Carbonyl difluorene (ketone) oxime ester compound, product containing same and application of carbonyl difluorene (ketone) oxime ester compound

Abstract

The invention belongs to the technical field of photocuring, and relates to a carbonyl difluorene (ketone) oxime ester compound, a product containing the same and application of the carbonyl difluorene (ketone) oxime ester compound. Specifically, the structure of the compound is shown as a formula (A), and compared with an existing commercial photoinitiator, the probability of oxime ester bond breakage is reduced, and material storage and transportation are facilitated. # imgabs0 #

Description

Technical Field

[0001] The invention belongs to the technical field of photocuring, and relates to a carbonyl difluorene (ketone) oxime ester compound, a product containing the same, and an application of the same in the field of photocuring. 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, which has a simple operation process and excellent color characteristics, heat resistance and light resistance. 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 and its derivatives, benzyl ketal, acyl phosphine oxide, benzophenone / amine, etc. have the disadvantages of low sensitivity, poor solubility and weak storage stability, which will directly affect the transparency and heat resistance of color photoresist and cannot meet the requirements for making 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. Among them, the oxime ester photoinitiator Quanta cure PDO was widely used commercially. Although this compound has high photoinitiating 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 larger conjugated systems and stronger intramolecular electron transfer characteristics, the stability and photosensitivity of this type of oxime ester compounds are greatly improved.

[0004] Oxime ester bond cleavage is a common mechanism in photoinitiators, especially under light conditions. However, the cleavage of oxime ester bonds may bring some potential hazards to photoinitiators, mainly including:

[0005] 1) Reduced photostability: The oxime ester bond is easily broken under light, which may affect the photostability of the photoinitiator, resulting in its performance degradation during storage and use.

[0006] 2) Potential environmental impact: Since the cleavage of the oxime ester bond may produce small molecules, these substances may have a certain impact on the environment. For example, if these small molecules are persistent organic pollutants, they may exist in the environment for a long time, posing a potential risk to the ecosystem.

[0007] 3) Human health risks: Free radicals or other small molecules generated by the cleavage of oxime ester bonds may pose certain health risks to the human body, especially if not properly controlled.

[0008] 4) Increased application difficulty: If the small molecular fragments produced by the breakage of the oxime ester bond are not effectively removed, they will easily remain in the entire application system, causing problems such as malfunction of the application equipment and affecting the quality of the final product.

[0009] Therefore, even if the existing photoinitiators have excellent application performance, how to solve the problem of oxime ester bond breakage in oxime ester compounds used as photoinitiators and reduce these potential hazards has become one of the current research directions of oxime ester photoinitiators. Summary of the invention

[0010] Problem that the invention aims to solve

[0011] In view of the above problems existing in the prior art, the present invention provides a series of novel carbonyl difluorene (ketone) oxime ester compounds, products containing the same, and applications thereof in the field of photocuring, in order to solve the above problems.

[0012] Solutions for solving problems

[0013] In a first aspect, the present invention provides a carbonyl difluorene (keto) oxime ester compound as shown in formula (A),

[0014]

[0015] in,

[0016] Each A is independently absent or represents a carbonyl group;

[0017] Every R 1 are each independently selected from substituted or unsubstituted C 1-20 Alkyl and substituted or unsubstituted C 3-20 Cycloalkyl;

[0018] Every R 2 are each independently selected from substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 3-20 Cycloalkyl and substituted or unsubstituted C 6-20 Aryl;

[0019] Every R3 are each independently selected from hydrogen, nitro, cyano, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 6-20 Aryl acyl and substituted or unsubstituted 4-20 membered heteroaryl acyl;

[0020] When the alkyl, cycloalkyl, aryl and heteroaryl groups are substituted by one or more substituents, each substituent is independently selected from C 1-20 Alkyl, C 3-20 Cycloalkyl, C 6-20 Aryl and 4-20 membered heteroaryl;

[0021] The heteroaryl group contains 1 to 3 heteroatoms independently selected from N, O and S.

[0022] In a second aspect, the present invention provides a polymerizable composition comprising the compound in the first part.

[0023] Preferably, the polymerizable composition further comprises at least one of the following components:

[0024] a) acrylic resin prepolymer;

[0025] b) Solvent.

[0026] More preferably, the polymerizable composition comprises the following components in parts by weight: 2-6 parts of the compound in the first part; 94-98 parts of the acrylic resin prepolymer; and 100 parts of the solvent.

[0027] In a third aspect, the present invention provides a photosensitive composition comprising the compound in the first part.

[0028] Preferably, the photosensitive composition further comprises at least one of the following components:

[0029] a) alkali soluble resin;

[0030] b) photopolymerizable compounds;

[0031] c) Solvent.

[0032] More preferably, the photosensitive composition comprises the following components in parts by weight: 1-5 parts of the compound in the first part; 10-20 parts of the alkali-soluble resin; 5-10 parts of the photopolymerizable compound; and 80-100 parts of the solvent.

[0033] In the fourth part, the present invention provides a photoresist comprising the following components:

[0034] i) the compounds in Part I;

[0035] ii) alkali soluble resin;

[0036] iii) photopolymerizable compounds;

[0037] iv) Auxiliary agents.

[0038] Preferably, the auxiliary agent is selected from solvents, colorants, fillers, dispersants, antioxidants, ultraviolet absorbers, curing accelerators and thermal polymerization inhibitors.

[0039] In the fifth part, the present invention provides the use of the compound in the first part, the polymerizable composition in the second part, the photosensitive composition in the third part or the photoresist in the fourth part in the field of photocuring.

[0040] Effects of the Invention

[0041] Compared with existing commercial photoinitiators, the oxime ester compound of the present invention greatly reduces the vibration within the molecule due to its rigid structure, so that after absorbing ultraviolet light, less energy is transferred to the oxime ester bond, reducing the probability of oxime ester bond breaking and facilitating material storage and transportation. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 This is a graph showing the relationship between the HPLC deterioration ratio of oxime ester compounds and time. DETAILED DESCRIPTION

[0043] Carbonyl difluorene (keto) oxime ester compounds

[0044] In order to solve the problem of easy breakage of oxime ester bonds in photoinitiator molecules in the prior art, the present invention provides a carbonyl difluorene (ketone) oxime ester compound, the structure of which can be shown as formula (A):

[0045]

[0046] in,

[0047] Each A is independently absent or represents a carbonyl group;

[0048] Every R 1 are each independently selected from substituted or unsubstituted C 1-20 Alkyl and substituted or unsubstituted C 3-20 Cycloalkyl;

[0049] Every R 2 are each independently selected from substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 3-20 Cycloalkyl and substituted or unsubstituted C 6-20 Aryl;

[0050] Every R 3are each independently selected from hydrogen, nitro, cyano, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 6-20 Aryl acyl and substituted or unsubstituted 4-20 membered heteroaryl acyl;

[0051] When the alkyl, cycloalkyl, aryl and heteroaryl groups are substituted by one or more substituents, each substituent is independently selected from C 1-20 Alkyl, C 3-20 Cycloalkyl, C 6-20 Aryl and 4-20 membered heteroaryl;

[0052] The heteroaryl group contains 1 to 3 heteroatoms independently selected from N, O and S.

[0053] In one embodiment of the present invention, the structure of the carbonyl difluorene (keto) oxime ester compound may be as shown in formula (I) or formula (II):

[0054]

[0055] in,

[0056] R 1 , R 2 and R 3 As defined in formula (A).

[0057] In one embodiment of the present invention, in formula (A), formula (I) and formula (II), each R 1 Can be independently selected from C 1-20 Alkyl and C 3-20 Cycloalkyl.

[0058] In one embodiment of the present invention, in formula (A), formula (I) and formula (II), each R 1 Can be independently selected from C 1-8 Alkyl and C 3-8 Cycloalkyl.

[0059] In one embodiment of the present invention, in formula (A), formula (I) and formula (II), each R 1 The radicals may be each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, 2,4,4-trimethylpentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.

[0060] In one embodiment of the present invention, in formula (A), formula (I) and formula (II), each R 1Each may be independently selected from methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, 2,4,4-trimethylpentyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

[0061] In one embodiment of the present invention, in formula (A), formula (I) and formula (II), each R 1 The groups may be each independently selected from a methyl group, an ethyl group, a 2,4,4-trimethylpentyl group and a cyclohexyl group.

[0062] In one embodiment of the present invention, in formula (A), formula (I) and formula (II), each R 2 Can be independently selected from C 1-20 Alkyl, C 3-20 Cycloalkyl and C 6-20 Aryl.

[0063] In one embodiment of the present invention, in formula (A), formula (I) and formula (II), each R 2 Can be independently selected from C 1-6 Alkyl, C 3-6 Cycloalkyl and C 6-10 Aryl.

[0064] In one embodiment of the present invention, in formula (A), formula (I) and formula (II), each R 2 Each may be independently selected from methyl, ethyl, n-propyl, n-butyl, phenyl, naphthyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

[0065] In one embodiment of the present invention, in formula (A), formula (I) and formula (II), each R 2 The groups may each be independently selected from methyl and phenyl.

[0066] In one embodiment of the present invention, in formula (A), formula (I) and formula (II), each R 3 can be independently selected from hydrogen, nitro, cyano, C 1-20 Alkyl, 4-20 membered heteroaryl acyl and C 1-20 Alkyl, C 3-20 Cycloalkyl, C 6-20 Aryl or 4-20 membered heteroaryl substituted C 6-20 Aryl acyl.

[0067] In one embodiment of the present invention, in formula (A), formula (I) and formula (II), each R 3 can be independently selected from hydrogen, nitro, cyano, C 1-6 Alkyl, 4-10 membered heteroaryl acyl and C 1-6 Alkyl, C 3-6 Cycloalkyl, C6-10 Aryl or 4-10 membered heteroaryl substituted C 6-10 Aryl acyl;

[0068] In one embodiment of the present invention, in formula (A), formula (I) and formula (II), each R 3 Each may be independently selected from hydrogen, nitro, cyano, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, indole-2-carbonyl, isoindole-2-carbonyl, benzofuran-2-carbonyl, isobenzofuran-2-carbonyl, benzothiophene-2-carbonyl, isobenzothiophene-2-carbonyl, 2-methylbenzoyl, 2,4-dimethylbenzoyl, 2,6-dimethylbenzoyl and 2,4,6-trimethylbenzoyl.

[0069] In one embodiment of the present invention, in formula (A), formula (I) and formula (II), each R 3 Each may be independently selected from hydrogen, nitro, cyano and 2-methylbenzoyl.

[0070] In one embodiment of the present invention, the structure of the carbonyl difluorene (keto) oxime ester compound may be as shown in any one of Formula (1-1) to Formula (1-4) and Formula (2-1) to Formula (2-4):

[0071]

[0072] in,

[0073] R 1 and R 2 As defined in formula (A), formula (I) or formula (II);

[0074] In formula (1-4) and formula (2-4), each R 4 are each independently selected from substituted or unsubstituted C 6-20 aryl and substituted or unsubstituted 4-20 membered heteroaryl.

[0075] In one embodiment of the present invention, in formula (1-4) and formula (2-4), each R 4 may be independently selected from 4-20 membered heteroaryl and 1-20 Alkyl, C 3-20 Cycloalkyl, C 6-20 Aryl or 4-20 membered heteroaryl substituted C 6-20 Aryl.

[0076] In one embodiment of the present invention, in formula (1-4) and formula (2-4), each R 4 may be independently selected from 4-10 membered heteroaryl and 1-6 Alkyl, C3-6 Cycloalkyl, C 6-10 Aryl or 4-10 membered heteroaryl substituted C 6-10 Aryl.

[0077] In one embodiment of the present invention, in formula (1-4) and formula (2-4), each R 4 Each may be independently selected from indol-2-yl, isoindol-2-yl, benzofuran-2-yl, isobenzofuran-2-yl, benzothiophen-2-yl, isobenzothiophen-2-yl, 2-methylphenyl, 2,4-dimethylphenyl, 2,6-dimethylphenyl and 2,4,6-trimethylphenyl.

[0078] In one embodiment of the present invention, in formula (1-4) and formula (2-4), each R 4 Each may independently be 2-methylphenyl.

[0079] In one embodiment of the present invention, the carbonyl difluorene (keto) oxime ester compound can be selected from the following compounds:

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086] Products containing carbonyl difluorene (ketone) oxime ester photoinitiators

[0087] The carbonyl difluorene (ketone) oxime ester compound of the present invention can be used as a photopolymerization initiator (or photoinitiator) in the field of photocuring, for example, as a photoinitiator component in a polymerizable composition, a photosensitive composition or a photoresist.

[0088] To this end, the present invention provides a polymerizable composition (photosensitive resin), which may contain the above-mentioned carbonyldifluorene (keto)oxime ester compound of the present invention as a photoinitiator.

[0089] In one embodiment of the present invention, the polymerizable composition (photosensitive resin) may further comprise at least one of the following components:

[0090] a) acrylic resin prepolymer;

[0091] b) Solvent.

[0092] In one embodiment of the present invention, the acrylic resin prepolymer may be an acrylic mixture, for example, a mixture of (meth)acrylic acid and one or more esters thereof, or a mixture of two or more (meth)acrylates.

[0093] In one embodiment of the present invention, the acrylic resin prepolymer can be a mixture of methacrylic acid and methacrylate alcohol esters, for example, a mixture of methacrylic acid, methyl methacrylate and isobornyl methacrylate, especially a mixture of the three in a weight ratio of 1:1:1.

[0094] In one embodiment of the present invention, the acrylic resin prepolymer can be prepared by the following method: methacrylic acid, methyl methacrylate and isobornyl methacrylate are dissolved in propylene glycol methyl ether acetate, and reacted under the catalysis of azobisisobutyronitrile to obtain the acrylic resin prepolymer.

[0095] In one embodiment of the present invention, in the method for preparing the acrylic resin prepolymer,

[0096] The weight ratio of the sum of the weights of methacrylic acid, methyl methacrylate and isobornyl methacrylate to the weight ratio of propylene glycol methyl ether acetate is 1:5 to 5:5, preferably 3:5; and / or,

[0097] The weight ratio of the sum of the weights of methacrylic acid, methyl methacrylate and isobornyl methacrylate to the weight of azobisisobutyronitrile is 40:1-80:1, preferably 60:1; and / or,

[0098] The reaction temperature is 60-90°C, preferably 70-80°C; and / or,

[0099] The reaction time is 1-3 h, preferably 2 h.

[0100] In one embodiment of the present invention, the solvent may be an ether, for example, a cyclic ether.

[0101] In one embodiment of the present invention, the solvent may be tetrahydrofuran.

[0102] In one embodiment of the present invention, the polymerizable composition may include the following components in parts by weight:

[0103] 2-6 parts of the above-mentioned carbonyl difluorene (ketone) oxime ester compound of the present invention as a photoinitiator;

[0104] Acrylic resin prepolymer 94-98 parts;

[0105] 100 parts of solvent.

[0106] In one embodiment of the present invention, the polymerizable composition may include the following components in parts by weight:

[0107] 3-5 parts of the above-mentioned carbonyl difluorene (ketone) oxime ester compound of the present invention as a photoinitiator;

[0108] Acrylic resin prepolymer 95-97 parts;

[0109] 100 parts of solvent.

[0110] In one embodiment of the present invention, the polymerizable composition may include the following components in parts by weight:

[0111] 4 parts of the carbonyl difluorene (ketone) oxime ester compound of the present invention as a photoinitiator;

[0112] Acrylic resin prepolymer 96 parts;

[0113] 100 parts of solvent.

[0114] The present invention also provides a photosensitive composition, which may contain the above-mentioned carbonyl difluorene (keto) oxime ester compound of the present invention as a photoinitiator.

[0115] In one embodiment of the present invention, the photosensitive composition may further comprise at least one of the following components:

[0116] a) alkali soluble resin;

[0117] b) photopolymerizable compounds;

[0118] c) Solvent.

[0119] In one embodiment of the present invention, the alkali-soluble resin may be an acrylic copolymer, for example, a copolymer of (meth)acrylic acid and one or more esters thereof, or a copolymer of two or more (meth)acrylic esters.

[0120] In one embodiment of the present invention, the alkali-soluble resin may be a copolymer of methacrylic acid, alkyl methacrylate and hydroxyalkyl methacrylate, for example, a copolymer of methacrylic acid, methyl methacrylate, n-butyl methacrylate and hydroxyethyl methacrylate, especially a copolymer in which the weight ratio of the four is 4:2:11:3.

[0121] In one embodiment of the present invention, the photopolymerizable compound may be a photopolymerizable compound having an ethylenically unsaturated structure, for example, may be a (meth)acrylate polyol ester.

[0122] In one embodiment of the present invention, the photopolymerizable compound may be trimethylolpropane triacrylate.

[0123] In one embodiment of the present invention, the solvent may be a glycol monoether, for example, a glycol monofatty ether.

[0124] In one embodiment of the present invention, the solvent may be ethyl cellosolve (ie, ethylene glycol monoethyl ether).

[0125] In one embodiment of the present invention, the photosensitive composition may include the following components in parts by weight:

[0126] 1-5 parts of the above-mentioned carbonyl difluorene (ketone) oxime ester compound of the present invention as a photoinitiator;

[0127] 10-20 parts of alkali soluble resin;

[0128] 5-10 parts of photopolymerizable compound;

[0129] 80-100 parts of solvent.

[0130] In one embodiment of the present invention, the photosensitive composition may include the following components in parts by weight:

[0131] 2-4 parts of the above-mentioned carbonyl difluorene (ketone) oxime ester compound of the present invention as a photoinitiator;

[0132] 12-18 parts of alkali soluble resin;

[0133] 6-8 parts of photopolymerizable compound;

[0134] 80-90 parts of solvent.

[0135] In one embodiment of the present invention, the photosensitive composition may include the following components in parts by weight:

[0136] 3.0 parts of the carbonyl difluorene (ketone) oxime ester compound of the present invention as a photoinitiator;

[0137] 15.5 parts of alkali soluble resin;

[0138] 6.4 parts of photopolymerizable compound;

[0139] 87.7 parts of solvent.

[0140] In one embodiment of the present invention, the photosensitive composition may be composed of the carbonyldifluorene (keto)oxime ester compound of the present invention as a photoinitiator, an alkali-soluble resin, a photopolymerizable compound and a solvent.

[0141] The present invention also provides a photoresist, which may include the following components:

[0142] i) the above-mentioned carbonyl difluorene (keto) oxime ester compound of the present invention as a photoinitiator;

[0143] ii) alkali soluble resin;

[0144] iii) photopolymerizable compounds;

[0145] iv) Auxiliary agents.

[0146] In one embodiment of the present invention, the auxiliary agent in the photoresist can be selected from solvents, colorants, fillers, dispersants, antioxidants, ultraviolet absorbers, curing accelerators and thermal polymerization inhibitors.

[0147] In one embodiment of the present invention, the photoresist may comprise the following components:

[0148] i-1) the above-mentioned carbonyl difluorene (ketone) oxime ester compound of the present invention as a photoinitiator;

[0149] ii-1) alkali-soluble resin;

[0150] iii-1) a photopolymerizable compound;

[0151] iv-1) Solvent and optionally colorant.

[0152] Application of products in the field of light curing

[0153] The present invention provides the use of the carbonyl difluorene (ketone) oxime ester compound, polymerizable composition, photosensitive composition or photoresist in the field of photocuring.

[0154] The present invention is described in more detail below by specific examples, but the present invention is not limited to these examples. Unless otherwise specified, the reagents, materials and instruments used in these examples can be obtained by conventional commercial means.

[0155] <Synthesis of Compound A>

[0156] With reference to the synthesis method of compound 2-3-4 in CN108137445B, compound 2-3-1 (4-bromo-9,9'-spirobifluorene) is replaced by 4-bromo-9,9-dimethyl-9H-fluorene, 4-bromo-9,9-dimethyl-2-nitro-9H-fluorene, 4-bromo-9,9-dimethyl-9H-fluorene-2-carbonitrile, (4-bromo-9,9-dimethyl-9H-fluorene-2-yl)(o-tolyl)methanone, etc., to obtain a series of compounds A as the starting materials for synthesizing the compounds of the present invention.

[0157] Example 1: Synthesis of Compound 18 (1) Synthesis of Compound S1:

[0158]

[0159] Add bis(9,9-dimethyl-9H-fluoren-4-yl)methanone (50 g) and dichloroethane (250 mL) as compound A to the reaction flask, then add aluminum chloride (32.1 g) at 0-10°C, half an hour later, add propionyl chloride (22.3 g) as compound B dropwise at 0-10°C, then warm to room temperature for 2 hours. After the reaction, pour the reaction solution into ice water, separate the liquid, and obtain an organic phase containing compound S1 for later use.

[0160] (2) Synthesis of compound S2:

[0161]

[0162] The organic phase containing compound S1 was added to the reaction flask, followed by hydroxylamine hydrochloride (18.4 g) and sodium acetate (29.6 g), and the temperature was raised to reflux for reaction for 3 h. After the reaction was completed, the temperature was lowered and filtered to remove inorganic salts, and the filter cake was rinsed with a small amount of dichloroethane. After the filtrate was concentrated, it was slurried with ethanol and filtered to obtain solid compound S2 (58.3 g) with a yield of 86.8%.

[0163] (3) Synthesis of Compound 18:

[0164]

[0165] The above compound S2 (58.3 g) and dichloroethane (300 mL) were added to the reaction flask, then cooled to 0-5°C, and benzoyl chloride (32.3 g) as compound C was added dropwise for 1 h. After the reaction was completed, alkali solution was added for neutralization, and then washed with water until neutral, separated, and the organic phase was concentrated and slurried with ethanol to obtain solid compound 18 (68.1 g) with a yield of 85%.

[0166] MS (ESI+): m / z 765.34 [M+H] + .

[0167] 1 H NMR (500 MHz, CDCl 3 ): δ8.12-8.05(m,4H),7.93(d,J=7.4Hz,2H),7.84(d,J=7.3Hz,2H),7.68(s,2H),7.62-7. 55(m,2H),7.54-7.42(m,10H),2.86(q,J=7.2Hz,4H),1.55(s,12H),1.19(t,J=7.2Hz,6H).

[0168] Example 2: Synthesis of Compound 25

[0169] (1) Synthesis of compound S4:

[0170]

[0171] According to the method in Example 1, an organic phase containing compound S1 was obtained. The above organic phase was added to the reaction bottle, cooled to 35-45°C, and 68% nitric acid (19.3g) was added dropwise. After the addition was completed, it was kept warm for 1h. Water was added, washed once with water, and then washed once with a saturated sodium carbonate aqueous solution. The organic phase was recovered under reduced pressure, methanol (200mL) was added, the temperature was raised to 50-60°C, stirred for 1h, cooled to 15-20°C, and filtered to obtain a yellow solid compound S4 (51.8g) with a yield of 69.6%.

[0172] (2) Synthesis of compound S5:

[0173]

[0174] The above compound S4 (51.8 g) was added to the reaction flask, followed by hydroxylamine hydrochloride (12.8 g) and sodium acetate (20.6 g), and the temperature was raised to reflux for reaction for 3 h. After the reaction was completed, the temperature was lowered and filtered to remove inorganic salts, and the filter cake was rinsed with a small amount of dichloroethane. After the filtrate was concentrated, it was slurried with ethanol to obtain solid compound S5 (47.1 g) with a yield of 86.7%.

[0175] (3) Synthesis of Compound 25:

[0176]

[0177] The above compound S5 (47.1 g) and dichloroethane (250 mL) were added to the reaction flask, and then the temperature was lowered to 0-5°C, and acetyl chloride (13.2 g) as compound C 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 organic phase was concentrated and slurried with ethanol to obtain a yellow solid compound 25 (46.9 g) with a yield of 87.6%.

[0178] MS (ESI+): m / z 703.23 [M+H] + .

[0179] 1 H NMR (500 MHz, CDCl 3 ): δ8.65(s,2H),8.46(s,2H),7.95(d,J=7.4Hz,2H),7.80(s,2H),7.65(d,J=7.4Hz,2H),2.54(s,6H),2.55(s,6H),1.56(s,12H).

[0180] Example 3: Synthesis of Compound 65

[0181] (1) The synthetic route of compound S6 is as follows:

[0182]

[0183] Compound S1 (50 g) was obtained according to the method in Example 1. Compound S1, 36 wt% concentrated hydrochloric acid (120 g) and 4 M / L hydrogen chloride ethyl acetate solution (45 g) were added to the reaction bottle, stirred until completely dissolved, cooled to 10-15°C, sodium nitrite (14.4 g) was added, and the reaction was continued for 2 h. After adding water to quench the reaction, the liquids were separated, and the organic phase was concentrated to obtain a viscous liquid containing compound S6.

[0184] (2) Synthesis of Compound 65:

[0185]

[0186] The viscous liquid containing compound S6 and dichloroethane (270 mL) were added to the reaction flask, and then the temperature was lowered to 0-5°C, and benzoyl chloride (29.3 g) as compound C 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 organic phase was concentrated and slurried with ethanol to obtain solid compound 65 (64.4 g) with a yield of 85.5%.

[0187] MS (ESI+): m / z 793.33 [M+H] + .

[0188] 1 H NMR (500 MHz, CDCl 3 ): δ8.14-8.08(m,6H),8.04(d,J=7.8Hz,2H),7.98(d,J=7.9Hz,2H),7.90(d,J =7.3Hz,2H),7.64-7.55(m,2H),7.53-7.43(m,8H),2.53(s,6H),1.56(s,12H).

[0189] Example 4: Synthesis of Compound 89

[0190] (1) Synthesis of compound S7:

[0191]

[0192] Compound S4 (50 g) was obtained according to the method in Example 2. Compound S4, 36 wt% concentrated hydrochloric acid (100 g) and 4 M / L hydrogen chloride ethyl acetate solution (30 g) were added to the reaction bottle, stirred until completely dissolved, cooled to 10-15°C, sodium nitrite (12.3 g) was added, and the reaction was continued for 2 h. After adding water to quench the reaction, the liquids were separated, and the organic phase was concentrated to obtain a viscous liquid containing compound S7.

[0193] (2) Synthesis of Compound 89:

[0194]

[0195] The viscous liquid containing compound S7 and dichloroethane (250 mL) were added to the reaction flask, and then the temperature was lowered to 0-5°C, and benzoyl chloride (25 g) as compound C was added dropwise to react for 1 h. After the reaction was completed, alkali solution was added for neutralization, and then washed with water until neutral, separated, and the organic phase was concentrated and slurried with ethanol to obtain solid compound 89 (53.6 g) with a yield of 74.9%.

[0196] MS (ESI+): m / z 883.35 [M+H] + .

[0197] 1 H NMR (500 MHz, CDCl 3 ): δ8.70(s,2H),8.46(s,2H),8.14-8.03(m,8H),7.97(d,J=8.0Hz,2H),7.60-7.52(m,2H),7.45-7.40(m,4H),2.45(s,6H),1.56(s,12H).

[0198] Examples 5-9: Synthesis of Compounds 1, 48, 104, 113 and 121

[0199] Referring to the synthetic routes in Examples 1-4, and selecting the corresponding compound A, compound B and compound C, the compounds of Examples 5-9 in Table 1 were prepared respectively.

[0200] Table 1

[0201]

[0202] Example 10: Preparation of Photosensitive Composition 1

[0203] Trimethylolpropane triacrylate (6.4 g), Compound 18 (3 g) and ethyl cellosolve (87.7 g) were added to the acrylic copolymer (15.5 g), and the mixture was sufficiently stirred to obtain a photosensitive composition 1.

[0204] The acrylic copolymer is obtained by the following method: 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 are dissolved in 300 parts by mass of ethyl cellosolve, 0.75 parts by mass of azobisisobutyronitrile is added under a nitrogen atmosphere, and then reacted at 70° C. for 5 hours to obtain an acrylic copolymer.

[0205] Examples 11-18: Preparation of Photosensitive Composition 2-9

[0206] Except that compound 18 was replaced by the compounds in Table 2, the photosensitive compositions in Examples 11-18 and Comparative Examples 1-4 were obtained by referring to the method in Example 10.

[0207] Table 2

[0208]

[0209] Among them, as a control compound, the structure of the compound used as a photoinitiator in Comparative Examples 1-4 is shown below.

[0210]

[0211] <Hardness test>

[0212] The photosensitive compositions of Examples 10-18 and Comparative Examples 1-4 were coated on a polyethylene terephthalate film having a thickness of 50 μm using a #3 rod coater. A light irradiation device with a belt conveyor was used to irradiate the film with light from a high-pressure mercury lamp having a line power of 80 W / cm. The distance from the lamp to the belt conveyor was set to 10 cm, and the line speed of the belt conveyor was set to 8 cm / min. After curing, the film was placed at room temperature for 24 hours, and then the pencil hardness was measured at a load of 1 kg using a pencil hardness tester. The test results are shown in Table 3.

[0213] Table 3

[0214] Example Photoinitiator compounds Pencil hardness Example 10 18 3H Embodiment 11 25 3H Example 12 65 3H Example 13 89 3H Embodiment 14 1 3H Embodiment 15 48 3H Example 16 104 3H Embodiment 17 113 3H Embodiment 18 121 3H Comparative Example 1 OXE02 1H Comparative Example 2 345 1H Comparative Example 3 340 3H Comparative Example 4 346 3H Comparative Example 5 347 1H

[0215] As can be seen from Table 3, the curing hardness of the photosensitive compositions based on the compounds of the present invention in Examples 10-18 is significantly higher than that of the photosensitive compositions based on OXE02, 345 and 347 in Comparative Examples 1, 2 and 5, and is comparable to the curing hardness of the photosensitive compositions based on 340 and 346 in Comparative Examples 3-4, indicating that the compounds of the present invention are suitable for application in the field of photocuring.

[0216] Example 19: Preparation of polymerizable composition (photosensitive resin) 1

[0217] Acrylic resin prepolymer (96 g), compound 18 (4 g) and tetrahydrofuran (100 g) were added into a reaction container at 35° C., reacted for 6 hours, and stirred evenly to obtain a polymerizable composition 1.

[0218] The above-mentioned acrylic resin prepolymer is prepared 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.

[0219] Examples 20-27: Preparation of polymerizable compositions 2-9

[0220] Except that compound 18 was replaced by the compounds in Table 4, the polymerizable compositions in Examples 20-27 and Comparative Examples 6-10 were obtained by referring to the method in Example 19.

[0221] Table 4

[0222] Example Acrylic resin prepolymer Photoinitiator compounds Tetrahydrofuran Embodiment 19 96g 18(4g) 100g Embodiment 20 96g 25(4g) 100g Embodiment 21 96g 65(4g) 100g Embodiment 22 96g 89(4g) 100g Embodiment 23 96g 1(4g) 100g Embodiment 24 96g 48(4g) 100g Embodiment 25 96g 104(4g) 100g Embodiment 26 96g 113(4g) 100g Embodiment 27 96g 121(4g) 100g Comparative Example 6 96g OXE02(4g) 100g Comparative Example 7 96g 345(4g) 100g Comparative Example 8 96g 340(4g) 100g Comparative Example 9 96g 346(4g) 100g Comparative Example 10 96g 347(4g) 100g

[0223] The polymerizable compositions of Examples 19 to 27 and Comparative Examples 6 to 10 were evaluated for photosensitivity according to the following method.

[0224] <Evaluation of photosensitivity under irradiation with blue and green light sources>

[0225] The polymerizable compositions of Examples 19-27 and Comparative Examples 6-10 were coated on a glass substrate using a spin coater, 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 19-27 and Comparative Examples 5-8 were cured under irradiation with a blue light source and a green light source, respectively. Table 5 shows the exposure required to complete the curing, and the smaller the value, the better the photosensitivity.

[0226] Table 5

[0227]

[0228] As can be seen from Table 5, under the irradiation of blue and green light sources, the energy required for curing the polymerizable composition containing the compound of the present invention is significantly less than that required for curing the polymerizable composition containing the control compounds (OXE02, 345, 340, 346 and 347). Compared with the compounds (OXE02, 345, 340, 346 and 347) used in Comparative Examples 6-10, the compound of the present invention has more excellent photosensitive activity and is useful as a photoinitiator for optical applications.

[0229] <UV Light Stability Test>

[0230] Solutions of Compound 1, OXE02, 340 and 347 were respectively prepared in methacrylic acid at a concentration of 2% wt, and the HPLC deterioration rate of each sample was measured over time under light irradiation (sampling and determination were carried out on the 1st, 2nd, 3rd, 5th, 6th, 7th and 13th days respectively).

[0231] Preparation of the test solution was as follows: Under a yellow light, 0.015 g of the sample was weighed and dissolved in 10 ml of acetonitrile.

[0232] The conditions of HPLC were as follows:

[0233] instrument Waters 2695 Elution method Isocratic elution Chromatographic columns C18,5μm Mobile phase flow rate / ml / min 1 Column specification / mm Φ4.6×150 Detection wavelength / nm 254nm Column temperature / ℃ 40 Analysis time (min) 30 Mobile phase Acetonitrile: water = 90:10, v / v Injection volume (μl) 1

[0234] It can be seen that Figure 1 compared with 347, due to its rigid planar structure, Compound 1 of the present invention inhibits the internal vibration of the molecule, reduces the deterioration phenomenon caused by energy transfer, and finally shows the best stability under light irradiation, which facilitates the storage and transportation of the material.

[0235] The above is only the specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention can easily think of changes or substitutions, which should be covered within the protection scope of the present invention.

Claims

1. A compound as shown in formula (A), in, Each A is independently absent or represents a carbonyl group; Each R1 is independently selected from substituted or unsubstituted C 1-20 Alkyl and substituted or unsubstituted C 3-20 Cycloalkyl; Each R2 is independently selected from substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 3-20 Cycloalkyl and substituted or unsubstituted C 6-20 Aryl; Each R3 is independently selected from hydrogen, nitro, cyano, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 6-20 Aryl acyl and substituted or unsubstituted 4-20 membered heteroaryl acyl; When the alkyl, cycloalkyl, aryl and heteroaryl groups are substituted by one or more substituents, each substituent is independently selected from C 1-20 Alkyl, C 3-20 Cycloalkyl, C 6-20 Aryl and 4-20 membered heteroaryl; The heteroaryl group contains 1 to 3 heteroatoms independently selected from N, O and S.

2. The compound according to claim 1, characterized in that The compound is as shown in formula (I) or formula (II): in, R1, R2 and R3 are as defined in claim 1.

3. The compound according to claim 1 or 2, characterized in that Each R1 is independently selected from C 1-20 Alkyl and C 3-20 Cycloalkyl; Preferably, each R1 is independently selected from C 1-8 Alkyl and C 3-8 Cycloalkyl; More preferably, each R1 is independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, 2,4,4-trimethylpentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl; Further preferably, each R1 is independently selected from methyl, ethyl, 2,4,4-trimethylpentyl and cyclohexyl.

4. The compound according to any one of claims 1 to 3, characterized in that Each R2 is independently selected from C 1-20 Alkyl, C 3-20 Cycloalkyl and C 6-20 Aryl; Preferably, each R2 is independently selected from C 1-6 Alkyl, C 3-6 Cycloalkyl and C 6-10 Aryl; More preferably, each R2 is independently selected from methyl, ethyl, n-propyl, n-butyl, phenyl, naphthyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl; Further preferably, each R2 is independently selected from methyl and phenyl.

5. The compound according to any one of claims 1 to 4, characterized in that Each R3 is independently selected from hydrogen, nitro, cyano, C 1-20 Alkyl, 4-20 membered heteroaryl acyl and C 1-20 Alkyl, C 3-20 Cycloalkyl, C 6-20 Aryl or 4-20 membered heteroaryl substituted C 6-20 Aryl acyl; Preferably, each R3 is independently selected from hydrogen, nitro, cyano, C 1-6 Alkyl, 4-10 membered heteroaryl acyl and C 1-6 Alkyl, C 3-6 Cycloalkyl, C 6-10 Aryl or 4-10 membered heteroaryl substituted C 6-10 Aryl acyl; More preferably, each R3 is independently selected from hydrogen, nitro, cyano, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, indole-2-carbonyl, isoindole-2-carbonyl, benzofuran-2-carbonyl, isobenzofuran-2-carbonyl, benzothiophene-2-carbonyl, isobenzothiophene-2-carbonyl, 2-methylbenzoyl, 2,4-dimethylbenzoyl, 2,6-dimethylbenzoyl and 2,4,6-trimethylbenzoyl; Further preferably, each R3 is independently selected from hydrogen, nitro, cyano and 2-methylbenzoyl.

6. The compound according to any one of claims 1 to 4, characterized in that The compound is represented by any one of formula (1-1) to formula (1-4) and formula (2-1) to formula (2-4): in, R1 and R2 are as defined in any one of claims 1 to 4; In formula (1-4) and formula (2-4), each R4 is independently selected from substituted or unsubstituted C 6-20 aryl and substituted or unsubstituted 4-20 membered heteroaryl.

7. The compound according to claim 6, characterized in that Each R4 is independently selected from 4-20 membered heteroaryl and C 1-20 Alkyl, C 3-20 Cycloalkyl, C 6-20 Aryl or 4-20 membered heteroaryl substituted C 6-20 Aryl; Preferably, each R4 is independently selected from 4-10 membered heteroaryl and C 1-6 Alkyl, C 3-6 Cycloalkyl, C 6-10 Aryl or 4-10 membered heteroaryl substituted C 6-10 Aryl; More preferably, each R4 is independently selected from indol-2-yl, isoindol-2-yl, benzofuran-2-yl, isobenzofuran-2-yl, benzothiophen-2-yl, isobenzothiophen-2-yl, 2-methylphenyl, 2,4-dimethylphenyl, 2,6-dimethylphenyl and 2,4,6-trimethylphenyl; More preferably, each R4 is independently 2-methylphenyl.

8. A compound selected from the following compounds:

9. A polymerizable composition comprising the compound according to any one of claims 1 to 8; Preferably, the polymerizable composition further comprises at least one of the following components: a) acrylic resin prepolymer; b) solvent; More preferably, the polymerizable composition comprises the following components in parts by weight: 2-6 parts of the compound according to any one of claims 1-8; 94-98 parts of acrylic resin prepolymer; and 100 parts of solvent.

10. A photosensitive composition comprising the compound according to any one of claims 1 to 8; Preferably, the photosensitive composition further comprises at least one of the following components: a) alkali soluble resin; b) photopolymerizable compounds; c) solvent; More preferably, the photosensitive composition comprises the following components in parts by weight: 1-5 parts of the compound according to any one of claims 1-8; 10-20 parts of an alkali-soluble resin; 5-10 parts of a photopolymerizable compound; and 80-100 parts of solvent.

11. A photoresist comprising the following components: i) a compound according to any one of claims 1 to 8; ii) alkali soluble resin; iii) photopolymerizable compounds; iv) auxiliary agents; Preferably, the auxiliary agent is selected from solvents, colorants, fillers, dispersants, antioxidants, ultraviolet absorbers, curing accelerators and thermal polymerization inhibitors.

12. Use of the compound according to any one of claims 1 to 8, the polymerizable composition according to claim 9, the photosensitive composition according to claim 10 or the photoresist according to claim 11 in the field of photocuring.

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