An oxime ester photoinitiator containing a naphthalene structure, its preparation method and application

Abstract

The present invention provides an oxime ester photoinitiator containing a naphthalene structure, a preparation method thereof and an application. The photoinitiator has a structure shown by the following structural formula (I) or (II): #imgabs0# In the oxime ester photoinitiator of the present application, a naphthalene ring structure is introduced, so that the initiation activity of the photoinitiator is moderate, and a suitable sensitivity can be effectively controlled to achieve the purpose of uniform curing; and the groups of R1 to R 11 are used to modify the naphthalene ring, which is beneficial to improving the sensitivity of the above-mentioned photoinitiator, and can improve the film-forming property, photosensitivity, transmittance and adhesion when preparing a photosensitive resin.

Description

Technical Field

[0001] The present invention relates to the field of organic chemistry, and in particular, to an oxime ester photoinitiator containing a naphthalene structure, a preparation method and an application thereof. Background Art

[0002] The use of oxime ester compounds as photoinitiators has been widely recognized. Designing and synthesizing new oxime ester photoinitiators that meet the conditions of various application scenarios has always been a research hotspot in the field of photocuring. Since oxime ester photoinitiators have high sensitivity, they can be used in photopolymerizable compositions containing colorants in applications such as color filters and black matrices used in color televisions, liquid crystal displays, solid-state imaging elements, cameras, etc. Oxime ester initiators generally have high initiation activity. However, in some special application scenarios, high initiation activity is unnecessary because it causes uneven curing between the surface layer and the deep layer of the cured layer. Summary of the Invention

[0003] The main object of the present invention is to provide an oxime ester photoinitiator containing a naphthalene structure, a preparation method and an application thereof, so as to solve the problem of uneven curing between the surface layer and the deep layer of the cured layer caused by the high initiation activity of oxime ester photoinitiators in the prior art.

[0004] To achieve the above object, according to one aspect of the present invention, there is provided an oxime ester photoinitiator containing a naphthalene structure, and the photoinitiator has a structure shown in the following structural formula (I) or (II):

[0005]

[0006] Wherein, R1 is selected from any one of the following groups: substituted or unsubstituted C1-C 20 alkyl, substituted or unsubstituted C3-C 20 cycloalkyl, substituted or unsubstituted C6-C 20 aryl, substituted or unsubstituted C4-C 20 heteroaryl, substituted or unsubstituted C3-C 20 alicyclic heterocyclic group, substituted C1-C 20 alkyl includes C3-C 12 cycloalkyl-substituted C1-C 10 alkyl, substituted or unsubstituted C2-C in which at least one -CH2- is replaced by an ether bond or a thioether bond 20 alkyl, substituted C6-C 20 aryl includes C6-C substituted by C1-C6 alkyl 20 aryl, C6-C substituted by C1-C 10 alkoxy-substituted C6-C 20 aryl, C1-C 10alkylthio-substituted C6-C 20 aryl, C1-C8 acyl-substituted C6-C 20 aryl, C1-C8 acyloxy-substituted C6-C 20 aryl, C1-C8 oxyacyl-substituted C6-C 20 aryl, halogen atom-substituted C6-C 20 aryl, cyano-substituted C6-C 20 aryl or nitro-substituted C6-C 20 aryl; substituted C4-C 20 heteroaryl including C1-C6 straight-chain alkyl or branched-chain alkyl-substituted C4-C 20 heteroaryl, substituted C3-C 20 alicyclic heterocyclic group including C1-C6 straight-chain alkyl or branched-chain alkyl-substituted C3-C 20 alicyclic heterocyclic group, substituted C3-C 20 cycloalkyl including C1-C 10 alkyl-substituted C3-C 12 cycloalkyl;

[0007] R2 is selected from any one of the following groups: substituted or unsubstituted C1-C 20 alkyl, substituted or unsubstituted C3-C 20 cycloalkyl, substituted or unsubstituted C6-C 20 aryl, substituted or unsubstituted C4-C 20 heteroaryl, substituted or unsubstituted C3-C 20 alicyclic heterocyclic group, substituted or unsubstituted benzoyl, substituted C1-C 20 alkyl including at least one -CH2- being replaced by -O-, -S-, substituted C2-C 20 straight-chain alkyl or branched-chain alkyl, C3-C 12 cycloalkyl-substituted C1-C 10 alkyl, using a C3-C containing O, N or S heteroatom and double bond 12 heterocyclic group as a capping group C1-C 10 alkyl, substituted C3-C 20 cycloalkyl including C1-C 10 alkyl-substituted C3-C 12 cycloalkyl, substituted C6-C 20 aryl including C6-C substituted by C1-C6 straight-chain alkyl or branched-chain alkyl, nitro, C1-C8 alkoxy, C1-C8 alkylthio 20 aryl, substituted benzoyl including at least one hydrogen atom in the phenyl being replaced by C1-C6 straight-chain alkyl or branched-chain alkyl, OR 12, SR 13 The group obtained by substitution, wherein R 12 is selected from a straight-chain alkyl or branched-chain alkyl of C1-C 10 ; R 13 is selected from a straight-chain alkyl or branched-chain alkyl of C1-C 10 .

[0008] R3, R4, R5, R8, R9, R 10 , R 11 independently represent hydrogen, a substituted or unsubstituted alkyl of C1-C6, or an acyl of C2-C8;

[0009] R6 and R7 independently represent an alkyl of C1-C 10 , an alkyl of C1-C substituted by a cycloalkyl of C3-C6 10 , a haloalkyl of C1-C 10 , and at least one -CH2- in the alkyl or haloalkyl may be substituted by ;

[0010] n is 0, 1 or 2.

[0011] To achieve the above object, according to one aspect of the present invention, there is provided a method for preparing a photoinitiator of the above structural formula (I), the preparation method comprising: Step S1, reacting a compound having the structure shown in structural formula (III) with hydroxylamine hydrochloride to obtain a first intermediate, and the structural formula (III) is The first intermediate has the structure shown in structural formula (IV) Step S2, subjecting the first intermediate to an esterification reaction with an acyl chloride or acid anhydride to obtain a photoinitiator of structural formula I.

[0012] According to another aspect of the present invention, there is provided a method for preparing a photoinitiator of the above structural formula (II), the preparation method comprising: Step S1', reacting a compound having the structure shown in structural formula (III) with nitrite to obtain a second intermediate, and the second intermediate has the structural formula shown in structural formula (V) Step S2', subjecting the second intermediate to an esterification reaction with an acyl chloride or acid anhydride to obtain a photoinitiator of structural formula (II).

[0013] According to still another aspect of the present invention, there is provided a photosensitive resin composition, comprising an alkali-soluble resin, an acrylate monomer and a photoinitiator, and the photoinitiator comprises any one of the above naphthalene-containing oxime ester photoinitiators.

[0014] According to still another aspect of the present invention, there is provided a cured product, which is prepared by irradiating the above photosensitive resin composition with energy rays.

[0015] Applying the technical solution of the present invention, the oxime ester photoinitiator in the present application introduces a naphthalene ring structure, so that the initiation activity of the photoinitiator is moderate, and the appropriate sensitivity can be effectively controlled to achieve the purpose of uniform curing; and the groups of R1 to R 11 are used to modify the naphthalene ring, which is beneficial to improving the sensitivity of the above-mentioned photoinitiator, and can improve the film-forming property, photosensitivity, transmittance and adhesion when preparing the photosensitive resin. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] The specification drawings forming a part of the present application are used to provide a further understanding of the present invention. The schematic embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation to the present invention. In the drawings:

[0017] Figure 1 shows the NMR spectrum of intermediate 1a in Example 1;

[0018] Figure 2 shows the NMR spectrum of intermediate 1b in Example 1;

[0019] Figure 3 shows the NMR spectrum of intermediate 1c in Example 1;

[0020] Figure 4 shows the NMR spectrum of intermediate 1d in Example 1;

[0021] Figure 5 shows the NMR spectrum of compound 1 in Example 1;

[0022] Figure 6 shows a schematic diagram of the photosensitive resin composition provided by the present application forming a pattern of a color filter for a liquid crystal display;

[0023] Figure 7 shows a schematic diagram of the photosensitive resin composition of the comparative example of the present application forming a pattern of a color filter for a liquid crystal display. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0024] It should be noted that, without conflict, the embodiments in the present application and the features in the embodiments can be combined with each other. The present invention will be described in detail below with reference to the drawings and in combination with the embodiments.

[0025] As analyzed in the background art of the present application, in the prior art, the oxime ester photoinitiator has the problem of uneven curing between the surface layer and the deep layer of the cured layer due to high initiation activity. To solve this problem, the present application provides an oxime ester photoinitiator containing a naphthalene structure, its preparation method and application.

[0026] In a typical embodiment of the present application, an oxime ester photoinitiator containing a naphthalene structure is provided, and the photoinitiator has the structure shown in the following structural formula (I) or (II):

[0027]

[0028] Among them, R1 is selected from any one of the following groups: substituted or unsubstituted C1-C 20 alkyl, substituted or unsubstituted C3-C 20 cycloalkyl, substituted or unsubstituted C6-C 20 aryl, substituted or unsubstituted C4-C 20 heteroaryl, substituted or unsubstituted C3-C 20 alicyclic heterocyclic group, substituted C1-C 20 alkyl includes C3-C 12 cycloalkyl-substituted C1-C 10 alkyl, substituted or unsubstituted C2-C in which at least one -CH2- is replaced by an ether bond or a thioether bond 20 alkyl, substituted C6-C 20 aryl includes C6-C 20 aryl substituted by C1-C6 alkyl, C1-C 10 aryl substituted by C1-C 20 alkoxy, C1-C 10 aryl substituted by C1-C 20 alkylthio, C1-C8 acyl-substituted C6-C 20 aryl, C1-C8 acyloxy-substituted C6-C 20 aryl, C1-C8 oxyacyl-substituted C6-C 20 aryl, halogen atom-substituted C6-C 20 aryl, cyano-substituted C6-C 20 aryl or nitro-substituted C6-C 20 aryl; substituted C4-C 20 heteroaryl includes C4-C 20 heteroaryl substituted by C1-C6 linear or branched alkyl, substituted C3-C 20 alicyclic heterocyclic group includes C3-C 20 alicyclic heterocyclic group substituted by C1-C6 linear or branched alkyl, substituted C3-C 20 cycloalkyl includes C1-C 10 cycloalkyl substituted by C3-C 12 alkyl;

[0029] R2 is selected from any one of the following groups: substituted or unsubstituted C1-C 20alkyl, substituted or unsubstituted C3-C 20 cycloalkyl, substituted or unsubstituted C6-C 20 aryl, substituted or unsubstituted C4-C 20 heteroaryl, substituted or unsubstituted C3-C 20 alicyclic heterocyclic group, substituted or unsubstituted benzoyl group, substituted C1-C 20 alkyl includes at least one -CH2- being replaced by -O-, -S-, substituted C2-C 20 linear alkyl or branched alkyl of C3-C 12 alkyl substituted by cycloalkyl of C1-C 10 alkyl with a C3-C containing O, N or S heteroatom and double bond 12 alkyl capped by a heterocyclic group of C1-C 10 substituted C3-C 20 cycloalkyl includes C1-C 10 alkyl-substituted C3-C 12 cycloalkyl, substituted C6-C 20 aryl includes C6-C substituted by linear alkyl or branched alkyl of C1-C6, nitro group, C1-C8 alkoxy group, C1-C8 alkylthio group 20 aryl, substituted benzoyl group includes a group obtained by substituting at least one hydrogen atom in the phenyl group with linear alkyl or branched alkyl of C1-C6, OR 12 , SR 13 substituted group, wherein, R 12 is selected from linear alkyl or branched alkyl of C1-C 10 ; R 13 is selected from linear alkyl or branched alkyl of C1-C 10 ;

[0030] R3, R4, R5, R8, R9, R 10 , R 11 independently represent hydrogen, substituted or unsubstituted alkyl of C1-C6, acyl of C2-C8; R6, R7 independently represent alkyl of C1-C 10 alkyl substituted by cycloalkyl of C3-C6 of C1-C 10 alkyl, alkyl or haloalkyl of C1-C 10 haloalkyl, at least one -CH2- in the alkyl or haloalkyl can be replaced by substituted; n is 0, 1 or 2.

[0031] The oxime ester photoinitiator in this application introduces a naphthalene ring structure, making the initiation activity of the photoinitiator moderate, and can effectively control the appropriate sensitivity to achieve the purpose of uniform curing; and by using R1 to R 11The modification of the naphthalene ring by the group is beneficial to improving the sensitivity of the above photoinitiator and can improve the film-forming property, photosensitivity, transmittance and adhesion when preparing the photosensitive resin.

[0032] To improve the sensitivity of the above photoinitiator, R1 is selected from any one of the following groups:

[0033] Substituted or unsubstituted C1-C 10 alkyl, substituted or unsubstituted C3-C 10 cycloalkyl, substituted or unsubstituted C6-C 12 aryl, substituted or unsubstituted C4-C 10 heteroaryl, substituted or unsubstituted C3-C 10 alicyclic heterocyclic group,

[0034] Preferably, the substituted C1-C 10 alkyl includes C3-C8 cycloalkyl-substituted C1-C 10 alkyl, substituted or unsubstituted C2-C7 alkyl in which at least one -CH2- is replaced by an ether bond or a thioether bond; preferably unsubstituted C1-C 10 alkyl is C1-C8 alkyl, more preferably including methyl, ethyl, propyl or isopropyl;

[0035] Preferably, the substituted C6-C 12 aryl includes C1-C3 alkyl-substituted C6-C 12 aryl, preferably unsubstituted C6-C 12 aryl includes phenyl, naphthyl, biphenyl;

[0036] Preferably, the substituted C4-C 10 heteroaryl includes C1-C 10 linear alkyl or branched alkyl-substituted C4-C 10 heteroaryl, preferably unsubstituted C4-C 10 heteroaryl includes furyl, thiophenyl, pyridine, 2-furyl, quinolinyl;

[0037] Preferably, the substituted C3-C 10 alicyclic heterocyclic group includes C1-C 10 linear alkyl or branched alkyl-substituted C3-C 10 alicyclic heterocyclic group;

[0038] Preferably, the substituted C3-C 10 cycloalkyl includes C1-C 10 alkyl-substituted C3-C 10 cycloalkyl, preferably unsubstituted cycloalkyl includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl;

[0039] Preferably, R2 is selected from substituted or unsubstituted C1-C 10 alkyl, substituted or unsubstituted C3-C 10 cycloalkyl, substituted or unsubstituted C6-C 12 aryl, substituted or unsubstituted C4-C 10 heteroaryl, substituted or unsubstituted C3-C 10 alicyclic heterocyclic group, substituted or unsubstituted benzoyl group; preferably, the substituted C1-C 10 alkyl includes at least one -CH2- being replaced by -O-, -S-, substituted C2-C 10 linear alkyl or branched alkyl, C3-C8 cycloalkyl-substituted C1-C 10 alkyl, C1-C 10 alkyl with a C3-C6 heterocyclic group containing O, N or S heteroatoms and double bonds as the capping group; preferably, the substituted C3-C 10 cycloalkyl includes C1-C6 alkyl-substituted C3-C 10 cycloalkyl;

[0040] Preferably, the substituted C6-C 12 aryl includes C6-C 12 aryl substituted by linear alkyl or branched alkyl of C1-C6, nitro, C1-C5 alkoxy;

[0041] Preferably, the substituted benzoyl group includes a group obtained by replacing at least one hydrogen atom in the phenyl group with linear alkyl or branched alkyl of C1-C6, OR 12 , SR 13 , where R 12 is selected from linear alkyl or branched alkyl of C1-C 10 ; R 13 is selected from linear alkyl or branched alkyl of C1-C 10 ;

[0042] Preferably, R3, R4, R5, R8, R9, R 10 , R 11 represent hydrogen, substituted or unsubstituted C1-C3 alkyl, C2-C3 acyl group;

[0043] Preferably, R6 and R7 independently represent C1-C5 alkyl, C1-C5 haloalkyl, and at least one -CH2- in the alkyl or haloalkyl can be replaced by ;

[0044] n is 1.

[0045] In order to improve the sensitivity of the above photoinitiator, R1 is selected from any one of the following groups:

[0046] Substituted or unsubstituted C1-C 10 alkyl, substituted or unsubstituted C3-C 10 cycloalkyl, substituted or unsubstituted C6-C 10 aryl, substituted or unsubstituted C4-C6 heteroaryl, substituted or unsubstituted C3-C6 alicyclic heterocyclic group;

[0047] Preferably, the substituted C1-C 10 alkyl includes C3-C6 cycloalkyl-substituted C1-C 10 alkyl, substituted or unsubstituted C2-C5 alkyl in which at least one -CH2- is replaced by an ether bond or a thioether bond; preferably, the unsubstituted C1-C 10 alkyl is C1-C5 alkyl, more preferably including methyl, ethyl, propyl or isopropyl;

[0048] Preferably, the substituted C6-C 10 aryl includes C1-C3 alkyl-substituted C6-C 10 aryl, preferably the unsubstituted C6-C 10 aryl includes phenyl, naphthyl;

[0049] Preferably, the substituted C4-C6 heteroaryl includes C1-C3 straight-chain or branched-chain alkyl-substituted C4-C6 heteroaryl, and preferably the unsubstituted C4-C6 heteroaryl includes furyl, thienyl;

[0050] Preferably, the substituted C3-C6 alicyclic heterocyclic group includes C1-C3 straight-chain or branched-chain alkyl-substituted C3-C6 alicyclic heterocyclic group;

[0051] Preferably, the substituted C3-C 10 cycloalkyl includes C1-C3 alkyl-substituted C3-C 10 cycloalkyl, and preferably the unsubstituted cycloalkyl includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl;

[0052] Preferably, R2 is selected from substituted or unsubstituted C1-C 10 alkyl, substituted or unsubstituted C3-C 10 cycloalkyl, substituted or unsubstituted C6-C 10 aryl, substituted or unsubstituted C4-C 10 heteroaryl, substituted or unsubstituted C3-C 10 alicyclic heterocyclic group, substituted or unsubstituted benzoyl;

[0053] Preferably, the substituted C1-C 10 alkyl includes at least one -CH2- replaced by -O-, -S-, substituted C2-C 10The linear or branched alkyl group, C3-C6 cycloalkyl-substituted C1-C 10 alkyl group, and C1-C 10 alkyl group capped with a C3-C6 heterocyclic group containing an O, N, or S heteroatom and a double bond;

[0054] Preferably, the substituted C3-C 10 cycloalkyl group includes a C3-C 10 cycloalkyl group substituted with a C1-C6 alkyl group;

[0055] Preferably, the substituted C6-C 10 aryl group includes a C6-C 10 aryl group substituted with a linear or branched C1-C6 alkyl group, nitro group, or C1-C5 alkoxy group;

[0056] Preferably, the substituted benzoyl group includes a group obtained by substituting at least one hydrogen atom in the phenyl group with a linear or branched C1-C6 alkyl group, OR 12 , SR 13 , where R 12 is selected from a linear or branched C1-C 10 alkyl group; R 13 is selected from a linear or branched C1-C 10 alkyl group;

[0057] Preferably, R3, R4, R5, R8, R9, R 10 , R 11 represent hydrogen, a substituted or unsubstituted C1-C3 alkyl group, or a C2-C3 acyl group;

[0058] Preferably, R6 and R7 independently represent a C1-C5 alkyl group, a C1-C5 haloalkyl group, and at least one -CH2- in the alkyl group or haloalkyl group can be substituted. More preferably, R6 and R7 independently represent a C1-C5 alkyl group;

[0059] n is 1.

[0060] To further improve the sensitivity of the photoinitiator, R1 is methyl, ethyl, phenyl, naphthyl, ethoxy, o-methylphenyl, m-trimethylphenyl, m-dimethylphenyl, o-dimethylphenyl, cyclopropyl, cyclohexyl, thiophenyl, furyl, cyclohexyl-substituted propyl, or cyclohexyl-substituted ethyl;

[0061] Preferably, R2 is any one of methyl, ethyl, propyl, hexyl, heptyl, cyclohexyl, phenyl, thiophenyl, furyl, cyclopentyl-substituted methyl, cyclopentyl-substituted ethyl, cyclopentyl-substituted propyl, cyclohexyl-substituted methyl, cyclohexyl-substituted ethyl, cyclohexyl-substituted propyl, methyl ester propionate, p-nitrophenyl, o-methylphenyl, and benzoyl;

[0062] Preferably, R3, R4, R5, R8, R9, R 10 , R 11 represent hydrogen, methyl, ethyl, propionyl, acetyl; preferably, R6 and R7 independently represent methyl, ethyl, propyl, butyl, pentyl, acetyl; n is 1.

[0063] To further improve the sensitivity of the photoinitiator, R1 is methyl, ethyl, phenyl, naphthyl, ethoxy, o-methylphenyl, m-trimethylphenyl, cyclopropyl, cyclohexyl, thienyl, furyl, cyclohexyl-substituted propyl or cyclohexyl-substituted ethyl,

[0064] preferably, R2 is any one of methyl, ethyl, propyl, hexyl, heptyl, cyclohexyl, phenyl, thienyl, furyl, cyclopentyl-substituted methyl, cyclopentyl-substituted ethyl, cyclohexyl-substituted methyl, cyclohexyl-substituted ethyl, methyl ester propionate, p-nitrophenyl, o-methylphenyl, benzoyl;

[0065] Preferably, R3, R4, R5, R8, R9, R 10 , R 11 represent hydrogen, methyl, ethyl, propionyl, acetyl;

[0066] preferably, R6 and R7 independently represent methyl, ethyl, propyl, butyl, pentyl, acetyl;

[0067] n is 1.

[0068] In some embodiments, the photoinitiator is selected from any one or more of the following compounds:

[0069]

[0070]

[0071]

[0072]

[0073]

[0074] In another typical embodiment of the present application, a preparation method of the photoinitiator of the above structural formula (I) is provided, and the preparation method includes: Step S1, reacting the compound of the structure shown in structural formula (III) with hydroxylamine hydrochloride to obtain a first intermediate, and the structural formula (III) is The first intermediate has the structure shown in structural formula (IV) Step S2, subjecting the first intermediate to an esterification reaction with an acyl chloride or an acid anhydride to obtain the photoinitiator of structural formula (I).

[0075] The preparation method of the present application is simple. By introducing a naphthalene ring structure into the oxime ester photoinitiator obtained by the preparation method of the present application, the initiation activity of the photoinitiator is moderate, and an appropriate sensitivity can be effectively controlled to achieve the purpose of uniform curing. By modifying the naphthalene ring, the groups from R1 to R 11 are increased, which is beneficial to improving the sensitivity of the above-mentioned photoinitiator, and can improve the film-forming property, photosensitivity, transmittance and adhesion when preparing the photosensitive resin.

[0076] The above preparation method can refer to the prior art. In some embodiments, in order to improve the reaction rate and conversion rate, the above step S1 is carried out with a catalyst, and the catalyst is an ammonium salt catalyst. Preferably, the ammonium salt catalyst is ammonium acetate and / or ammonium formate. Preferably, step S1 is carried out in a first solvent, and the first solvent is selected from one or more of methanol, ethanol, isopropanol, and tert-butanol. Preferably, the reaction temperature of step S1 is 60-90°C, and preferably, the reaction time of step S1 is 10-16 h.

[0077] The above preparation method can refer to the prior art. In some embodiments, in order to improve the yield of the esterification reaction as much as possible, in step S2, the catalyst for the esterification reaction is a base catalyst. Preferably, the base catalyst is selected from one or more of triethylamine, pyridine, diisopropylethylamine, potassium hydroxide, sodium hydroxide or sodium hydride. Preferably, the temperature of the esterification reaction is -10-60°C, preferably, the temperature of the esterification reaction is 0-25°C. Preferably, the esterification reaction is carried out in a second solvent, and the second solvent is selected from one or more of diethyl ether, acetonitrile, tert-butyl methyl ether, tetrahydrofuran, vinyl acetate, toluene, xylene, acetone, methyl ethyl ketone, dichloromethane, chloroform, chlorobenzene, dimethylacetamide, and dimethylformamide.

[0078] In another typical embodiment of the present application, a preparation method of a photoinitiator of the above structural formula (II) is provided. The preparation method includes: step S1', reacting a compound of the structure shown in structural formula (III) with nitrite to obtain a second intermediate, and the second intermediate has the structural formula shown in structural formula (V) Step S2', carrying out an esterification reaction on the second intermediate with an acyl chloride or an acid anhydride to obtain a photoinitiator of structural formula (II).

[0079] The above preparation method can refer to the prior art. In some embodiments, in order to improve the reaction rate and conversion rate, in step S1', the nitrite is sodium nitrite or isopentyl nitrite. Preferably, the reaction in step S1' is carried out under the action of a catalyst, and the catalyst is an acid catalyst. Preferably, the acid catalyst is selected from concentrated hydrochloric acid. Preferably, the reaction in step S1' is carried out in a third solvent. Preferably, the third solvent is selected from one or more of dichloromethane, chloroform, 1,2-dichloroethane, and ethyl acetate. Preferably, the temperature of the reaction in step S1' is 0-90°C, and the reaction time in step S1' is 1-10 h.

[0080] The above preparation method can refer to the prior art. In some embodiments, in order to maximize the yield of the esterification reaction, in step S2', the catalyst for the esterification reaction is a base catalyst. Preferably, the base catalyst is selected from one or more of triethylamine, pyridine, diisopropylethylamine, potassium hydroxide, sodium hydroxide, or sodium hydride. Preferably, the temperature of the esterification reaction is -10-60°C, preferably 0-25°C. Preferably, the esterification reaction is carried out in a fourth solvent. Preferably, the fourth solvent is selected from one or more of diethyl ether, acetonitrile, tert-butyl methyl ether, tetrahydrofuran, vinyl acetate, toluene, xylene, acetone, methyl ethyl ketone, dichloromethane, chloroform, chlorobenzene, dimethylacetamide, and dimethylformamide.

[0081] The compound with the structure shown in the above structural formula (III) is a known material in the prior art. In order to facilitate those skilled in the art to implement the preparation method of the present application, in some embodiments, the present application provides a preparation process for the compound with the structure shown in the structural formula (III). The above preparation process includes: Step A, subjecting 1,4-naphthoquinone and a cyclopentadiene monomer to a catalytic addition reaction to obtain 1,4-methanoanthracene-9,10-dione; Step B, subjecting 1,4-methanoanthracene-9,10-dione and a sulfuric acid diester to a catalytic alkylation reaction to obtain a third intermediate, and the third intermediate has the structural formula shown in structural formula (VI) Step C, subjecting the third intermediate to a hydrogenation reaction to obtain a hydrogenation product, and the hydrogenation product has the structure shown in structural formula (VII) Step D, subjecting the hydrogenation product acyl chloride compound to a Friedel-Crafts reaction to obtain a compound with the structure shown in structural formula (III).

[0082] In some embodiments, in the above step A, the catalytic addition reaction uses an acidic catalyst, and the acidic catalyst can be selected from acetic acid, hydrochloric acid, sulfuric acid, perchloric acid, hydrobromic acid, hydroiodic acid, nitric acid, alkyl sulfonic acid, aryl sulfonic acid, sulfonic acid resin, or acidic soil, etc. The reaction temperature is usually 20-100°C, and the reaction time is usually 1-5 h;

[0083] In some embodiments, in the above step B, the catalyst for the alkylation reaction is a basic catalyst or an alkali metal catalyst, preferably KOH, NaOH, NaOCH3, organic amine, sodium methoxide, sodium ethoxide, etc. The above sulfate ester may be dimethyl sulfate, ethyl ester, etc.

[0084] In some embodiments, in the above step C, a metal catalyst is used for the hydrogenation reaction. The metal catalyst may be Raney nickel, palladium on carbon, palladium hydroxide, etc. The reaction temperature is usually 20 to 100 °C, and the reaction time is usually 1 to 5 h. The reaction pressure of the hydrogenation reaction is normal pressure or pressure hydrogenation. The above reaction pressure is usually from normal pressure to 10 kg.

[0085] In some embodiments, in the above step D, a Lewis acid catalyst is used as the catalyst for the Friedel-Crafts reaction, which may be AlCl3, FeCl3, etc. The reaction temperature is usually -10 °C to 50 °C, and the reaction time is usually 1 to 5 h.

[0086] In another typical embodiment of the present application, a photosensitive resin composition is provided, which includes an alkali-soluble resin, an acrylate monomer, and a photoinitiator. The photoinitiator includes the above-mentioned oxime ester photoinitiator containing a naphthalene structure.

[0087] The photosensitive resin composition in the present application uses the above-mentioned oxime ester photoinitiator containing a naphthalene structure. By introducing a naphthalene ring structure, the initiation activity of the photoinitiator is moderate, and an appropriate sensitivity can be effectively controlled to achieve the purpose of uniform curing; and by modifying the naphthalene ring, the groups from R1 to R 11 are increased, and the film-forming property, photosensitivity, transmittance, and adhesion can be improved when preparing the photosensitive resin composition.

[0088] In addition to the above-mentioned oxime ester photoinitiator containing a naphthalene structure shown in the above structural formulas (I) and (II), the above photoinitiator may also include any photoinitiator in the prior art. The photosensitive resin composition of the present application may further include a sensitizer, a surfactant, etc.

[0089] There is no particular limitation on the content of the photoinitiator in the photosensitive resin composition. In order to achieve the purpose of uniform curing, in the above photosensitive resin composition, the content of the photoinitiator is 0.5 to 5 parts. For example, the weight content of the oxime ester photoinitiator of the present application is 0.5 to 5 parts.

[0090] From the aspects of the sensitivity of the composition and the effects generated after exposure, such as heat resistance, solvent resistance, etc., the content of the alkali-soluble resin is preferably 15 to 50 parts, and the alkali-soluble resin is preferably a (meth)acrylate copolymer. Examples of the alkali-soluble resin (b) include: (meth)acrylic acid / (meth)acrylic acid methyl ester copolymer, (meth)acrylic acid / (meth)acrylic acid benzyl ester copolymer, (meth)acrylic acid / (meth)acrylic acid-2-hydroxyethyl / (meth)acrylic acid benzyl ester copolymer, (meth)acrylic acid / (meth)acrylic acid methyl ester / polystyrene macromonomer copolymer, (meth)acrylic acid / (meth)acrylic acid methyl ester / polymethyl methacrylate macromonomer copolymer, (meth)acrylic acid / (meth)acrylic acid benzyl ester / polystyrene macromonomer copolymer, (meth)acrylic acid / (meth)acrylic acid benzyl ester / polymethyl methacrylate macromonomer copolymer, (meth)acrylic acid / (meth)acrylic acid-2-hydroxyethyl / (meth)acrylic acid benzyl ester / polystyrene macromonomer copolymer, (meth)acrylic acid / (meth)acrylic acid-2-hydroxyethyl / (meth)acrylic acid benzyl ester / polymethyl methacrylate macromonomer copolymer, methacrylic acid / styrene / (meth)acrylic acid benzyl ester / N-phenyl maleimide copolymer, (meth)acrylic acid / succinic acid mono[2-(meth)acryloyloxyethyl] / styrene / (meth)acrylic acid benzyl ester / N-phenyl maleimide copolymer, (meth)acrylic acid / succinic acid mono[2-(meth)acryloyloxyethyl] / styrene / (meth)allyl acrylate / N-phenyl maleimide copolymer, (meth)acrylic acid / styrene / (meth)acrylic acid benzyl ester / glycerol mono(meth)acrylate / N-phenyl maleimide copolymer, (meth)acrylic acid / ω-carboxypolycaprolactone mono(meth)acrylate / styrene / (meth)acrylic acid benzyl ester / glycerol mono(meth)acrylate / N-phenyl maleimide copolymer and other carboxyl-containing copolymer molecules.

[0091] For the purpose of achieving uniform curing and easy control of the film thickness, the content of the acrylate monomer is preferably 10 to 30 parts. The acrylate monomer can be a monofunctional, difunctional, or polyfunctional acrylate.

[0092] Examples of the monofunctional acrylate include: methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isoamyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, decyl acrylate, dodecyl acrylate, octadecyl acrylate, isobornyl acrylate, cyclohexyl acrylate, benzyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-3-chloropropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2,2,2-trifluoroethyl acrylate, β-carboxyethyl acrylate, ω-carboxypolycaprolactone monoacrylate, etc.

[0093] As bifunctional acrylates, examples include: dicyclopenteny acrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, bisphenol A diacrylate, EO-modified bisphenol A diacrylate, PO-modified bisphenol A diacrylate, hydrogenated bisphenol A diacrylate, EO-modified hydrogenated bisphenol A diacrylate, PO-modified hydrogenated bisphenol A diacrylate, bisphenol F diacrylate, EO-modified bisphenol F diacrylate, PO-modified bisphenol F diacrylate, EO-modified tetrabromobisphenol A diacrylate, tricyclodecane dimethylol diacrylate, etc.

[0094] As polyfunctional acrylates, examples include: glycerol PO-modified triacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate monopropionate, dipentaerythritol hexaacrylate, tetramethylolmethane tetraacrylate, etc.; and ethoxylated or propoxylated products of the above acrylates, such as dicyclopentenyl oxyethyl acrylate, 2-hydroxy-3-allyloxypropyl acrylate, 2-acryloyloxyethyl-2-hydroxypropyl phthalate, 1,3-butanediol methyl ether acrylate, butoxyethyl acrylate, succinic acid monoacryloyloxyethyl ester, trimethylsilyloxyethyl acrylate or diphenyl-2-acryloyloxyethyl phosphate, etc.

[0095] The above photosensitive resin composition may optionally contain a colorant and / or a solvent. There is no particular limitation on the type of the colorant, and preferably the colorant is a pigment, such as inorganic or organic pigments like carbon black, C.I. Pigment Yellow 3, C.I. Pigment Red 7, C.I. Pigment Blue 15, C.I. Pigment Green 7, etc. There is no special limitation on the solvent as long as it can effectively dissolve other components of the composition. Exemplarily, the solvent can be those commonly used in photosensitive resin compositions, such as ethers, aromatic hydrocarbons, ketones, alcohols, esters or amides.

[0096] As ether solvents, it includes: ethylene glycol monoalkyl ethers, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether or ethylene glycol monobutyl ether; diethylene glycol dialkyl ethers, such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, etc.; alkylene glycol alkyl ether acetates, such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxypentyl acetate, etc.

[0097] As aromatic hydrocarbon solvents, it includes benzene, toluene, xylene, etc.

[0098] As ketone solvents, it includes methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, etc.

[0099] As alcohol solvents, it includes ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerol, etc.

[0100] As ester solvents, it includes ethyl lactate, butyl lactate, ethyl 3 - ethoxypropionate, methyl 3 - methoxypropionate, etc.

[0101] In terms of the drying and coating properties of the solvent, organic solvents with a boiling point of 100 - 200 °C are preferred, such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butyl lactate, ethyl 3 - ethoxypropionate, methyl 3 - methoxypropionate.

[0102] The above solvents can be used alone or in combination of two or more.

[0103] In another typical embodiment of the present application, a cured product is provided, which is prepared by irradiating the above photosensitive resin composition with energy rays.

[0104] The preparation method of the above cured product includes: mixing the components of the above photosensitive resin composition together, stirring evenly to dissolve or disperse them. When mixing, a mixer such as a ball mill can be used; coating the above photosensitive resin composition on a support or substrate, and irradiating with energy rays to form a cured product.

[0105] There is no special limitation on the above support. A support on which the cured product can be peeled off and has good light transmittance is preferred, such as various plastic films like polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly(alkyl methacrylate), poly(methacrylate) copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride - vinyl acetate copolymer, polytetrafluoroethylene, polytrifluoroethylene, cellulose - based film, nylon film, etc. There is no special limitation on the above substrate, such as printed circuit board, glass plate, synthetic resin film, paper, metal plate, etc. There is no special limitation on the coating method of the above photocurable composition, and it can be appropriately selected according to the purpose, such as spraying, roll coating, wire bar coating, etc.

[0106] The photosensitive resin composition in this application can be applied to coatings for coating substrates such as plastics, metals, glasses, ceramics, woods, walls, and optical fibers; protective film materials such as hard coating agents, antifouling films, antireflection films, and impact buffer films; photocuring adhesives, adhesives, photo-decomposable coatings, coating films, and molded articles; optical recording media such as holographic imaging materials; optical molding resins, for example, inks (resins) for 3D printing, photoresists for electronic circuit and semiconductor manufacturing, and photoresists for electronic materials such as color filters, black matrices, and dry films in displays; interlayer insulating films, light extraction films, brightness enhancement films, and sealing materials; printing inks for screen printing, offset printing, intaglio printing, etc., and photocuring inks for inkjet printing; optical components such as lenses, lens arrays, optical waveguides, light guide plates, light diffusing plates, and diffraction elements; light spacers, rib walls, materials for nanoimprinting, etc. More specifically, for example, the photosensitive resin composition of the present invention can be used in color photoresists (RGB), black matrices (BM), photo-spacers, semiconductor photoresists, inks, etc.

[0107] The following further describes the present application in detail with specific examples, which should not be construed as limiting the scope claimed in the present application.

[0108] Example 1: Preparation of Compound 1

[0109]

[0110] Step (1):

[0111]

[0112] Add 500 g of dicyclopentadiene into a 1 L single-necked flask. When the internal temperature is heated to 160 - 170 °C, dicyclopentadiene depolymerizes and distills out from the top of the column. Collect the fraction with a top temperature of 39 - 43 °C, which is cyclopentadiene. Add 546.7 g of 1,4-naphthoquinone, 500 mL of methanol, and 500 mL of acetic acid into a 3 L four-necked flask in sequence. Heat to 40 - 50 °C and dropwise add 570 g of freshly distilled cyclopentadiene. It takes about 3 h to finish the dropwise addition. After the dropwise addition, continue to stir at room temperature for 2 hours, and monitor the reaction progress by TLC. After the reaction is completed, remove the solvent to obtain a brown solid, and slurry it with methanol to obtain 531 g of brown solid 1a with a purity of 97%.

[0113] Step (2):

[0114]

[0115] Add 158 g of intermediate 1a, 1500 mL of ethanol to a 3 L four-necked flask. While maintaining the temperature below 60 °C, simultaneously add 400 g of dimethyl sulfate and 528 g of 24% liquid caustic soda dropwise. Monitor the reaction progress by TLC. After the reaction is completed, remove the ethanol, add water, precipitate the solid, and filter to obtain the crude product. Pulverize the crude product with methanol to obtain 345 g of brown methylation product 1b with a purity of 99.3%.

[0116] Step (3):

[0117]

[0118] Add 345 g of intermediate 1b and 17 g of palladium-carbon to a 2 L four-necked flask, and add 1000 mL of ethyl acetate. Bubble hydrogen gas in at atmospheric pressure or under pressure. Monitor the reaction progress by HPLC. After the reaction is completed, filter to remove the palladium-carbon catalyst and remove the solvent to obtain 300 g of brown hydride 1c with a purity of 99.3%.

[0119] Step (4):

[0120]

[0121] Add 246 g of intermediate 1c, 1500 mL of dichloromethane, and 254 g of aluminum trichloride to a 3 L four-necked flask. Under nitrogen protection, control the internal temperature at 0 - 10 °C and add 150 g of acetyl chloride dropwise. Monitor the reaction progress by TLC. After the reaction is completed, slowly add the reaction solution to dilute hydrochloric acid aqueous solution to quench the reaction. Separate the organic layer, wash the organic layer with water, remove the solvent, and obtain 200 g of pale yellow 1d with a purity of 99% through column chromatography.

[0122] Step (5):

[0123]

[0124] Add 100 g of intermediate 1d, 500 mL of methanol, 34 g of ammonium acetate, and 36 g of hydroxylamine hydrochloride to a 1 L four-necked flask. Stir at 40 - 50 °C. Monitor the reaction progress by TLC. After the reaction is completed, remove the methanol, add water, extract with dichloromethane, and remove the dichloromethane to obtain 75 g of 1e with a purity of 98%.

[0125] Step (6):

[0126]

[0127] Add 50 g of intermediate 1e, 100 mL of dichloromethane, and 33 g of acetic anhydride to a 1 L four-necked flask. Stir at room temperature. Monitor the reaction progress by TLC. After the reaction is completed, remove the dichloromethane, and slurry with a mixed solution of ethyl acetate:n-hexane in a ratio of 1:7 to obtain 34 g of white solid 1 with a purity of 99.5%.

[0128] The structures of some intermediates and Compound 1 were confirmed by NMR spectra as shown in Figures 1 to 5 .

[0129] Preparation of Compound 2 in Example 2

[0130]

[0131] For Compound 2, acetic anhydride was replaced with benzoyl chloride or benzoic anhydride, and the others were the same as Compound 1.

[0132] 1 H NMR(500MHz,Chloroform-d)δ8.19(d,J=1.5Hz,1H),8.16–8.11(m,2H),7.92(d,J=7.5Hz,1H),7.63–7.57(m,1H),7.51–7.44(m,3H),4.07(s,3H),4.05(s,3H),3.87–3.79(m,2H),2.59(s,3H),2.47–2.40(m,1H),2.30–2.23(m,1H),2.17–1.94(m,4H).

[0133] Preparation of Compound 3 in Example 3

[0134]

[0135] For Compound 3, acetic anhydride was replaced with furanoyl chloride, and the others were the same as Compound 1.

[0136] 1 H NMR(500MHz,Chloroform-d)δ8.36(d,J=1.5Hz,1H),7.92–7.83(m,2H),7.51(dd,J=7.5,1.5Hz,1H),7.46(dd,J=7.5,1.6Hz,1H),6.61(t,J=7.5Hz,1H),4.08(s,3H),4.06(s,3H),3.88–3.77(m,2H),2.59(s,3H),2.50–2.39(m,1H),2.31–2.22(m,1H),2.16–1.97(m,4H).

[0137] Preparation of Compound 4 in Example 4

[0138]

[0139] Intermediate 1c was obtained from Intermediate 1f through a Friedel-Crafts reaction, and the process was the same as the preparation of Intermediate 1d.

[0140] Add intermediate 1f (83.8 g, 0.27 mol), 900 g of dichloromethane, isoamyl nitrite (123.1 g, 1.05 mol) and concentrated hydrochloric acid (111 g, 1.13 mol) to a 2 L reaction flask. Stir at room temperature (20 - 25 °C) for 6 h, then add 500 g of water. Stir for 20 min and let it stand for liquid separation. Separate the lower organic phase, wash the organic phase with water until neutral and concentrate. Add 300 g of methanol to the concentrate, stir well at room temperature for 10 - 12 h to precipitate an off-white solid. Filter, wash the filter cake with methanol, and dry the obtained solid in a blast oven at 60 °C for 5 h to obtain 62.0 g of off-white intermediate 4a, with a yield of 60% and a purity of 95%.

[0141] Compound 4 is obtained by acylating intermediate 4a with acetyl chloride or acetic anhydride, and the process is the same as step (6) of compound 1.

[0142] 1 H NMR (500 MHz, Chloroform-d) δ8.18 (d, J = 1.5 Hz, 1H), 8.02 (d, J = 7.5 Hz, 1H), 7.84 (dd, J = 7.5, 1.5 Hz, 1H), 4.07 (d, J = 1.4 Hz, 6H), 3.82 (ddtt, J = 8.6, 7.0, 5.1, 1.5 Hz, 2H), 2.48–2.40 (m, 1H), 2.30–2.23 (m, 1H), 2.18 (s, 3H), 2.12 (s, 3H), 2.11–1.98 (m, 4H).

[0143] Preparation of Compound 5 in Example 5

[0144]

[0145] For compound 5, replace acetic anhydride with benzoyl chloride or benzoic anhydride, and the others are the same as compound 4.

[0146] 1 H NMR (500 MHz, Chloroform-d) δ8.34 (d, J = 1.6 Hz, 1H), 8.16–8.10 (m, 2H), 8.06 (d, J = 7.5 Hz, 1H), 7.89 (dd, J = 7.5, 1.5 Hz, 1H), 7.64–7.57 (m, 1H), 7.50–7.44 (m, 2H), 4.05 (d, J = 3.1 Hz, 6H), 3.88–3.77 (m, 2H), 2.48–2.39 (m, 1H), 2.31–2.23 (m, 1H), 2.21 (s, 3H), 2.14–1.99 (m, 4H).

[0147] Preparation of Compound 6 in Example 6

[0148]

[0149] For Compound 6, acetic anhydride was replaced with furanoyl chloride, and the others were the same as Compound 4.

[0150] 1 H NMR(500MHz,Chloroform-d)δ8.31(d,J=1.4Hz,1H),8.06(d,J=7.5Hz,1H),7.93(dd,J=7.5,1.6Hz,1H),7.85(dd,J=7.5,1.5Hz,1H),7.51(dd,J=7.5,1.5Hz,1H),6.61(t,J=7.5Hz,1H),4.05(s,6H),3.89–3.78(m,2H),2.50–2.39(m,1H),2.31–2.21(m,4H),2.16–1.98(m,4H).

[0151] Referring to the methods of Examples 1, 2, 3, 4, 5, and 6, by replacing the corresponding raw materials, other compounds of Formula (I) and (II) shown in Table 1 below were synthesized.

[0152] Table 1

[0153]

[0154]

[0155]

[0156] Sensitivity evaluation:

[0157] By formulating an exemplary photosensitive resin composition, the film-forming properties of the photoinitiators represented by Formula (I) and Formula (II) of the present invention were evaluated.

[0158] 1. Prepare a photosensitive resin composition with the following composition

[0159]

[0160]

[0161] In the above composition, the photoinitiator is an oxime ester compound represented by Formula I and Formula II disclosed in the present invention or a photoinitiator known in the prior art (for comparison).

[0162] 2. Film formation

[0163] The photosensitive resin composition having the above composition is stirred under a yellow light, taken on a glass substrate and formed into a film by spin coating, pre-dried at 90 °C for 120 seconds to obtain a coating film with a dry film thickness of 2 μm. The above coating film is exposed with an ELS exposure machine, and the exposure amount is 100 mJ / cm 2 , developed with a 2% NaOH aqueous solution for 120 seconds, and hard-baked at 220 °C for 30 min to fix the pattern.

[0164] 3. Performance evaluation

[0165] (1) Transmittance

[0166] The maximum transmittance (T%) of the coating film after hard baking at wavelengths of 300-400 nm is measured with a UV-visible spectrophotometer. The greater the transmittance, the more light can reach the bottom of the coating film, and the better the bottom curing. The specific evaluation criteria are as follows:

[0167] Grade 1: 95% or more;

[0168] Grade 2: Greater than 90% and less than 95%;

[0169] Grade 3: Greater than 85% and less than 90%;

[0170] Grade 4: Less than 85%.

[0171] The evaluation results are shown in Table 2.

[0172] (2) Evaluation of pattern shape

[0173] ① Pattern linearity

[0174] The shape of the substrate surface is observed using a scanning electron microscope (SEM), and the evaluation criteria are as follows:

[0175] ○: The pattern is straight, without wrinkling or tearing;

[0176] ×: Wrinkling or tearing is observed.

[0177] ② Cone angle

[0178] The angle formed between the side surface 1 of the pattern and the color filter substrate 1a is the cone angle θ. The pattern formed by the photosensitive resin composition for the color filter of a liquid crystal display is generally trapezoidal, as Figure 6As shown, at this time, the cone angle θ formed between the side surface 1 of the pattern and the color filter substrate 1a is an acute angle; regarding the cone angle θ, ideally it is 90 degrees to ensure the picture quality. However, there is light leakage or bleeding at the pattern boundary. When the cone angle θ exceeds 90 degrees, the light leakage phenomenon is obvious, and this phenomenon is alleviated when the cone angle θ is less than 90 degrees. When the pattern is used in a display panel or a display device, it is most ideal that the cone angle θ is 70 degrees or more and 85 degrees or less. If the bottom of the coating film is not sufficiently cured and the surface curing and bottom curing are uneven, then undercutting of the cured film may occur during development, as Figure 7 (Comparative Example) shows that at this time, the cone angle θ is greater than 90 degrees, seriously damaging the pattern quality. The bonding angle (cone angle θ) between the pattern and the substrate is measured by a scanning electron microscope (SEM), and the evaluation criteria are as follows:

[0179] ○: The cone angle θ is 70 degrees or more and 85 degrees or less;

[0180] △: The cone angle θ is 86 degrees or more and 90 degrees or less;

[0181] □: The cone angle θ is 91 degrees or more and 100 degrees or less;

[0182] ×: The cone angle θ is 100 degrees or more.

[0183] (3) Adhesion evaluation

[0184] Referring to GB9286-88 "Cross-Cutting Test for Paint and Varnish Films", the adhesion of the coating film is evaluated by the cross-cut test method. It is divided into 0-5 levels (a total of 6 levels) according to the degree of damage. Among them, the best is level 0, and none of the small grids on the film surface fall off; level 5 is extremely poor, and serious peeling occurs on the film surface.

[0185] The evaluation results are shown in Table 2.

[0186] Table 2

[0187]

[0188]

[0189] The structures of the existing photoinitiators, namely compounds A, B, C, and D, for comparison are as follows:

[0190]

[0191] From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects:

[0192] The oxime ester photoinitiator in this application introduces a naphthalene ring structure, making the initiation activity of the photoinitiator moderate, which can effectively control the appropriate sensitivity to achieve the purpose of uniform curing; and by modifying the naphthalene ring, increasing R1 to R 11The group is beneficial to improving the sensitivity of the above-mentioned photoinitiator, and can improve the film-forming property, photosensitivity, transmittance and adhesion when preparing the photosensitive resin.

[0193] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A naphthalene-structured oxime ester photoinitiator, characterized in that, The photoinitiator has the structure shown in the following structural formula (I) or (II): Among them, R1 is selected from any one of the following groups: Substituted or unsubstituted C1-C 10 alkyl, substituted or unsubstituted C3-C 10 cycloalkyl, substituted or unsubstituted C6-C 12 aryl, substituted or unsubstituted C4-C 10 heteroaryl, substituted or unsubstituted C3-C 10 alicyclic heterocyclic group, The substituted C1-C 10 alkyl group is selected from C1-C 10 alkyl group substituted by a C3-C8 cycloalkyl group, a substituted or unsubstituted C2-C7 alkyl group in which at least one -CH2- is substituted by an ether bond or a thioether bond; The substituted C6-C 12 aryl is selected from C6-C 12 aryl substituted with C1-C3 alkyl; The substituted C4-C 10 The heteroaryl group is selected from C1-C 10 The straight-chain alkyl or branched-chain alkyl-substituted C4-C 10 The heteroaryl group; The substituted C3-C 10 The alicyclic heterocyclic group is selected from C1-C 10 The straight-chain alkyl or branched-chain alkyl-substituted C3-C 10 The alicyclic heterocyclic group; The substituted C3-C 10 cycloalkyl group is selected from C1-C 10 alkyl-substituted C3-C 10 cycloalkyl group; R2 is selected from any one of the following groups: Substituted or unsubstituted C1-C 10 alkyl, substituted or unsubstituted C3-C 10 cycloalkyl, substituted or unsubstituted C6-C 12 aryl, substituted or unsubstituted C4-C 10 heteroaryl, substituted or unsubstituted C3-C 10 alicyclic heterocyclic group, substituted or unsubstituted benzoyl group; the substituted C1-C 10 alkyl is selected from at least one -CH2- being -O-, -S- substituted C2-C 10 linear or branched alkyl group, C3-C8 cycloalkyl-substituted C1-C 10 alkyl group, C1-C 10 alkyl group capped with a C3-C6 heterocyclic group containing an O, N or S heteroatom and a double bond; The substituted C3-C 10 The cycloalkyl group is selected from C3-C 10 cycloalkyl group substituted with a C1-C6 alkyl group; The substituted C6-C 12 The aryl group is selected from C6-C 12 aryl groups substituted with a straight-chain or branched-chain alkyl group having 1 to 6 carbon atoms, a nitro group, or an alkoxy group having 1 to 5 carbon atoms; The substituted benzoyl group is selected from groups obtained by substituting at least one hydrogen atom in the phenyl group with a straight-chain alkyl group or a branched-chain alkyl group having 1 to 6 carbon atoms, OR 12 , SR 13 , wherein R 12 is selected from a straight-chain alkyl group or a branched-chain alkyl group having 1 to C 10 ; R 13 is selected from a straight-chain alkyl group or a branched-chain alkyl group having 1 to C 10 ; R3, R4, R5, R8, R9, R 10 , R 11 represent hydrogen, an alkyl group having 1 to 3 carbon atoms; R6 and R7 independently represent an alkyl group having 1 to 5 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms, and at least one —CH2— in the alkyl group or haloalkyl group may be replaced by substituted; n is 1.

2. The photoinitiator according to claim 1, characterized in that, The unsubstituted C1-C 10 alkyl groups in R1 are selected from methyl, ethyl, propyl or isopropyl.

3. The photoinitiator according to claim 1, characterized in that, The aforementioned R1 is selected from any one of the following groups: The substituted or unsubstituted C1-C 10 alkyl group, the substituted or unsubstituted C3-C 10 cycloalkyl group, the substituted or unsubstituted C6-C 10 aryl group, the substituted or unsubstituted C4-C6 heteroaryl group, the substituted or unsubstituted C3-C6 alicyclic heterocyclic group; The substituted C1-C 10 alkyl group is selected from C1-C 10 alkyl groups substituted by C3-C6 cycloalkyl groups, substituted or unsubstituted C2-C5 alkyl groups in which at least one -CH2- is replaced by an ether bond or a thioether bond; the unsubstituted C1-C 10 alkyl group is a C1-C5 alkyl group; The substituted C6-C 10 aryl is selected from C6-C 10 aryl substituted with C1-C3 alkyl, and the unsubstituted C6-C 10 aryl is selected from phenyl and naphthyl; The substituted C4-C6 heteroaryl is a C4-C6 heteroaryl substituted by a C1-C3 straight-chain alkyl or branched-chain alkyl, and the unsubstituted C4-C6 heteroaryl is selected from furyl and thiophenyl; The substituted C3-C6 alicyclic heterocyclic group is a C4-C6 alicyclic heterocyclic group substituted by a C1-C3 straight-chain alkyl or branched-chain alkyl; The substituted C3-C 10 The cycloalkyl group is selected from C3-C 10 cycloalkyl group substituted by C1-C3 alkyl group; and / or, R2 is selected from the substituted or unsubstituted C1-C 10 alkyl group, the substituted or unsubstituted C3-C 10 cycloalkyl group, substituted or unsubstituted C6-C 10 aryl group, the substituted or unsubstituted C4-C 10 heteroaryl group, the substituted or unsubstituted C3-C 10 alicyclic heterocyclic group, the substituted or unsubstituted benzoyl group; The substituted C6-C 10 The aryl group is selected from C6-C aryl groups substituted with a straight-chain or branched-chain alkyl group having 1 to 6 carbon atoms, a nitro group, or an alkoxy group having 1 to 5 carbon atoms. 10 aryl group.

4. The photoinitiator according to claim 3, characterized in that, The aforementioned R6 and R7 independently represent a C1-C5 alkyl.

5. The photoinitiator according to claim 1, characterized in that, The aforementioned R1 is methyl, ethyl, phenyl, naphthyl, ethoxy, o-methylphenyl, m-trimethylphenyl, m-dimethylphenyl, o-dimethylphenyl, cyclopropyl, cyclohexyl, thiophenyl, furyl, cyclohexyl-substituted propyl or cyclohexyl-substituted ethyl, and / or, the aforementioned R2 is any one of methyl, ethyl, propyl, hexyl, heptyl, cyclohexyl, phenyl, thiophenyl, furyl, cyclopentyl-substituted methyl, cyclopentyl-substituted ethyl, cyclopentyl-substituted propyl, cyclohexyl-substituted methyl, cyclohexyl-substituted ethyl, cyclohexyl-substituted propyl, methyl ester propionate, p-nitrophenyl, o-methylphenyl, benzoyl; and / or, said R3, R4, R5, R8, R9, R 10 , R 11 represent hydrogen, methyl, ethyl; and / or, the aforementioned R6 and R7 independently represent methyl, ethyl, propyl, butyl, pentyl, acetyl.

6. The photoinitiator according to claim 5, characterized in that, The aforementioned R1 is methyl, ethyl, phenyl, naphthyl, ethoxy, o-methylphenyl, m-trimethylphenyl, cyclopropyl, cyclohexyl, thiophenyl, furyl, cyclohexyl-substituted propyl or cyclohexyl-substituted ethyl, and / or, the aforementioned R2 is any one of methyl, ethyl, propyl, hexyl, heptyl, cyclohexyl, phenyl, thiophenyl, furyl, cyclopentyl-substituted methyl, cyclopentyl-substituted ethyl, cyclohexyl-substituted methyl, cyclohexyl-substituted ethyl, methyl ester propionate, p-nitrophenyl, o-methylphenyl, benzoyl.

7. The photoinitiator according to claim 1, characterized in that, The photoinitiator is selected from any one or more of the following compounds:

8. A method for preparing a photoinitiator of the structural formula (I) according to any one of claims 1 to 7, characterized in that, The preparation method includes: Step S1, react the compound with the structure shown in formula (III) with hydroxylamine hydrochloride to obtain a first intermediate, and the formula (III) is The first intermediate has the structure shown in formula (IV) In step S2, the first intermediate is subjected to an esterification reaction with an acyl chloride or an acid anhydride to obtain the photoinitiator of structural formula (I).

9. The preparation method according to claim 8, characterized in that, In step S1, the reaction is catalyzed by a catalyst, the catalyst is an ammonium salt catalyst, and / or step S1 is carried out in a first solvent, the first solvent is selected from one or more of methanol, ethanol, isopropanol, tert-butanol, and / or the reaction temperature of step S1 is 60-90 °C, and / or the reaction time of step S1 is 10-16 h.

10. The preparation method according to claim 9, characterized in that, The ammonium salt catalyst is ammonium acetate and / or ammonium formate.

11. The preparation method according to claim 8, characterized in that, In step S2, the catalyst for the esterification reaction is a base catalyst, and / or the temperature of the esterification reaction is -10-60 °C, and / or the esterification reaction is carried out in a second solvent, the second solvent is selected from one or more of diethyl ether, acetonitrile, tert-butyl methyl ether, tetrahydrofuran, vinyl acetate, toluene, xylene, acetone, methyl ethyl ketone, dichloromethane, chloroform, chlorobenzene, dimethylacetamide, dimethylformamide.

12. The preparation method according to claim 11, characterized in that, The base catalyst is selected from one or more of triethylamine, pyridine, diisopropylethylamine, potassium hydroxide, sodium hydroxide or sodium hydride; and / or, the temperature of the esterification reaction is 0 to 25 °C.

13. A method for preparing a photoinitiator of the structural formula (II) according to any one of claims 1 to 7, characterized in that, The preparation method includes: Step S1', reacting the compound having the structure shown in formula (III) with nitrite to obtain a second intermediate, wherein the second intermediate has the structure shown in formula (V) Step S2', subjecting the second intermediate to an esterification reaction with an acyl chloride or an acid anhydride to obtain the photoinitiator of the structural formula (II).

14. The preparation method according to claim 13, characterized in that, In the step S1', the nitrite is sodium nitrite or isoamyl nitrite, and / or, the reaction in the step S1' is carried out under the action of a catalyst, the catalyst is an acid catalyst, and / or, the reaction in the step S1' is carried out in a third solvent, the third solvent is selected from one or more of dichloromethane, chloroform, 1,2-dichloroethane, ethyl acetate, and / or, the temperature of the reaction in the step S1' is 0 to 90 °C, and the reaction time in the step S1' is 1 to 10 h.

15. The preparation method according to claim 14, characterized in that, The acid catalyst is selected from concentrated hydrochloric acid.

16. The preparation method according to claim 13, characterized in that, In the step S2', the catalyst for the esterification reaction is a base catalyst, and / or, the temperature of the esterification reaction is -10 to 60 °C, and / or, the esterification reaction is carried out in a fourth solvent, the fourth solvent is selected from one or more of diethyl ether, acetonitrile, tert-butyl methyl ether, tetrahydrofuran, vinyl acetate, toluene, xylene, acetone, methyl ethyl ketone, dichloromethane, chloroform, chlorobenzene, dimethylacetamide, dimethylformamide.

17. The preparation method according to claim 16, characterized in that, The base catalyst is selected from one or more of triethylamine, pyridine, diisopropylethylamine, potassium hydroxide, sodium hydroxide or sodium hydride, and / or, the temperature of the esterification reaction is 0 to 25 °C.

18. A photosensitive resin composition, comprising an alkali-soluble resin, an acrylate monomer and a photoinitiator, characterized in that, The photoinitiator includes the naphthalene-structured oxime ester photoinitiator according to any one of claims 1 to 7.

19. The photosensitive resin composition according to claim 18, characterized in that,By mass, in the photosensitive resin composition, the content of the photoinitiator is 0.5 to 5 parts; and / or, the content of the alkali-soluble resin is 15 to 50 parts, and / or, the content of the acrylate monomer is 10 to 30 parts.

20. A cured product, characterized in that The cured product is prepared by irradiating the photosensitive resin composition according to any one of claims 18 to 19 with energy rays.

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