Nitrocarbazole (ketone) oxime ester compound and photoinitiator containing same

Abstract

The invention belongs to the technical field of photocuring, and particularly relates to a nitrocarbazole (ketone) oxime ester compound and a photoinitiator containing the compound, and the compound has a structure as shown in a formula (I). The compound has high curing hardness and excellent photosensitive activity, can be used as a photoinitiator, and is especially suitable for a UV-light source. # imgabs0 #

Description

Technical Field

[0001] The invention belongs to the technical field of photocuring, and in particular relates to a nitrocarbazole (ketone) oxime ester compound and a photoinitiator containing the compound. Background Art

[0002] Color photoresist is an important material for color filters, mainly composed of three polymer materials: red, green and blue. In recent years, with the increase in demand for televisions and the continuous expansion of panel factories, the demand for color photoresist has continued to grow. The traditional methods for making color photoresist include dyeing and electroprecipitation. These traditional methods all use metal Cr, but metal Cr is highly toxic and pollutes seriously. Therefore, the more advanced pigment dispersion method is currently used to make color photoresist. Its operation process is simple, and its color characteristics, heat resistance, light resistance and other properties are very excellent. The preparation of pigment photoresist is the key technology of the pigment dispersion method, and photoinitiator is one of the important raw materials for making photoresist. However, traditional photoinitiators, such as benzoin derivatives, benzyl ketal, acyl phosphine oxide, benzophenone / amine, etc., have the disadvantages of low sensitivity, poor solubility and poor storage stability, which will directly affect the transparency and heat resistance of color photoresist and cannot meet the production of high-quality pigment photoresist.

[0003] In 1904, A Werner first reported the photochemical properties of oxime ester compounds. In 1970, oxime ester compounds began to be used as photoinitiators. The oxime ester photoinitiator Quantacure PDO was widely used commercially. Although the compound has high photoinitiation activity, it has poor stability and was soon replaced by other free radical initiators. In recent years, some people have introduced groups that can increase the molecular conjugation surface into the oxime ester compound molecules, further improving the initiation efficiency and stability of oxime ester derivatives, and attracting attention to the preparation and application of oxime ester photoinitiators. The more typical ones are the research of Hisatoshi Kura et al. on the introduction of diphenyl sulfide groups into oxime ester compounds and the research of Dietliker K et al. on the introduction of carbazole groups into oxime ester compounds. Because these groups have a larger conjugated system and stronger intramolecular electron transfer characteristics, the stability and photosensitivity of oxime ester compounds are greatly improved.

[0004] Existing carbazole oxime photoinitiators meet the requirements of liquid crystal flat panel displays to a certain extent. On the other hand, by introducing electron-withdrawing groups such as nitro groups into the structure of carbazole oxime compounds, the interaction between DA causes the ultraviolet absorption spectrum to be red-shifted to a certain extent. For example, by introducing -NO2 on the carbazole ring, the absorption spectrum of carbazole oxime compounds can be red-shifted, with relatively large absorption at 365-405nm. At present, UV-curing exposure machines have gradually changed from mercury lamps to UV-LED lamps. With the improvement of LDI exposure machines and the improvement of production efficiency, many fields have directly used computer graphics and direct printing due to the process and equipment of laser direct drawing, and no longer use masks.

[0005] Currently, there are not many photoinitiators that show excellent application performance under UV-light excitation, so there is a continuous demand for such highly photosensitized, low-cost and UV-light-compatible photoinitiators. Summary of the invention

[0006] Problem that the invention aims to solve

[0007] The present invention aims to provide a nitrocarbazole (ketone) oxime ester compound and a photoinitiator containing the compound. The compound has excellent photosensitivity, high curing hardness and is suitable for a photoinitiator of a UV-light source.

[0008] Solutions for solving problems

[0009] In a first aspect, the present invention provides a compound having a structure shown in formula (I):

[0010]

[0011] in,

[0012] X is absent or represents a carbonyl group;

[0013] R1 represents C1-C 20 Alkyl or C3~C 20 Cycloalkyl;

[0014] R2 represents C1-C 20 Alkyl, C3~C 20 Cycloalkyl or C6-C 20 Aryl;

[0015] R3 represents nitro or is replaced by one or more C1~C 20 Alkyl substituted or unsubstituted C6~C 20 Arylcarbonyl;

[0016] R4 represents a hydrogen atom, a nitro group, a cyano group, a C1-C 20 Alkyl, -S(C1~C 20 Alkyl), -O(C1~C 20 alkyl), C6~C 20 aryl, 4-20 membered heterocyclic group substituted or unsubstituted by one or more R5, C6-C 20 arylcarbonyl, 5-20 membered heteroarylcarbonyl substituted or unsubstituted by one or more R5, or -C(R6)=NOC(=O)-R7; if present, R6 and R7 each independently represent C1-C 20 alkyl;

[0017] If the groups represented by R1, R2 and R4 have an alkylene moiety, the methylene group may be interrupted 1 to 5 times by one or more -CH=CH-, -C≡C-, -CH=N-, -O-, -S-, -C(=O)-O-, -C(=O)-S-, -C(=O)-NH- or -NH-C(=O)-O-;

[0018] If present, each R5 independently represents C1 to C 20 Alkyl, C3~C 20 Cycloalkyl or C6~C 20 Aryl.

[0019] In some embodiments, the compound has a structure shown in Formula (Ia) or Formula (Ib):

[0020]

[0021] Preferably, the compound has a structure shown in formula (Ib):

[0022]

[0023] wherein R1, R2, R3 and R4 have the same meanings as those described in formula (I).

[0024] In some embodiments, at least one of R3 and R4 represents nitro.

[0025] In some preferred embodiments, R3 represents nitro.

[0026] In some embodiments, the compound has a structure shown in Formula (Ia-1) or Formula (Ib-1):

[0027]

[0028] Preferably, the compound has a structure shown in formula (Ib-1):

[0029]

[0030] wherein R1, R2 and R4 have the same meanings as those described in formula (I).

[0031] In some embodiments, the compound has a structure shown in Formula (Ia-2) or Formula (Ib-2):

[0032]

[0033] Preferably, the compound has a structure shown in formula (Ib-2):

[0034]

[0035] wherein R1, R2 and R4 have the same meanings as those described in formula (I).

[0036] In some embodiments, R1 represents C1-C 20 Alkyl or C3~C 10 The cycloalkyl group is preferably methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, isononyl, n-undecyl, n-dodecyl, 1,3,3-trimethylbutyl, 2,4,4-trimethylpentyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, and more preferably methyl, ethyl, n-hexyl or 1,3,3-trimethylbutyl.

[0037] In some embodiments, R2 represents C1-C 20 Alkyl, C3~C 10 Cycloalkyl or C6~C 10 The aryl group is preferably a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a phenyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group or a cyclohexyl group, and more preferably a methyl group, an ethyl group or a phenyl group.

[0038] In some embodiments, R4 represents a hydrogen atom, a nitro group, a cyano group, a C1-C 20 Alkyl, -S(C1~C 20 Alkyl), one or more C1~C 20 Alkyl substituted or unsubstituted C6~C 20 Aryl ketone group, one or more C1~C 20 an alkyl-substituted or unsubstituted 5- to 20-membered heteroaryl ketone group or -C(R5)=NOC(=O)-R6; R5 and R6 each independently represent C1 to C 20 Preferably, R4 represents a hydrogen atom, a nitro group or one or more C1 to C 20 Alkyl substituted or unsubstituted C6~C20 Aryl ketone group.

[0039] In some embodiments, the compounds of the present invention are selected from the following compounds:

[0040]

[0041]

[0042]

[0043]

[0044]

[0045]

[0046]

[0047]

[0048] In a second aspect, the present invention provides a photopolymerization initiator comprising the compound described in the first aspect.

[0049] In some embodiments, the photopolymerization initiator comprises the compound described in the first aspect as an active ingredient.

[0050] In a third aspect, the present invention provides a photosensitive composition comprising the photopolymerization initiator described in the second aspect and a polymerizable compound having an ethylenically unsaturated bond.

[0051] In some embodiments, the photopolymerization initiator and the polymerizable compound having an ethylenically unsaturated bond are used in a ratio of 1:(1-99) in parts by weight.

[0052] In some embodiments, the photosensitive composition further contains an inorganic compound.

[0053] In some embodiments, the inorganic compound may include but is not limited to: metal oxides such as nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, aluminum oxide; silicon dioxide, layered clay minerals, Milori blue, calcium carbonate, magnesium carbonate, cobalt series, manganese series, glass powder, mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides, aluminum silicate, calcium silicate, aluminum hydroxide, platinum, gold, silver, copper, etc.; among which, the inorganic compound is preferably titanium oxide, silicon dioxide, layered clay minerals, silver, etc.

[0054] In a fourth aspect, the present invention provides an alkali-developable photosensitive resin composition, which contains the photopolymerization initiator described in the second aspect and an alkali-developable compound having an ethylenically unsaturated bond.

[0055] In a fifth aspect, the present invention provides a colored alkali-developable photosensitive resin composition, which contains the alkali-developable photosensitive resin composition described in the fourth aspect and a colorant.

[0056] In a sixth aspect, the present invention provides a chemical for electronic industry, comprising the photopolymerization initiator described in the second aspect.

[0057] In some embodiments, the electronic industrial chemical is an anti-corrosion ink, a solder resist ink, a coating or an adhesive.

[0058] In a seventh aspect, the present invention provides a photoresist comprising at least one photopolymerization initiator as described in the second aspect.

[0059] In some embodiments, the photoresist further contains a multifunctional acrylate monomer, an alkali-soluble resin, an auxiliary agent, a colorant, and a solvent.

[0060] In an eighth aspect, the present invention provides an article obtained by processing using any material of the electronic industry chemicals described in the sixth aspect or the photoresist described in the seventh aspect as a raw material.

[0061] In some embodiments, the article is a printed circuit board (PCB), an LCD display, an OLED display, a solar panel, a consumer electronic product, or a semiconductor device.

[0062] In some embodiments, the consumer electronic product is a mobile phone, a television, or a computer.

[0063] Effects of the Invention

[0064] The nitrocarbazole (ketone) oxime ester compound of the present invention has high curing hardness, strong stability, excellent photosensitivity, and can be used as a photoinitiator, especially a photoinitiator suitable for UV-light sources. In addition, compared with commercial photoinitiators, the synthesis route of the compound of the present invention adopts Friedel-Crafts reaction instead of alkylation reaction, which reduces one step of alkylation reaction and further reduces production costs. DETAILED DESCRIPTION

[0065] Various exemplary embodiments, features and aspects of the present invention will be described in detail below. The word "exemplary" used here means "used as an example, embodiment or illustrative". Any embodiment described here as "exemplary" is not necessarily interpreted as being superior or better than other embodiments.

[0066] In addition, in order to better illustrate the present invention, numerous specific details are provided in the following specific embodiments. It should be understood by those skilled in the art that the present invention can be implemented without certain specific details. In other examples, methods, means, equipment and steps well known to those skilled in the art are not described in detail in order to highlight the subject matter of the present invention.

[0067] Unless otherwise stated, the units used in this specification are all international standard units, and the numerical values ​​and numerical ranges appearing in the present invention should be understood to include the inevitable systematic errors in industrial production.

[0068] In this specification, the word "may" means both performing a certain process and not performing a certain process.

[0069] In this specification, the references to "some specific / preferred embodiments", "other specific / preferred embodiments", "embodiments", etc., mean that the specific elements (e.g., features, structures, properties and / or characteristics) described in connection with the embodiments are included in at least one embodiment described herein, and may or may not exist in other embodiments. In addition, it should be understood that the elements may be combined in various embodiments in any suitable manner.

[0070] [Definition of terms]

[0071] In this specification, "photoinitiator" or "photopolymerization initiator" refers to a type of compound that can absorb energy under light, thereby initiating polymerization, cross-linking and curing of monomers.

[0072] In this specification, the numerical range expressed using "a numerical value A to a numerical value B" means a range including the endpoints numerical values ​​A and B.

[0073] In the present specification, when "normal temperature" or "room temperature" is used, the temperature may be 15°C to 30°C, further 15°C to 25°C, for example, 20°C.

[0074] In the present invention, "alkyl" refers to a monovalent saturated aliphatic hydrocarbon group, which can be a straight chain group or a branched chain group. The alkyl group in the present invention can be "C1-C 20 Alkyl", "C1-C 15 Alkyl", "C1-C 10"C1-C5 alkyl", "C1-C5 alkyl" or "C1-C3 alkyl" means that the group is an alkyl group and the number of carbon atoms in the carbon chain is between 1-20, 1-15, 1-10, 1-5 or 1-3, respectively. The alkyl group in the present invention can be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl, neopentyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, n-hexyl, n-heptyl, n-octyl, isononyl, n-decyl, n-undecyl, n-dodecyl, 1,3,3-trimethylbutyl, 2,4,4-trimethylpentyl, etc.

[0075] In the present invention, "cycloalkyl" refers to a monocyclic, bicyclic or polycyclic monovalent saturated aliphatic hydrocarbon group with a specific number of carbon atoms. The cycloalkyl group in the present invention includes monocyclic cycloalkyl and condensed ring cycloalkyl (including spirocyclic alkyl, paracycloalkyl, bridged cycloalkyl), for example, "C3-C 20 Cycloalkyl", "C3-C 15 Cycloalkyl", "C3-C 10 The cycloalkyl group in the present invention may be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopropyl, 2-ethyl-cyclopentyl, dimethylcyclobutyl, etc.

[0076] In the present invention, "heterocyclyl" refers to a saturated or partially saturated monocyclic or polycyclic non-aromatic substituent having ring carbon atoms and at least one ring heteroatom, for example, a "3-20 membered heterocyclyl" containing 3 to 20 ring atoms, wherein 1, 2, 3 or more ring atoms are selected from N, O or S, and the remaining ring atoms are C. The heterocyclyl in the present invention may be a "3-20 membered heterocyclyl", "3-14 membered heterocyclyl", "3-12 membered heterocyclyl", "4-11 membered heterocyclyl", "3-8 membered heterocyclyl", "4-8 membered heterocyclyl", "4-7 membered heterocyclyl", "4-6 membered heterocyclyl", "5-10 membered heterocyclyl", "5-8 membered heterocyclyl" or "5-6 membered heterocyclyl", and the number of heteroatoms may be 1, 2 or 3.

[0077] In the present invention, "aryl" refers to a group containing 6 to 20 carbon atoms (C6-C 20 aryl), or 6-18 carbon atoms (C6-C 18 aryl), or 6-12 carbon atoms (C6-C 12 aryl), or 6-10 carbon atoms (C6-C 10 The term "aryl" refers to a monocyclic, bicyclic, tricyclic, tetracyclic or pentacyclic aromatic carbocyclic ring system of the present invention. Examples of aryl groups may include phenyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, fluorenyl, and the like.

[0078] In the present invention, "heteroaryl" refers to an aromatic monocyclic or polycyclic ring system containing a 5-20 membered structure (5-20 membered heteroaryl), or a 5-18 membered structure (5-18 membered heteroaryl), or a 5-12 membered structure (5-12 membered heteroaryl), or a 5-10 membered structure (5-10 membered heteroaryl), or a 5-6 membered structure (5-6 membered heteroaryl), wherein at least one ring atom is a heteroatom and the remaining atoms are carbon, the heteroatoms are independently selected from N, O or S, and the number of heteroatoms is preferably 1, 2 or 3. Examples of heteroaryl groups may include carbazolyl, furanyl, thienyl, oxazolyl, thiazolyl, isoxazolyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, quinolyl, isoquinolyl, pteridinyl, purinyl, indolyl, isoindolyl, indazolyl, benzofuranyl, benzothienyl, benzopyridinyl, benzopyrimidinyl, benzopyrazinyl, benzimidazolyl, and the like.

[0079] In the present invention, "carbonyl" refers to "-C(=O)-".

[0080] In the present invention, "nitro" refers to "-NO2".

[0081] In the present invention, "cyano" refers to "-CN".

[0082] Example

[0083] The embodiments of the present invention will be described in detail below in conjunction with the examples, but those skilled in the art will appreciate that the following examples are only used to illustrate the present invention and should not be considered to limit the scope of the present invention. If no specific conditions are specified in the examples, they are carried out according to normal conditions or the conditions recommended by the manufacturer. If the manufacturer is not specified for the reagents or instruments used, they are all conventional products that can be obtained commercially.

[0084] Example 1: Synthesis of Compound 92

[0085] Synthesis of compound S1:

[0086]

[0087] 100 g of 3-nitrocarbazole (as compound A) and 400 g of ethylene dichloride were added to the reaction flask, followed by 48 g of propionyl chloride (as compound B) at 0-10°C, and then the temperature was raised to room temperature and reacted overnight. After the reaction was completed, water was added and the liquid was separated to obtain an organic phase containing compound S1 for later use.

[0088] Synthesis of compound S2:

[0089]

[0090] The organic phase containing compound S1 was added to the reaction flask, followed by 48.7 g of hydroxylamine hydrochloride and 69.4 g of sodium acetate, and the temperature was raised to reflux for 3 h. After the reaction was completed, the temperature was lowered, the inorganic salts were removed by suction filtration, and the filter cake was rinsed with a small amount of dichloroethane. After the organic phase was concentrated, ethanol was used for pulping to obtain compound S2 (solid, 109 g, yield 82%).

[0091] Synthesis of compound 92:

[0092]

[0093] Add 100 g of the above compound S2 and 400 mL of dichloroethane to the reaction bottle, then cool to 0-5°C, drop 30.5 g of acetyl chloride (as compound C), react for 1 h, and after the reaction is complete, add alkali solution for neutralization, wash with water until neutral, separate the liquids, concentrate the organic phase, and slurry with ethanol to obtain compound 92 (yellow solid, 105.2 g, yield 91.6%). MS (ESI+): m / z 326.25 [M+H] + . 1 H NMR (500MHz, CDCl3) δ9.25 (s, 1H), 8.20-8.11 (m, 2H), 7.98 (d, J = 9.0Hz, 1H), 7.52 (d, J = 6.6Hz, 1H), 7. 38(d,J=7.8Hz,1H),7.30(t,J=7.6Hz,1H),2.81(q,J=6.8Hz,2H),2.13(s,3H),1.25(t,J=6.8Hz,3H).

[0094] Example 2: Synthesis of Compound 19

[0095] Synthesis of compound S3:

[0096]

[0097] Add 50 g of compound S1, 100 g of concentrated hydrochloric acid, and 30 g of hydrogen chloride ethyl acetate solution to the reaction bottle, stir until completely dissolved, and then cool to 10-15°C; add 15.4 g of sodium nitrite, continue to react at this temperature for 2 h, add water to quench the reaction, separate the liquids, and concentrate the organic phase to obtain a viscous liquid, namely compound S3.

[0098] Synthesis of compound 19:

[0099]

[0100] The above viscous liquid (compound S3) and 400 mL of dichloroethane were added to the reaction flask, then the temperature was lowered to 0-5°C, 16.1 g of acetyl chloride (as compound D) was added dropwise, and the reaction was continued for 1 h. After the reaction was completed, an alkali solution was added for neutralization, and then the mixture was washed with water until neutral, and the liquid was separated. After the organic phase was concentrated, the mixture was slurried with ethanol to obtain compound 19 (solid, 49.2 g, yield 77.8%). MS (ESI+): m / z 340.05 [M+H] + . 1 H NMR (500MHz, CDCl3) δ9.25(s,1H),8.36(d,J=9.0Hz,1H),8.24(d,J=9.0Hz,1H),8.15(d,J=8.8Hz,1 H),7.70(d,J=6.6Hz,1H),7.42(d,J=7.5Hz,1H),7.31(d,J=8.2,Hz,1H),2.50(s,3H),2.19(s,3H).

[0101] Embodiments 3 to 6

[0102] Referring to the synthetic route of compound 92 in Example 1, compound A, compound B and compound C were replaced by the compounds in Table 1 to prepare a series of specific compounds of the present invention (see Table 1).

[0103] Table 1

[0104]

[0105] Embodiments 7 to 10

[0106] Referring to the synthetic route of compound 19 in Example 2, compound A, compound B and compound D were replaced with the compounds in Table 2 to prepare a series of specific compounds of the present invention (see Table 2).

[0107] Table 2

[0108]

[0109] in, The preparation method is referred to CN109232383A;

[0110] The preparation method refers to WO2021177654A1, except that the starting material N-ethylcarbazole is replaced by carbazole.

[0111] Example 11: Preparation of Photosensitive Composition No. 1

[0112] 6.4 g of trimethylolpropane triacrylate, 3 g of compound 92, and 87.7 g of ethyl cellosolve were added to 15.5 g of an acrylic copolymer, and the mixture was sufficiently stirred to obtain a photosensitive composition No. 1.

[0113] The acrylic copolymer was obtained by dissolving 20 parts by mass of methacrylic acid, 15 parts by mass of hydroxyethyl methacrylate, 10 parts by mass of methyl methacrylate and 55 parts by mass of butyl methacrylate in 300 parts by mass of ethyl cellosolve, adding 0.75 parts by mass of azobisisobutyronitrile under a nitrogen atmosphere, and reacting the mixture at 70° C. for 5 hours to obtain the acrylic copolymer.

[0114] Examples 12 to 20: Preparation of Photosensitive Compositions No. 2 to No. 10

[0115] Photosensitive polymerizable compositions No. 2 to No. 10 were obtained by the same method as in Example 11 except that compound 92 was replaced with the compounds shown in Table 3 below.

[0116] Comparative Examples 1 to 4: Preparation of Photosensitive Compositions No. 11 to No. 14

[0117] Photosensitive polymerizable compositions Nos. 11 to 14 were obtained by the same method as in Example 11 except that compound 92 was replaced with the compounds shown in Table 3 below.

[0118] Table 3

[0119]

[0120] The structures of the compounds involved in the comparative examples are as follows:

[0121]

[0122] Effect example 1: Hardness test

[0123] The photosensitive compositions prepared in Examples 11 to 20 and Comparative Examples 1 to 4 were coated on a polyethylene terephthalate film having a thickness of 50 μm using a #3 rod coater. The light of a high-pressure mercury lamp of 80 W / cm was irradiated thereon using a light irradiation device with a leather conveyor. The distance from the lamp to the leather conveyor was set to 10 cm, and the linear speed of the leather conveyor was set to 8 cm / min. After curing, the film was placed at room temperature for 24 hours, and then the pencil hardness at a load of 1 kg was measured using a pencil hardness tester. The test results are shown in Table 4.

[0124] Table 4

[0125] Example Pencil hardness Embodiment 11 3H Example 12 3H Embodiment 13 3H Embodiment 14 3H Embodiment 15 3H Example 16 3H Embodiment 17 3H Embodiment 18 3H Embodiment 19 3H Embodiment 20 3H Comparative Example 1 1H Comparative Example 2 3H Comparative Example 3 3H Comparative Example 4 3H

[0126] As shown in Table 4, the curing hardness of the compounds in Examples 11 to 20 is significantly higher than that of the compound OXE02 in Comparative Example 1, and is comparable to the hardness of the compounds 339, 340 and 341 in Comparative Examples 2 to 4. The results show that the change of the oxime ester substitution site has little effect on the change of the curing hardness, while the nitro substituent on the carbazole ring has a greater effect on the change of the curing hardness.

[0127] Preparation Example of Polymerizable Composition (Photosensitive Resin)

[0128] Embodiment 21

[0129] 96 g of acrylic resin prepolymer, 4 g of compound 92 (prepared in Example 1) and 100 g of tetrahydrofuran were added to a reaction container at 35° C., reacted for 6 hours, and stirred evenly to obtain polymerizable composition No. 1.

[0130] The acrylic resin prepolymer is obtained by the following method: 10 parts by mass of methacrylic acid, 10 parts by mass of methyl methacrylate and 10 parts by mass of isobornyl methacrylate are dissolved in 50 parts by mass of propylene glycol methyl ether acetate, and the reaction system is kept warm at 70-80°C for 2 hours under the catalysis of 0.5 parts by mass of azobisisobutyronitrile (AIBN) to obtain an acrylic resin prepolymer.

[0131] Embodiments 22 to 30

[0132] Polymerizable compositions No. 2 to No. 10 were prepared by following the method of Example 21 except that compound 92 was replaced by the compounds shown in Table 5 below.

[0133] Comparative Examples 5 to 8

[0134] Polymerizable compositions No. 11 to No. 14 were prepared by following the method of Example 21 except that compound 92 was replaced by the compounds shown in Table 5 below.

[0135] Table 5

[0136] Example Polymerizable composition Acrylic resin prepolymer Compound Tetrahydrofuran Embodiment 21 No.1 96g Compound 92 100g Embodiment 22 No.2 96g Compound 19 100g Embodiment 23 No.3 96g Compound 62 100g Embodiment 24 No.4 96g Compound 63 100g Embodiment 25 No.5 96g Compound 133 100g Embodiment 26 No.6 96g Compound 106 100g Embodiment 27 No.7 96g Compound 4 100g Embodiment 28 No.8 96g Compound 9 100g Embodiment 29 No.9 96g Compound 24 100g Embodiment 30 No.10 96g Compound 144 100g Comparative Example 5 No.11 96g OXE02 100g Comparative Example 6 No.12 96g 339 100g Comparative Example 7 No.13 96g 340 100g Comparative Example 8 No.14 96g 341 100g

[0137] Effect Example 2: Evaluation of photosensitivity under blue and green light sources

[0138] The polymerizable compositions of Examples 21 to 30 and Comparative Examples 5 to 8 were evaluated for photosensitivity according to the following method.

[0139] The polymerizable compositions of Examples 21 to 30 and Comparative Examples 5 to 8 were coated on a glass substrate using a spin coater, and heated to 100°C for 2 minutes at a rotation speed of 1500 rpm using a coating machine, and cooled to room temperature to form a coating film on the surface of the glass substrate. Then, the polymerizable compositions of Examples 21 to 30 and Comparative Examples 5 to 8 were cured under irradiation with a blue light source and a green light source, respectively. The data shown in Table 6 represent the exposure amount of the required light energy, and the smaller the value, the better the photosensitivity. The results are shown in Table 6.

[0140] Table 6

[0141]

[0142] As can be seen from Table 6, under the irradiation of blue and green light sources, the energy required for curing the polymerizable composition to which the oxime ester compound of the present invention is added is significantly less than the energy required for curing by adding the compounds used in the comparative examples (OXE02, 339, 340 and 341). The oxime ester compound of the present invention has excellent photosensitivity compared with the compounds used in comparative examples 5 to 8 (OXE02, 339, 340 and 341).

[0143] As described above, when the oxime ester compound of the present invention is used, the photosensitivity is excellent, indicating that the oxime ester compound of the present invention can be used as a photoinitiator for optical purposes.

[0144] It should be noted that, although the technical solution of the present invention is introduced with specific examples, those skilled in the art will appreciate that the present invention should not be limited thereto.

[0145] The embodiments of the present invention have been described above, and the above description is exemplary, not exhaustive, and is not limited to the disclosed embodiments. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. The selection of terms used herein is intended to best explain the principles of the embodiments, practical applications, or technical improvements in the market, or to enable other persons of ordinary skill in the art to understand the embodiments disclosed herein.

Claims

1. A compound having a structure represented by formula (I): in, X is absent or represents a carbonyl group; R1 represents C1-C 20 Alkyl or C3~C 20 Cycloalkyl; R2 represents C1-C 20 Alkyl, C3~C 20 Cycloalkyl or C6-C 20 Aryl; R3 represents nitro or is replaced by one or more C1~C 20 Alkyl substituted or unsubstituted C6~C 20 Arylcarbonyl; R4 represents a hydrogen atom, a nitro group, a cyano group, a C1-C 20 Alkyl, -S(C1~C 20 Alkyl), -O(C1~C 20 alkyl), C6~C 20 aryl, 4-20 membered heterocyclic group substituted or unsubstituted by one or more R5, C6-C 20 arylcarbonyl, 5-20 membered heteroarylcarbonyl substituted or unsubstituted by one or more R5, or -C(R6)=NOC(=O)-R7; if present, R6 and R7 each independently represent C1-C 20 alkyl; If the groups represented by R1, R2 and R4 have an alkylene moiety, the methylene group may be interrupted 1 to 5 times by one or more -CH=CH-, -C≡C-, -CH=N-, -O-, -S-, -C(=O)-O-, -C(=O)-S-, -C(=O)-NH- or -NH-C(=O)-O-; If present, each R5 independently represents C1 to C 20 Alkyl, C3~C 20 Cycloalkyl or C6~C 20 Aryl.

2. The compound according to claim 1, characterized in that The compound has a structure shown in formula (Ia) or formula (Ib): wherein R1, R2, R3 and R4 have the same meanings as those defined in claim 1.

3. The compound according to claim 1 or 2, characterized in that At least one of R3 and R4 represents a nitro group.

4. The compound according to any one of claims 1 to 3, characterized in that R1 represents C1~C 20 Alkyl or C3~C 10 Cycloalkyl, preferably methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, isononyl, n-undecyl, n-dodecyl, 1,3,3-trimethylbutyl, 2,4,4-trimethylpentyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, more preferably methyl, ethyl, n-hexyl or 1,3,3-trimethylbutyl; R2 represents C1~C 20 Alkyl, C3~C 10 Cycloalkyl or C6~C 10 The aryl group is preferably a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a phenyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group or a cyclohexyl group, and more preferably a methyl group, an ethyl group or a phenyl group.

5. The compound according to any one of claims 1 to 4, characterized in that R4 represents a hydrogen atom, a nitro group, a cyano group, a C1-C 20 Alkyl, -S(C1~C 20 Alkyl), one or more C1~C 20 Alkyl substituted or unsubstituted C6~C 20 Aryl ketone group, one or more C1~C 20 an alkyl-substituted or unsubstituted 5- to 20-membered heteroaryl ketone group or -C(R5)=NOC(=O)-R6; R5 and R6 each independently represent C1 to C 20 alkyl; Preferably, R4 represents a hydrogen atom, a nitro group or one or more C1-C 20 Alkyl substituted or unsubstituted C6~C 20 Aryl ketone group.

6. The following compounds:

7. A photopolymerization initiator, comprising the compound according to any one of claims 1 to 6; further, the photopolymerization initiator comprises the compound according to any one of claims 1 to 6 as an active ingredient.

8. A photosensitive composition comprising the photopolymerization initiator according to claim 7 and a polymerizable compound having an ethylenically unsaturated bond; preferably, the ratio of the photopolymerization initiator to the polymerizable compound having an ethylenically unsaturated bond is 1:(1-99) in parts by weight; Furthermore, the photosensitive composition further contains an inorganic compound. 9 . An alkali-developable photosensitive resin composition comprising the photopolymerization initiator according to claim 7 and an alkali-developable compound having an ethylenically unsaturated bond. 10 . A colored alkali-developable photosensitive resin composition comprising the alkali-developable photosensitive resin composition according to claim 9 and a colorant.

11. A chemical for electronic industry, comprising the photopolymerization initiator according to claim 7; preferably, the chemical for electronic industry is an anti-corrosion ink, a solder resist ink, a coating or an adhesive.

12. A photoresist, comprising at least one photopolymerization initiator according to claim 7; further, the photoresist further comprises a multifunctional acrylate monomer, an alkali-soluble resin, an auxiliary agent, a colorant and a solvent.

13. An article obtained by processing using any material of the electronic industry chemical according to claim 11 or the photoresist according to claim 12 as a raw material; preferably, the article is a printed circuit board, an LCD display, an OLED display, a solar panel, a consumer electronic product or a semiconductor device; more preferably, the consumer electronic product is a mobile phone, a television or a computer.

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