, and then add dropwise the dichloromethane solution of pentafluorobenzenesulfonyl chloride (pentafluorobenzenesulfonyl chloride 17.7g, dichloromethane 100.1g), After dripping, keep stirring at 40℃ for 4h, wash with water 3 times, distill dichloromethane at 40℃ under reduced pressure to ensure that there is no precipitation, then add 50.2g methanol to crystallize, control the temperature below 15℃, filter to obtain light yellow 29.9 g, is the compound represented by (A18).

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

¹ H NMR (400MHz, DMSO-d ₆ ): δ8.30–8.08(m,3H), 7.82–7.72(m,2H), 7.69–7.60(m,1H), 7.35–7.27(m,1H), 7.23 (t, J=7.4 Hz, 1H), 2.33 (s, 3H).

Preparation Example 8

Synthesis of photoacid generator (A20)

Add 10.1g of 3-methylcarbazole into a four-necked flask, dissolve it with 300.3g of toluene, add 23.7g of 4-bromophthalic anhydride under stirring, then add 0.2g of palladium acetate and tri-tert-butyl phosphine 1mL (1mol/L) and 7.1g of sodium tert-butoxide, vented with nitrogen, heated to 110°C under reflux, continued stirring for 4h, and then cooled to room temperature, the solution was brown. 70.2 g of 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 17.9 g of light yellow solid.

Dissolve 17.9 g of the obtained light yellow solid in 100.2 g of dichloromethane, add dropwise a mixed solution of hydroxylamine hydrochloride and ammonium acetate in dichloromethane (hydroxylamine hydrochloride 4.8 g, ammonium acetate 5.3 g, and dichloromethane 100.1 g). After the completion, heat and stir at 40°C for 2 hours. After cooling, wash with water 3 times to obtain a light yellow mixed solution, and then add camphorsulfonyl chloride solution in dichloromethane (camphorsulfonyl chloride 17.1g, dichloromethane 100.1g). Keep stirring at 40℃ for 1h, wash 3 times with water, distill dichloromethane at 40℃ under reduced pressure to ensure no precipitation, then add 50.2g of methanol to crystallize, control the temperature below 15℃, filter to obtain 19.6g of light yellow solid, namely This is the compound represented by (A20).

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

¹ H NMR (400MHz, CDCl ₃ ): δ8.09–8.01(m,1H), 7.97(d,J=7.5Hz,1H), 7.88(d,J=1.5Hz,1H), 7.81–7.59(m ,3H),7.42(d,J=7.5Hz,1H),7.32–7.16(m,3H),3.45–3.32(m,2H),2.46(d,J=0.9Hz,3H),2.30–2.20( m, 2H), 2.09 (d, J = 8.5 Hz, 1H), 1.88-1.61 (m, 4H), 1.03 (d, J = 1.5 Hz, 3H), 0.98 (d, J = 1.5 Hz, 3H).

Preparation Example 9

Synthesis of photoacid generator (A26)

Add 6.5g of 3-methoxymethylindole into a four-necked flask, dissolve it with 300.1g of toluene, add 11.3g of 4-bromophthalic anhydride under stirring, and then add 0.2g of acetic acid. Palladium, 1 mL (1 mol/L) of tri-tert-butyl phosphine and 18.5 g of potassium phosphate were heated to 110° C. to reflux, and stirring was continued for 16 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 11.6 g of light yellow solid.

Dissolve 7.0g of the obtained pale yellow solid in 100.2g of dichloromethane, add 3.4g of hydroxylamine hydrochloride and 3.7g of triethylamine, stir at 20°C for 0.5h, then heat to 60°C, after 6h, wash with water 3 times after cooling. A light yellow solution was obtained, and then the dichloromethane solution of camphorsulfonyl chloride (p-toluenesulfonyl chloride 13.1g, dichloromethane 100.1g) was added dropwise. After the addition, the temperature was kept at 40℃ and stirred for 1h. After cooling, it was washed 3 times with water at 40℃. Distill off dichloromethane under reduced pressure to ensure no precipitation, then add 50.2g of methanol to crystallize, control the temperature below 15°C, filter to obtain 15.3g of light yellow solid, which is the compound shown in (A26).

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

¹ H NMR (400MHz, CDCl ₃ ): δ7.96–7.85(m,2H), 7.84(d,J=1.4Hz,1H), 7.76–7.69(m,3H), 7.56(d,J=7.5Hz , 1H), 7.52 (d, J = 7.6 Hz, 1H), 7.37-7.08 (m, 4H), 3.86 (s, 3H), 2.46 (d, J = 0.9 Hz, 3H).

Preparation Example 10

Synthesis of photoacid generator (A47)

Add 6.8g of anhydrous zinc chloride, 100mL of dichloroethane, and 14.1g of acetyl chloride to a four-necked flask, stir at room temperature for 30min, and slowly add 5.8g of indole solution dissolved in 50mL of dichloroethane dropwise; after reacting at room temperature for 1 hour , The temperature is raised to 50 ℃ to continue the reaction, 13.6g of anhydrous zinc chloride powder is added in 3 times during the reaction, controlled by TLC, the conversion of raw materials is complete after 3 hours of reaction, dichloroethane is distilled out, and 50% potassium hydroxide is added 150 mL of the aqueous solution was extracted 3 times with anhydrous ether, the organic layers were combined, dried overnight with anhydrous magnesium sulfate, the ether solvent was removed, and recrystallized with dichloromethane/petroleum ether to obtain 6.2 g of light yellow needle-like crystals. ¹ H NMR(400MHz,CDCl3)δ8.97(d,J=8.4Hz,1H),8.25-8.17(m,2H),7.44(d,J=7.5Hz,1H),7.31-7.26(m,2H ), 2.55(s, 3H).

Put 5.8g of the obtained light yellow solid into a four-necked flask, dissolve it with 202.2g of toluene, add 11.42g of 4-bromophthalic anhydride under stirring, and then add 0.21g of bis(dibenzylidene Acetone) palladium, 10.2g triethylamine and 1mL (2mol/L) tri-tert-butyl phosphine, heated to 110°C and refluxed, kept stirring for 12h, controlled by HPLC, then cooled to room temperature, added water and stirred, filtered and separated, organic The layer was washed three times with water, and then toluene was distilled off under reduced pressure at 60° C. to obtain 11.2 g of solid.

The obtained solid 7.3 was dissolved in 151.5g of dichloromethane, and 2.5g of hydroxylamine hydrochloride and 3.2g of triethylamine were added dropwise. After the dropwise addition, the mixture was stirred at 25°C for 1h, and then heated to 70°C. After 6h, it was cooled and washed with water. A light yellow liquid is obtained by adding 1.1 g of pyridine and 3.2 g of trifluoromethanesulfonic anhydride, reacting at 0-5°C for 1 h, then washing with water 3 times, distilling dichloromethane under reduced pressure at 40°C, and then adding 50.2 g Methanol was crystallized to obtain 4.5 g of an off-white solid, which is the compound represented by (A47).

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

¹ H NMR (400MHz, CDCl ₃ ): δ8.41-8.16 (m, 2H), 8.08 (s, 1H), 8.01 (d, J = 7.5 Hz, 1H), 7.92 (d, J = 1.5 Hz, 1H ), 7.56-7.34 (m, 3H), 2.63 (s, 3H).

The preparation methods of compounds with other structural formulas will not be listed one by one. Those skilled in the art can use the above preparation examples as reference to appropriately react with the substrates with corresponding substituent groups, and select efficient preparation conditions through routine experiments. .

Comparative Example Compound

Comparative example 1

Non-ionic photoacid generator (B1)

Comparative example 2

Non-ionic photoacid generator (B2)

Comparative example 3

Non-ionic photoacid generator (B3)

Comparative example 4

Non-ionic photoacid generator (B4)

Performance evaluation

The performance evaluations of the photoacid generator compounds synthesized in Preparation Examples 1-10 and Comparative Example Compounds B1-B4 were carried out. The evaluation indicators included molar absorption coefficient, acid production, thermal decomposition temperature, solubility, and resist hardenability.

(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 coefficient (ε 365} ) of I rays (365 nm) was 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.

(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) is selected as the exposure light source, which is obtained from an ultraviolet irradiation light source device (IWATA UV-100D) with a specific exposure intensity through a 365nm band-pass filter (103Mw/cm ² ). 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) Thermal decomposition temperature

A differential thermogravimetric analyzer (Q600SDT) was used to measure the weight change of the compound from 30°C to 500°C at a temperature of 10°C/min in a nitrogen atmosphere, and the point at which the weight was reduced by 2% was taken as the thermal decomposition temperature.

(4) Solvent solubility

Take 1.0000g of the photoacid generating compound and add solvents (butyl acetate, cyclohexanone and PGMEA) at 25°C until the compound in each test tube is completely dissolved and clear. Record the mass of the organic solvent used. The solubility is expressed by the following formula.

(5) Hardenability 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 1.

Table 1

Table 1 continued

From the test results in Table 1, it can be seen that the photoacid generator of the present invention has a molar absorption coefficient of more than 7500 at 365nm, strong I-line absorption capacity, can make full use of light energy, and can ensure a high Utilization rate, and exhibits good resist curability and acid production. At the same time, the thermal decomposition temperature is above 200°C, and it has sufficient thermal stability.

Industrial availability

The photoacid generator with the structure represented by the general formula (A) of the present invention can be used in 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.

The industrial applicability of the above-mentioned photoacid generator will be described below in conjunction with the examples.

Composition Example 1

On the basis of Example 1-3, each raw material of the photosensitive composition was uniformly dissolved in 100% PGMEA (propylene glycol methyl ether acetate) to obtain a photosensitive composition with a solid content concentration of 20% (w/w) Things. The types and contents of resin component (A), aromatic carboxylic acid compound (B), and sulfonate photoacid generator (C) are shown in Table 2.

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 lower right of each structural unit represents the content of the structural 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.

Sulfonate esters photoacid generator (C) using the type C ₁ sulfonate esters photoacid generator having the formula structure:

Composition Example 2

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

The resin component (A) adopts A ₂ type resin, and the structural formula of each component is shown in formula A ₂₁ -formula A ₂₄ respectively. The value at the lower right of each structural unit represents the content of the structural unit in the resin (mass %).

The other component types and contents are shown in Table 2.

Composition Example 3

The difference between composition example 3 and composition example 1 is that:

The resin component (A) adopts A ₃ type resin, and the structural formula of each component is as shown in formula A ₃₁ -formula A _32. The value at the bottom right of each structural unit represents the content of the structural unit in the resin (mass %).

The other component types and contents are shown in Table 2.

Composition Example 4

The difference between composition example 4 and composition example 1 is that:

(1) Sulfonate photoacid generator (C) adopts C ₁₁ type sulfonate photoacid generator, its molecular formula structure is:

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

Composition Example 5

The difference between composition example 5 and composition example 1 is that:

(1) Sulfonate photoacid generator (C) adopts C ₁₂ type sulfonate photoacid generator, its molecular formula structure is:

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

Composition Example 6

The difference between composition example 6 and composition example 1 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 2.

Composition Example 7

The difference between composition example 7 and composition example 1 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 2.

Composition Example 8

The difference between composition example 8 and composition example 1 is that:

(1) The content of C ₁ 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 2.

Composition Example 9

The difference between composition example 9 and composition example 1 is that:

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

The other component types and contents are shown in Table 2.

Composition Example 10

The difference between composition example 10 and composition example 1 is that:

The mass ratio of the resin component (A), the aromatic carboxylic acid compound (B) and the sulfonate photoacid generator (C) is 80:5:1.

Composition Example 11

The difference between composition example 11 and composition example 1 is that:

The mass parts ratio of the resin component (A), the aromatic carboxylic acid compound (B), and the sulfonate photoacid generator (C) is 50:15:5.

Composition Comparative Example 1

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

The aromatic carboxylic acid compound (B) is not included in the raw material of the photosensitive composition.

The other component types and contents are shown in Table 2.

Composition Comparative Example 2

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

(1) Sulfonate photoacid generator (C) adopts C ₂ type sulfonate photoacid generator, its molecular formula structure is:

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

Composition Comparative Example 3

The difference between composition comparative example 3 and composition example 1 is that:

(1) Sulfonate photoacid generator (C) adopts C ₂ type sulfonate photoacid generator, its molecular formula structure is:

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

The photosensitive compositions prepared in Composition Examples 1-9 and Composition Comparative Examples 1-3 were evaluated for sensitivity and resolution by the following methods.

(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)

(3) Composition Examples 1-9, Composition Comparative Examples 1-3 The content and types of the raw material components in the photosensitive compositions prepared in Examples 1-9 and Comparative Examples 1-3 are shown in Table 2.

Table 2 Performance comparison of photosensitive composition

It can be seen from Table 2 that the resin component (A) having an acid group protected by a protecting group, an aromatic carboxylic acid compound (B) having a carboxyl group bonded to an aryl group, and a benzimide 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 does not contain the aromatic carboxylic acid compound (B), the photosensitive composition cannot obtain the required sensitivity and resolution. It can be seen from Composition Example 1, Composition Comparative Example 2 and Composition Comparative Example 3 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 is also poor.

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.

Taking the above-mentioned ideal embodiment according to the present invention as enlightenment, through the above-mentioned description content, relevant staff can make various changes and modifications without departing from the scope of the technical idea of the present invention. The technical scope of the present invention is not limited to the content of the description, and its technical scope must be determined according to the scope of the claims.

Claims (17)

1. A sulfonimide photoacid generator capable of high acid production in line I, with the structure shown in general formula (A):

   

   among them,

   R ₁ is 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;

   L is a C ₄ -C ₁₈ heterocyclic group containing N, S or O. Optionally, at least one hydrogen atom on L may be _{substituted by R 2} ; wherein,

   R _{2 is} selected from the following groups:

   halogen;

   A C ₁ -C ₂₀ linear or branched (halo) alkyl group, optionally, -CH ₂ -can be substituted by -O- or -S-;

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

   A C ₇ -C ₁₀ phenylalkyl group, optionally, -CH ₂ -may be substituted by -O-;

   R ₁ 'CO-, wherein R _1' represents C ₁ -C ₆ alkyl, a phenyl group, and optionally, at least one hydrogen atom in the phenyl group may be alkyl or C ₁ -C ₄ alkoxy is Substituted by

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

   C ₂ -C ₆ linear or branched alkenyl, optionally, -CH ₂ -can be substituted by -O-;

   A C ₂ -C ₄ alkenyl group terminated by a C ₆ -C _{10 aryl group;}

   C ₂ -C ₆ linear or branched alkynyl group;

   A C ₂ -C ₄ alkynyl group terminated by a C ₆ -C _{10 aryl 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;

   And when _{the number of R 2} is greater than 1, they may be the same or different from each other.
2. The sulfonimide photoacid generator according to claim 1, wherein the halogen is a fluorine, chlorine, bromine or iodine atom.
3. The sulfonimide photoacid generator according to claim 1, wherein the R ₁ is a C ₁ -C ₆ linear or branched perfluoroalkyl, perfluorophenyl, At least one hydrogen atom is substituted with a C ₁ -C ₆ alkyl or fluoroalkyl group or a camphor group. Preferably, the R ₁ is a C ₁ -C ₈ alkyl group, a perfluoromethyl group, a full Fluoroethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl, perfluorophenyl, camphor, p-methylphenyl, or perfluoromethylphenyl.
4. The sulfonimide photoacid generator according to claim 1, wherein the L is pyrrolyl, indolyl, 1,2-dihydroquinolinyl, morpholinyl, thienyl, pyridine Group, piperidinyl, pyrrolidinyl, imidazolyl, pyrazolyl, piperazinyl, phenothiazinyl, thiazolyl, benzothiazolyl or carbazolyl.
5. The sulfonimide photoacid generator according to claim 1 or 4, wherein the L is a pyrrolyl group, an indolyl group, or a 1,2-dihydroquinolinyl group attached to the N atom , Morpholinyl, imidazolyl or carbazolyl.
6. The sulfonimide photoacid generator according to any one of claims 1 to 5, wherein the L group is connected to the 4-position of the phenyl group, that is, the general formula (A) is as follows structure:

   
7. The sulfonimide photoacid generator according to claim 1, wherein the sulfonimide photoacid generator is selected from any compound represented by the following structures:

   

   

   

   

   

   
8. An acid generation method, characterized in that the sulfonimide photoacid generator according to any one of claims 1-7 is irradiated with active energy rays.
9. The acid generation method according to claim 8, wherein the active energy rays are active energy rays with a wavelength between 300-450 nm in the near ultraviolet region and the visible region, preferably with a wavelength of 365 nm (I line) Active energy rays.
10. A photosensitive composition comprising the following raw materials: a resin component and a sulfonate photoacid generator. The sulfonate photoacid generator includes benzimide sulfonate, and is characterized in that the benzoyl The iminosulfonate is the sulfonimide photoacid generator according to any one of claims 1 to 7, and preferably the ratio of the resin component to the sulfonate photoacid generator is 50 parts by mass. -80: 1-5, it is preferable that the mass content of the sulfonate-based photoacid generator is 1-5% relative to the mass of the solid content of the photosensitive composition.
11. The photosensitive composition according to claim 10, wherein the resin component comprises a resin having an acidic group protected by a protective group; the acidic group comprises at least one of a carboxyl group and a phenolic hydroxyl group And the content of the acidic groups accounts for 1-80% of the content of the resin component.
12. The photosensitive composition of claim 11, wherein the molecular formula of the protective group comprises:

    

    At least one of; of which

    R ₃ , R ₄ , and R ₅ all represent a C ₁ -C ₆ linear/branched alkyl group or a C ₁ -C ₁₀ linear/branched fluorinated alkyl group; and R ₃ , R ₄ , R _{Any two of 5} are suitable for bonding to each other to form a ring;

    R ₆ , R ₇ , and R ₈ all represent a C ₁ -C ₂₀ hydrocarbon group; _{any two of R 6} , R ₇ , and R ₈ are suitable for bonding to each other to form a ring;

    R ₉ represents a _{linear/branched/cyclic alkyl group having C 1} -C ₆ , and n is 0 or 1.
13. The photosensitive composition according to claim 10, wherein:

    The photosensitive composition further includes the following raw materials: an aromatic carboxylic acid compound;

    The aromatic carboxylic acid compound includes: at least one of a low molecular aromatic carboxylic acid compound or a high molecular aromatic carboxylic acid compound; wherein

    The low-molecular-weight aromatic carboxylic acid compound includes a monocarboxylic acid compound and a polycarboxylic acid compound with at least two carboxyl groups and/or substituents;

    The macromolecular aromatic carboxylic acid compound includes a macromolecular compound containing a carboxyl group bonded to an aromatic group and an unsaturated double bond;

    It is preferable that the mass content of the aromatic carboxylic acid compound is 3 to 35% with respect to the mass of the solid content of the photosensitive composition.
14. The photosensitive composition of claim 11, wherein the photosensitive composition further comprises the following raw materials: a bridging compound; the bridging compound contains at least two different types of crosslinking groups; The crosslinking group includes an epoxy group and an oxetanyl group; the bridging group compound includes: a bridging group low-molecular compound, a bridging group high molecular compound; wherein the bridging group low-molecular compound includes : At least one of bifunctional or higher-functional polyfunctional epoxy compounds, polyoxetane compounds, and vinyl-containing polymerizable monomers; the bridging group polymer compound includes: epoxy-containing At least one of the resin and unsaturated double bond-containing resin; preferably, the mass content of the bridging compound is 10-50% relative to the mass of the solid content of the photosensitive composition.
15. A pattern forming method, characterized in that it comprises:

    Coating the photosensitive composition according to any one of claims 11 to 14 on a carrier and pre-baking to form a coating film;

    Selectively expose part or all of the coating film;

    Heating after exposure; and

    The exposed coating film is developed with an alkaline developer.
16. An application of the photosensitive composition of any one of claims 11 to 14 in a protective film of an electronic component, an interlayer insulating material, or a pattern transfer material.
17. The sulfonimide photoacid generator according to any one of claims 1-7 or the photosensitive composition according to any one of claims 11 to 14 is used in the preparation of coatings, coating agents, inks, inkjets Application in inks, resist films, liquid resists, negative resists, positive resists, MEMS resists, negative photosensitive materials, stereolithography and micro stereolithography materials.

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