Pyrazoline sensitizer and preparation method therefor, and photosensitive resin composition comprising same and use thereof

Abstract

Provided are a pyrazoline sensitizer and a preparation method therefor, and a photosensitive resin composition comprising same and the use thereof. The pyrazoline sensitizer has a structure as represented by formula I. The pyrazoline sensitizer has a good sensitization effect and good compatibility with a resin, etc.; therefore, the photosensitive resin composition comprising the sensitizer is short in terms of curing time, has substantially improved ultraviolet curing efficiency, and is particularly suitable for an UV-LED photocuring system.

Description

A pyrazoline sensitizer, its preparation method, photosensitive resin composition containing the same and application Technical Field

[0001] The present application belongs to the technical field of photocurable materials, and specifically relates to a pyrazoline sensitizer, a preparation method thereof, a photosensitive resin composition containing the same, and applications thereof. Background Art

[0002] UV curing technology is widely used. Traditional UV curing uses medium / high pressure mercury lamps as irradiation light sources, which have disadvantages such as low efficiency in converting electrical energy into UV energy, the UV light generated is a continuous light source, resulting in weak intensity of the main absorbed UV light required for curing, low irradiation efficiency, and high energy consumption. In view of this, UV-LED light sources that can emit UV light with a narrow spectral bandwidth and high light intensity are considered to be good alternatives in the field of photocuring, and UV-LED light sources have advantages such as saving electricity and reducing thermal effects. However, photoinitiators suitable for mainstream UV-LEDs in the field of photocuring generally have poor performance and have disadvantages such as weak light absorption ability of the initiator, which limits the application of UV-LED in photocuring.

[0003] Sensitizers are an effective solution to these problems. Without substantially altering the photocurable composition system, the addition of sensitizers allows for continuous energy absorption and transfer, thereby overcoming issues such as the initiator's weak direct light absorption capacity. This improves light utilization, reduces curing time and costs, and enhances the curing effectiveness of UV-LED photocuring technology. Pyrazoline compounds, with their absorption wavelength between 380 and 410 nm, are particularly suitable as sensitizers in UV-LED photocuring systems. However, existing pyrazoline sensitizers exhibit poor sensitization and prolonged curing times.

[0004] Therefore, developing a pyrazoline sensitizer with good sensitization effect and moderate curing time is an urgent problem to be solved in this field.

[0005] Summary of the Invention

[0006] The following is a summary of the subject matter described in detail herein. This summary is not intended to limit the scope of the claims.

[0007] This application provides a pyrazoline sensitizer, a preparation method thereof, a photosensitive resin composition containing the pyrazoline sensitizer, and applications thereof. The pyrazoline sensitizer has excellent sensitization effects and good compatibility with resins and the like. This allows the photosensitive resin composition containing the pyrazoline sensitizer to have a short curing time and significantly improve ultraviolet light curing efficiency, making it particularly suitable for UV-LED light curing systems.

[0008] In a first aspect, the present application provides a pyrazoline sensitizer having a structure shown in Formula I:

[0009] wherein R1 and R2 are each independently selected from any one of H, halogen, carboxyl, nitro, cyano, amino, hydroxyl, C1-C20 straight or branched alkyl, C1-C20 straight or branched alkenyl, C3-C20 cycloalkyl, C1-C10 alkyl substituted with C3-C8 cycloalkyl, C3-C10 cycloalkyl substituted with C1-C20 alkyl, C2-C8 acyl or C6-C20 aryl; at least one -CH2- or -CH- in the C1-C20 straight or branched alkyl or C1-C20 straight or branched alkenyl may be independently replaced by -O-, -S-, -N(R)-, carbonyl, ester or At least one -CH2- in the C3-C10 cycloalkyl group may be substituted by at least one of -O-, -S- or -N(R)-; at least one -CH- in the C6-C20 aryl group may be substituted by at least one of -O-, -S- or -N(R)-; the R, R 1 Each is independently selected from H or a C1-C6 alkyl group; at least one H in the C1-C20 straight-chain or branched-chain alkyl group, C1-C20 straight-chain or branched-chain alkenyl group, and C3-C10 cycloalkyl group can be independently replaced by F; and the R1 and R2 can each independently form a ring with the benzene ring to which they are bonded.

[0010] The R3 is selected from a linear or branched C2 to C18 unsaturated group, wherein the C2 to C18 unsaturated group includes at least one phenyl group or The unsaturated groups include any one of cycloalkyl, alkene or alkyne groups; at least one methylene group in the C2 to C18 unsaturated groups can be independently replaced by -O-, -S-, -N(R')-, carbonyl, ester or At least one of the substitutions; said R', R 2 、R 3 Each is independently selected from H, C1-C6 alkyl, C3-C20 cycloalkyl, C1-C10 alkyl substituted with C3-C8 cycloalkyl, or C3-C10 cycloalkyl substituted with C1-C20 alkyl; the R 2 When selected from C1 to C6 alkyl groups, at least one methylene group in the C1 to C6 alkyl group may be substituted by -O-, -S- or imino; 2 The benzene ring to which it is bonded can form a ring; the R3 can form a ring with the benzene ring to which it is bonded; the dotted line indicates the connection site.

[0011] In the present application, the pyrazoline sensitizer is designed through a specific molecular structure, that is, a specific parent core structure is adopted, and specific substituents are selected at the same time, so that the pyrazoline sensitizer achieves a better sensitization effect. The photosensitive resin composition including the pyrazoline sensitizer has good compatibility, high sensitivity, high resolution, excellent developability, high adhesion, fast curing speed and high curing efficiency under ultraviolet light conditions, and has good applicability in the UV-LED light curing system.

[0012] Preferably, the R1 is selected from any one of H, amino, C2~C12 straight or branched alkyl or C6~C12 aryl; at least one -CH2- in the C2~C12 straight or branched alkyl may be substituted by at least one of -O-, -S-, -N(R")-, carbonyl or phenylene; and the R" is selected from H or C1~C6 alkyl.

[0013] Preferably, the R1 is selected from H, C2-C4 straight or branched alkyl, dimethylamino, Any one of phenyl or cyclohexyl; wherein, Indicates the connection site, and “*” indicates the fusion site.

[0014] Preferably, the C2-C4 straight-chain or branched alkyl group includes at least one of an ethyl group, a propyl group or a tert-butyl group.

[0015] In the present application, the C1-C20 may be, for example, C1, C2, C4, C6, C8, C10, C12, C14, C16, C18 or C20, etc. The C3-C10 may be, for example, C3, C4, C5, C6, C7, C8, C9 or C10, etc. The C2-C8 may be, for example, C2, C3, C4, C5, C6, C7 or C8; the C1-C6 may be, for example, C1, C2, C3, C4, C5 or C6; the C2-C18 may be, for example, C2, C4, C6, C8, C10, C12, C14, C16 or C18; the C2-C12 may be, for example, C2, C3, C4, C5, C6, C7, C8, C9, C10 or C12; the C6-C20 may be, for example, C6, C8, C10, C12, C14, C16, C18 or C20; the above all refer to the number of C in the group, and the same expressions hereinafter represent the same meaning and numerical range.

[0016] Preferably, the R2 is selected from any one of H, halogen, or C2-C12 linear or branched alkyl; preferably, at least one H in the C2-C12 linear or branched alkyl is substituted by F.

[0017] Preferably, R2 is selected from any one of H, trifluoromethyl or ethyl.

[0018] Preferably, R3 is selected from a linear or branched C2-C16 unsaturated group, wherein the C2-C16 unsaturated group includes at least one substituted or unsubstituted phenyl group; the unsaturated group includes an alkenyl group or an alkynyl group; the substituent in the substituted or unsubstituted phenyl group includes any one of an amino group, a C1-C4 linear or branched alkyl group, or a C1-C4 linear or branched alkoxy group; the substituent in the substituted or unsubstituted phenyl group and the benzene ring to which it is bonded can form a ring; at least one methylene group in the aforementioned group can be substituted by at least one of an oxygen group, a sulfur group, or an imine group.

[0019] Preferably, the R3 is selected from any one of the following groups:

[0020] Among them, R 31 、R 32 Each is independently selected from any one of H, a C1-C4 straight-chain or branched alkyl group, a C1-C4 straight-chain or branched alkoxy group, a dimethylamino group, a diethylamino group, or a C3-C8 cycloalkyl group (for example, a C3, C4, C5, C6, C7, or C8 cycloalkyl group); Indicates the attachment site.

[0021] Preferably, R3 is selected from styryl, phenylethynyl, 4-tert-butylstyryl, 4-tert-butylstyryl, 4-dimethylaminostyryl, 4-dimethylaminostyryl, 4-diethylaminostyryl, 4-diethylaminostyryl, 2-methoxystyryl, 2-methoxystyryl, or 4-cyclohexylphenylphenyl group.

[0022] Preferably, the pyrazoline sensitizer is selected from any one of the following compounds 1-13:

[0023] In this application, the selection of R1, R2 and R3 groups is crucial for the compound to function well. The three not only affect the solubility of the compound in the system, but also whether R2 and R3 can form an N—N—C conjugated structure with the main structure of Formula I is the key to whether the compound can produce a good sensitization effect.

[0024] In a second aspect, the present application provides a method for preparing the pyrazoline sensitizer according to the first aspect, the preparation method comprising the following steps:

[0025] (1) reacting the compound represented by formula II with the compound represented by formula III to obtain the intermediate compound represented by formula IV;

[0026] (2) reacting the intermediate compound obtained in step (1) with the compound of formula V to obtain the pyrazoline sensitizer;

[0027] or,

[0028] The preparation method comprises the following steps:

[0029] (11) reacting the compound represented by formula II with the compound represented by formula III-1 to obtain the intermediate compound represented by formula IV-1;

[0030] (12) reacting the intermediate compound obtained in step (11) with the compound represented by formula V to obtain the intermediate compound represented by formula I-1;

[0031] (13) reacting the intermediate compound obtained in step (12) with R3-H to obtain the pyrazoline sensitizer;

[0032] R1, R2, and R3 are all selected from the same range as in Formula I.

[0033] Preferably, the molar ratio of the compound of formula II to the compound of formula III in step (1), and the molar ratio of the compound of formula II to the compound of formula III-1 in step (11) are each independently 1:(0.5-1.5), wherein the specific value of (0.5-1.5) can be, for example, 0.5, 0.6, 0.8, 1, 1.2, 1.4 or 1.5, etc.

[0034] Preferably, the reactions in step (1) and step (11) are each independently carried out in an organic solvent.

[0035] Preferably, the organic solvent includes any one of dichloromethane, dichloroethane, methanol, ethanol or toluene, or a combination of at least two thereof.

[0036] Preferably, the reactions in step (1) and step (11) are each independently carried out in the presence of a basic substance.

[0037] Preferably, the alkaline substance includes at least one of sodium hydroxide, sodium methoxide, potassium ethoxide, butyl lithium or phenyl lithium.

[0038] Preferably, the reaction temperature of step (1) and step (11) is independently 10 to 30°C, for example, 10°C, 12°C, 15°C, 18°C, 20°C, 22°C, 25°C, 28°C or 30°C; the reaction time is independently 12 to 24h, for example, 12h, 14h, 16h, 18h, 20h, 22h or 24h.

[0039] Preferably, the molar ratio of the intermediate compound in step (2) and step (12) to the compound of formula V is independently 1:(1 to 1.2).

[0040] Preferably, the reactions in step (2) and step (12) are each independently carried out in the presence of an acidic substance.

[0041] Preferably, the acidic substance includes any one or both of acetic acid and methanesulfonic acid.

[0042] Preferably, the solvents for the reactions in step (2) and step (12) each independently include any one of dichloroethane, methanol, ethanol or toluene, or a combination of at least two thereof.

[0043] Preferably, the reaction temperature of step (2) and step (12) is independently 50 to 110°C, for example, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C or 110°C, etc.; the reaction time is independently 12 to 24h, for example, 12h, 14h, 16h, 18h, 20h, 22h or 24h, etc.

[0044] In the present application, the reaction temperature in step (2) and step (12) is determined according to the boiling points of different solvents, and is generally 50 to 110°C.

[0045] Preferably, the reaction in step (13) is carried out in the presence of a catalyst.

[0046] Preferably, the catalyst comprises Pd(dppf)Cl2.

[0047] Preferably, the reaction temperature in step (13) is 90-110°C, for example, 90°C, 92°C, 94°C, 98°C, 100°C, 102°C, 104°C, 106°C, 108°C or 110°C, etc.; the reaction time is 6-8h, for example, 6h, 7h or 8h, etc.

[0048] In the present application, in the process of preparing the pyrazoline sensitizer, the reaction reagents used are all known compounds in the prior art, which can be obtained commercially or conveniently prepared by existing synthesis methods.

[0049] In a third aspect, the present application provides a photosensitive resin composition, comprising the pyrazoline sensitizer according to the first aspect.

[0050] Preferably, the photosensitive resin composition further comprises a base resin, a photoinitiator and a carbon-carbon double bond-containing compound, wherein, by weight percentage, the photosensitive resin composition comprises 10-80% of the base resin (for example, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75% or 80%, etc.), 0.01-10% of the sensitizer (for example, 0.01%, 0.05%, 0.08%, 0.1%), 0.02% or 0.03% of the sensitizer. .1%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%, etc.), 0.1-20% (for example, 0.3%, 1%, 3%, 5%, 8%, 10%, 13%, 15%, 18% or 20%, etc.) of a photoinitiator, and 10-50% (for example, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% or 50%, etc.) of a carbon-carbon double bond-containing compound; the sensitizer includes the pyrazoline sensitizer as described in the first aspect.

[0051] In the present application, the pyrazoline sensitizer is used in combination with a photoinitiator to significantly improve the photocuring efficiency and the performance of the cured product.

[0052] Preferably, the matrix resin includes at least one of acrylic polymers, styrene polymers, epoxy polymers, aliphatic polyurethane acrylate polymers, aromatic polyurethane acrylate polymers, amide resins, amide epoxy resins, alkyd resins or phenolic resins.

[0053] In this application, the acrylic polymers, aliphatic polyurethane acrylate polymers, and aromatic polyurethane acrylate polymers are not limited to acrylic acid and acrylate, but refer to acrylic acid, acrylate and their derivatives, such as methacrylic acid polymers, aliphatic polyurethane methacrylate polymers or aromatic polyurethane methacrylate.

[0054] Preferably, the carbon-carbon double bond-containing compound includes any one or a combination of at least two of a compound obtained by reacting an α,β-unsaturated carboxylic acid with a polyol, a bisphenol A (meth)acrylate compound, a compound obtained by reacting an α,β-unsaturated carboxylic acid with a glycidyl group-containing compound, a (meth)acrylate compound having an urethane bond in the molecule, nonylphenoxypolyvinyloxyacrylate, γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl-phthalate, β-hydroxyethyl-β'-(meth)acryloyloxyethyl-phthalate, β-hydroxypropyl-β'-(meth)acryloyloxyethyl-phthalate, phthalic acid compounds or alkyl (meth)acrylates; further preferred are any one or a combination of at least two of a bisphenol A (meth)acrylate compound or a (meth)acrylate compound having an urethane bond in the molecule.

[0055] Preferably, the photoinitiator includes at least one of a bisimidazole compound, an acridine compound, an aromatic ketone compound, an anthraquinone compound, benzoin, a benzoin alkyl ether compound, an oxime ester compound, a triazine compound, a pyridine compound or a thioxanthone compound.

[0056] Preferably, the photoinitiator includes any one of photoinitiator 1173, 184, BDK, 907 or HABI-101, HABI-102, HABI-105, HABI-106, HABI-107, HABI-108, HABI-123, HABI-124 and HABI-125 produced by Changzhou Qiangli Electronic New Materials Co., Ltd., or a combination of at least two thereof.

[0057] Preferably, the photosensitive resin composition further includes 0.01-10% of other additives in terms of mass percentage, for example, 0.01%, 0.05%, 0.08%, 0.1%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%.

[0058] In the present application, the auxiliary agent includes a pigment, a solvent, etc., and the pigment includes an organic pigment and / or an inorganic pigment, including but not limited to a water-soluble pigment, a water-insoluble azo pigment, a phthalocyanine pigment, an acridone pigment, an isoindoline pigment, an indole anthrone pigment, an indole pigment or a pyrrole dione pigment, etc. The above pigments can be used alone or in combination, depending on the specific application requirements of the product.

[0059] The solvent includes ketones such as methyl ethyl ketone, butanone, cyclohexanone, heptanone or 3-heptanone; cyclic ethers such as tetrahydrofuran and pyran; cyclic esters such as γ-butyrolactone; (poly)alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether or tripropylene glycol monoethyl ether; aromatic hydrocarbons such as toluene, xylene or trimethylbenzene. These solvents may be used alone or in combination of two or more.

[0060] In a fourth aspect, the present application provides a use of the pyrazoline sensitizer according to the first aspect or the photosensitive resin composition according to the third aspect in a photocurable product.

[0061] Preferably, the photocurable product includes a dry film or a resin laminate prepared by photocuring.

[0062] The numerical range described in this application includes not only the point values ​​listed above, but also any point values ​​between the above numerical ranges that are not listed. Due to limited space and for the sake of simplicity, this application no longer exhaustively lists the specific point values ​​included in the range.

[0063] Compared with the related art, the beneficial effects of this application are:

[0064] In the present application, the pyrazoline sensitizer is designed through a specific molecular structure, that is, a specific mother core structure is adopted, and specific substituents are selected at the same time, so that the pyrazoline sensitizer can achieve a better sensitization effect with a smaller dosage. The photosensitive resin composition including the pyrazoline sensitizer has good compatibility, high sensitivity, high resolution, excellent developability, high adhesion, fast curing speed and high curing efficiency under ultraviolet light conditions, and has good applicability in the UV-LED light curing system.

[0065] Still other aspects will become apparent upon reading and understanding the detailed description. DETAILED DESCRIPTION

[0066] The technical solution of the present application is further described below through specific implementation methods. Those skilled in the art should understand that the embodiments are only used to help understand the present application and should not be regarded as specific limitations of the present application.

[0067] The raw materials used in the examples and comparative examples of the present application are all commercially available or can be prepared using conventional methods in the prior art.

[0068] Example 1

[0069] This embodiment provides a pyrazoline sensitizer, wherein the pyrazoline sensitizer is compound 1; and the preparation method of the pyrazoline sensitizer is as follows:

[0070] (1) Preparation of intermediate 1a

[0071] To a 250 mL four-necked flask, 17.7 g of N,N-diethyl-4-aminobenzaldehyde, 19.9 g of 4-bromoacetophenone, and 100 g of methanol were added at room temperature and stirred until completely dissolved. 3.24 g of sodium methoxide was added over approximately half an hour. The mixture was stirred at 25°C for 8 h. The reaction progress was monitored by simultaneous HPLC and TLC (EA:Hex = 1:10). The product gradually precipitated. The reaction was stopped when the starting material concentration was <1%. The filter cake was collected by filtration and dried to obtain 31.9 g of intermediate 1a (HPLC peak, 99.0%, yield 89%).

[0072] use 1 The structure of intermediate 1a was characterized by H-NMR, and the results are as follows.

[0073] 1 H-NMR (d6-DMSO, 500MHz): 1.1606-1.1918 (6H, t), 3.3097-3.3618 (4H, q), 6.7812-6.8094 (2H, m) , 7.4522-7.4811(1H,d), 7.5984-7.6601(4H,m), 7.7701-7.8104(1H,m), 7.8669-7.8886(2H,m).

[0074] (2) Preparation of intermediate 1b

[0075] To a 500 mL four-necked flask at room temperature, 35.8 g of intermediate 1a, 35 g of acetic acid, and 150 g of methanol were added, stirred, and heated to 55°C. 11.35 g of phenylhydrazine was added dropwise over half an hour. After the addition was complete, the mixture was incubated at 55°C for 24 hours. The reaction was monitored simultaneously by HPLC and TLC (EA:Hex = 1:10). When the concentration of intermediate 1a was ≤5%, the reaction was stopped and the system was cooled to room temperature. The filter cake was collected by suction and dried to obtain 42.5 g of intermediate 1b (HPLC:99.5%, yield 95%).

[0076] use 1 The structure of intermediate 1b was characterized by H-NMR, and the results are as follows:

[0077] 1H-NMR (d6-DMSO, 500MHz): 1.0148-1.0505 (6H, t), 3.0121-3.0726 (1H, dd), 3.2344-3.2917 (4H, m), 3.7698-3.2431 (1H, dd), 5.3027-5 .3424(1H,m), 6.5741-6.5854(2H,m), 6.5855-6.7328(1H,m), 7.0324-7.0520(4H,m), 7.1263-7.1623(2H,m), 7.5923-5.6805(4H,m).

[0078] (3) Preparation of Compound 1

[0079] To a dry 100-mL four-necked flask at room temperature were added 4.5 g of intermediate 1b, 1.6 g of p-tert-butylstyrene, and 50 mL of DMF, and stirred until the solution clarified. Pd(dppf)Cl2 was added under nitrogen, and the temperature was raised to 100°C for 8 h. The reaction was monitored simultaneously by HPLC and TLC (EA:Hex = 1:10). The reaction was stopped when the raw material content was ≤1%. The DMF was removed by concentration under reduced pressure to obtain a crude product, which was then washed twice with 100 mL of ethyl acetate (50 mL each wash). Column chromatography afforded 3.3 g of a bright yellow solid (mp 97.4-98.5°C, HPLC 99.6%, yield 62.6%).

[0080] use 1 The structure of compound 1 was characterized by H-NMR, and the results are as follows:

[0081] 1 H-NMR (d6-DMSO, 500MHz): 1.0238-1.0526 (6H, t), 1.2900 (9H, s), 3.0374-3.0926 (1H, dd ), 3.2445-3.2916 (4H, m), 3.7861-3.8654 (1H, dd), 5.3021-5.3518 (1H, dd), 6.5831-6.60 41(2H,d),6.6831-6.7235(1H,t),7.0464-7.0668(4H,dd),7.1313-7.3153(4H,m),7.391 4-7.4127(2H,d), 7.5375-7.5626(2H,d), 7.6336-7.6525(2H,d), 7.7233-7.7413(2H,d).

[0082] The synthetic route of compound 1 is as follows:

[0083] Examples 2 to 11

[0084] Examples 2 to 11 provide a pyrazoline sensitizer, which is compound 2 to compound 11. The preparation method of the pyrazoline sensitizer is the same as that of Example 1, except that the raw materials are and raw materials The raw materials with corresponding structures were replaced respectively, and other raw materials and reaction conditions were the same as those in Example 1.

[0085] use 1 The structure of compound 2-11 was characterized by H-NMR, and the results are as follows:

[0086] Compound 2: 1 H-NMR (d6-DMSO, 500MHz): 1.0237-1.0636 (6H, t), 1.3010 (9H, s), 3.0427-3.1073 ( 1H, dd), 3.2547-3.3045 (4H, q), 3.8022-3.8726 (1H, dd), 5.3464-5.3964 (1H, dd), 6 .5785-6.6086(2H,d),6.7088-6.7414(1H,t),7.0485-7.0667(4H,d),7.1464-7.1 577 (2H, t), 7.4564-7.5276 (4H, m), 7.5754-7.5954 (2H, d), 7.7625-7.7825 (2H, d).

[0087] Compound 3: 1 H-NMR (d6-DMSO, 500MHz): 1.0226-1.0526 (6H, t), 3.0309-3.0980 (1H, dd), 3.2380-3.2905 (4H, q), 3.7743-3.8722 (4H, m), 5.3113-5.3543 (1H, dd) ), 6.5815-6.6067(2H, d), 6.6934-6.7217(1H, t), 6.9606-7.0709(6H, m) , 7.1504-7.2033(2H,d), 7.2438-7.3027(2H,m), 7.4606-7.7428(6H,m).

[0088] Compound 4: 1H-NMR (d6-DMSO, 500MHz): 1.0107-1.0546 (6H, t), 3.0123-3.0754 (1H, dd), 3.2322-3.2884 (4H, q), 3.7725-3.984 (1H, dd), 5.3021-5. 3419 (1H, dd), 6.5734-6.5938 (2H, d), 6.6942-6.7328 (1H, t), 7.0315-7.0516 (4H, m), 7.1327-7.1633 (2H, t), 7.5941-7.6843 (4H, m).

[0089] Compound 5: 1 H-NMR (d6-DMSO, 500MHz): 1.2900 (9H, s), 3.0907-3.1489 (1H, dd), 3.8924-3 .9666(1H,dd),5.4726-5.5126(1H,dd),6.7242-6.7417(1H,t)7.0127-7.02 93(2H,d),7.1434-7.2048(2H,m),7.2416-7.3633(7H,m),7.3931-7.4147(2 H, d), 7.5423-7.5635 (2H, d), 7.6324-7.6515 (2H, d), 7.7335-7.7464 (2H, d).

[0090] Compound 6: 1 H-NMR (d6-DMSO, 500MHz): 1.8936-1.9528 (4H, m), 2.7027-2.8322 (4H, m), 3 .3722-3.4022(4H,m),3.6521-3.7224(2H,m),5.2587-5.2899(1H,m),6.812 7(2H,d),6.9418-7.0232(5H,m),7.1807-7.2108(2H,m),7.2838-7.3128(1H , m), 7.3336-7.3744 (2H, m), 7.4915-7.5152 (4H, m), 7.7216-7.7366 (2H, m).

[0091] Compound 7: 1H-NMR (d6-DMSO, 500MHz): 1.1144-1.1186 (6H, t), 1.1187-1.2654 (3H, t), 2.5878-2 .7732(2H,m),3.3216-3.3768(4H,m),3.6248-3.7000(1H,dd),3,7834-3.8584(1H, dd), 5.00-5.03 (1H, m), 6.7334-6.8443 (2H, m), 6.9557-7.0654 (5H, m), 7.1565-7.2 434(6H,m), 7.3567-7.4356(2H,m), 7.4567-7.5464(2H,m), 7.6966-7.7823(2H,m).

[0092] Compound 8: 1 H-NMR (d6-DMSO, 500MHz): 3.4000 (3H, s), 3.6421-3.6823 (1H, dd), 3.7824-3 .8242(1H,dd),4.0013-4.0352(1H,d),4.0832-4.1098(1H,d),4.8309-4.85 37(2H,m),5.2021-5.2441(1H,t),6.9028-7.0595(5H,m),7.1803-7.2499(4 H, m), 7.3838-7.4442 (3H, m), 7.5535-7.5681 (2H, m), 7.5950-7.7018 (4H, m).

[0093] Compound 9: 1 H-NMR (d6-DMSO, 500MHz): 1.9017-2.0386 (4H, m), 2.7523-2.8356 (4H, m), 3.3 742-3.4192 (6H, m), 3.4614-3, 7485 (10H, m), 3.7486-3.9045 (3H, m), 4.0014-4 .2037(2H,m),5.2157-5.2342(1H,m),6.8887-7.0487(7H,m),7.0488-7.0843( 2H, m), 7.1892-7, 2542 (4H, m), 7.4932-7.5767 (2H, m), 7.7348-7.7785 (2H, m).

[0094] Compound 10: 1H-NMR (d6-DMSO, 500MHz): 3.6267-3.7496 (2H, dd), 3.8400 (3H, s), 5.0157-5.0279 (1H, t), 6.8642-6.9245 (1H, dd), 6.9246-7.0681 (4H , m), 7.1639-7.2349 (2H, m), 7.2351-7.3572 (5H, m), 7.4471-7.5309 (2H, m), 7.5419-5676 (2H, m), 7.6379-7.6667 (2H, m).

[0095] Compound 11: 1 H-NMR (d6-DMSO, 500MHz): 3.6324-3.6624 (2H, m), 5.2365-5.2796 (1H, m), 6.8027-6.8120 (2H, m), 6.9216-7.1236 (7H, m) , 7.1424-7.1908(2H,m), 7.2630-7.3112(4H,m), 7.3839-7.4342(4H,m), 7.4716-7.5168(4H,m), 7.6826-7.7024(2H,m).

[0096] Comparative Examples 1 to 5

[0097] Comparative Examples 1 to 5 provide a sensitizer, which is respectively the comparative compound 1 Comparative Compound 2 Comparative compound 3 Comparative Compound 4 and comparative compound 5

[0098] Application Examples

[0099] This application example provides a photosensitive resin composition, which includes, in parts by weight, 100 parts of a base resin, 60 parts of a carbon-carbon double bond-containing compound, 5 parts of a photoinitiator HABI101, 25 parts of a solvent tetrahydrofuran, and 0.5 parts of a sensitizer; the sensitizers are the sensitizers provided in Examples 1 to 10 and Comparative Examples 1 to 5, respectively; the base resin is an acrylate copolymer, which is a copolymer (Mv = 10,000) obtained by mixing benzyl methacrylate, methacrylic acid, and hydroxyethyl methacrylate in a molar ratio of 70:10:20; the carbon-carbon double bond-containing compound is a monomer composed of ethoxylated trimethylolpropane triacrylate and ethoxylated bisphenol A dimethacrylate in a mass ratio of 1:5.

[0100] Blank example

[0101] The resin composition without adding the sensitizer was used as a blank example, and the other components and amounts were the same as those in the application example.

[0102] Performance Testing

[0103] (1) Compatibility evaluation

[0104] The photosensitive resin composition was thoroughly stirred and mixed, and then evenly coated on the surface of a 19 μm thick polyethylene terephthalate film serving as a support using a rod coater. The film was then dried in a dryer at 95°C for 4 minutes to form a photosensitive resin layer. The coating surface was then observed for precipitation of undissolved matter. Precipitation indicated poor compatibility, while absence of precipitation indicated good compatibility. The test results are shown in Table 1.

[0105] (2) Sensitivity performance evaluation

[0106] Sensitivity performance test under UV-LED

[0107] The photosensitive resin composition was stirred in the dark and cast on a PET template. A wire rod was used for coating and the solvent was removed by drying at 80°C for 3 minutes to form a coating with a thickness of about 38±2 μm. After exposure and development, the sensitivity (21 steps) of the full band / 365nm / 385nm / 405nm was observed (energy level 100mJ / cm 2 ); the test results are shown in Table 2.

[0108] (3) Resolution evaluation

[0109] The laminated substrate was exposed for 15 minutes through a line pattern mask with a width ratio of 1:1 between the exposed and unexposed parts, and then developed for twice the minimum development time. The minimum mask line width at which a cured resist line is normally formed was taken as the resolution value.

[0110] ○: The resolution value is 30 μm or less.

[0111] ◎: Resolution value is 30-50 μm (excluding end value).

[0112] ●: Resolution value is 50μm or above.

[0113] The test results are shown in Table 3.

[0114] (4) Development evaluation

[0115] The thickness of the photosensitive resin laminate is 40 μm and the area is 0.16 m 2 The photosensitive layer (resist layer) was dissolved in 200 mL of a 1 wt.% Na2CO3 aqueous solution and sprayed using a circulating sprayer at a spray pressure of 0.1 MPa for 3 hours. The developer was then left to stand for 1 day and the appearance of aggregates was observed.

[0116] ○: No coagulants: Almost no coagulants were found in the spray device, and very small amounts of coagulants were floating in the developer. These coagulants can be easily washed away with water.

[0117] ◎: Trace aggregates: Trace to small amounts of aggregates are visible on the spray device and are floating in the developer. They cannot be completely washed away with water.

[0118] ●: Agglutinates are visible on the entire spray device and floating in the developer. They cannot be completely washed off with water and most of them remain.

[0119] The test results are shown in Table 3.

[0120] (5) Adhesion evaluation

[0121] The laminated substrate was exposed for 15 minutes through a line pattern mask with a ratio of 1:100 between the width of the exposed part and the width of the unexposed part, and then developed for a development time twice the minimum development time. The minimum mask line width at which a cured resist line is normally formed was taken as the adhesion value.

[0122] ○: Adhesion value is 30 μm or less.

[0123] ◎: Adhesion value is 30-50 μm (excluding end value).

[0124] ●: Adhesion value is 50μm or more.

[0125] The test results are shown in Table 3.

[0126] Table 1

[0127] As can be seen from Table 1, the pyrazoline sensitizer provided in the present application has good compatibility with the components of the matrix resin, and no undissolved matter is precipitated on the surface after drying and film formation.

[0128] Table 2

[0129] As can be seen from Table 2, the pyrazoline sensitizer provided in the present application has a better photosensitizing effect than the control group, and the photocuring system under UV-LED light source can be successfully cured, which shows that the sensitizer of the present application has good applicability under the UV-LED photocuring system.

[0130] Table 3

[0131] As can be seen from Table 3, compared with Comparative Examples 1-5, the pyrazoline sensitizer provided in the present application can effectively improve the performance of the cured product; the photosensitive resin composition including the pyrazoline sensitizer has high resolution, excellent developability and high adhesion after curing; while the sensitizer structure shown in the comparative example, after curing, the photosensitive resin composition has poor resolution, developability and adhesion.

[0132] In summary, the pyrazoline sensitizer provided in the present application adopts a specific molecular structure design, so that the photosensitive resin combination including it has the advantages of good compatibility, high sensitivity, high resolution, excellent developability, and high adhesion. It has good hydrophilicity during development and can significantly reduce the amount of sludge in the developer during recycling, so that the developer can be reused multiple times and effectively used; it improves the curing efficiency of the UV-LED light curing system and has good applicability under the UV-LED light curing system.

[0133] The specific embodiments described above further illustrate the purpose, technical solutions and beneficial effects of this application. It should be understood that the above is only a specific embodiment of this application and is not intended to limit this application. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of this application should be included in the scope of protection of this application.

Claims

1. A pyrazoline sensitizer having a structure shown in Formula I: in, R1 and R2 are each independently selected from any one of H, halogen, carboxyl, nitro, cyano, amine, hydroxyl, C1-C20 straight or branched alkyl, C1-C20 straight or branched alkenyl, C3-C20 cycloalkyl, C1-C10 alkyl substituted with C3-C8 cycloalkyl, C3-C10 cycloalkyl substituted with C1-C20 alkyl, C2-C8 acyl or C6-C20 aryl; at least one -CH2- or -CH- in the C1-C20 straight or branched alkyl or C1-C20 straight or branched alkenyl may be independently replaced by -O-, -S-, -N(R)-, carbonyl, ester or At least one -CH2- in the C3-C10 cycloalkyl group may be substituted by at least one of -O-, -S- or -N(R)-; at least one -CH- in the C6-C20 aryl group may be substituted by at least one of -O-, -S- or -N(R)-; the R, R 1 Each is independently selected from H, C1-C6 alkyl; at least one H in the C1-C20 straight or branched alkyl, C1-C20 straight or branched alkenyl, C3-C10 cycloalkyl can be independently substituted by F; the R1 and R2 can each independently form a ring with the benzene ring to which they are bonded; The R3 is selected from a linear or branched C2-C18 unsaturated group, wherein the C2-C18 unsaturated group includes at least one phenyl group or The unsaturated groups include any one of cycloalkyl, olefin or alkynyl groups; at least one methylene group in the C2-C18 unsaturated groups can be independently replaced by -O-, -S-, -N(R')-, carbonyl, ester or At least one of the substitutions; said R′, R 2 , R 3 Each independently selected from H, C1-C6 alkyl, C3-C20 cycloalkyl, C3-C8 cycloalkyl substituted C1-C10 alkyl or C1-C20 alkyl substituted C3-C10 cycloalkyl; said R 2 When selected from C1-C6 alkyl groups, at least one methylene group in the C1-C6 alkyl group may be substituted by -O-, -S- or imino group; 2 The benzene ring to which it is bonded can form a ring; the R3 can form a ring with the benzene ring to which it is bonded; the dotted line indicates the connection site.

2. The pyrazoline sensitizer according to claim 1, wherein The R1 is selected from any one of H, amino, C2-C12 straight or branched alkyl or C6-C12 aryl; at least one -CH2- in the C2-C12 straight or branched alkyl may be substituted by at least one of -O-, -S-, -N(R")-, carbonyl or phenylene; the R" is selected from H or C1-C6 alkyl; Preferably, R1 is selected from H, C2-C4 straight or branched alkyl, dimethylamino, Any one of phenyl or cyclohexyl; wherein, indicates the connection site, "*" indicates the fusion site; Preferably, the C2-C4 straight-chain or branched alkyl group includes at least one of an ethyl group, a propyl group or a tert-butyl group.

3. The pyrazoline sensitizer according to claim 1 or 2, wherein The R2 is selected from any one of H, halogen or C2-C12 straight or branched alkyl; Preferably, at least one H in the C2-C12 straight or branched alkyl group is substituted by F; Preferably, R2 is selected from any one of H, trifluoromethyl or ethyl.

4. The pyrazoline sensitizer according to any one of claims 1 to 3, wherein The R3 is selected from a linear or branched C2-C16 unsaturated group, wherein the C2-C16 unsaturated group includes at least one substituted or unsubstituted phenyl group; the unsaturated group includes an alkenyl group or an alkynyl group; the substituent in the substituted or unsubstituted phenyl group includes any one of an amino group, a C1-C4 linear or branched alkyl group, or a C1-C4 linear or branched alkoxy group; the substituent in the substituted or unsubstituted phenyl group and the benzene ring to which it is bonded can form a ring; at least one methylene group in the aforementioned group can be substituted by at least one of an oxygen group, a sulfur group, or an imino group; Preferably, the R3 is selected from any one of the following groups: Among them, R 31 , R 32 Each is independently selected from any one of H, C1-C4 straight chain or branched alkyl, C1-C4 straight chain or branched alkoxy, dimethylamino, diethylamino or C3-C8 cycloalkyl; represents the junction site; Preferably, R3 is selected from styryl, phenylethynyl, 4-tert-butylstyryl, 4-tert-butylphenylethynyl, 4-dimethylaminostyryl, 4-dimethylaminophenylethynyl, 4-diethylaminostyryl, 4-diethylaminophenylethynyl, 2-methoxystyryl, 2-methoxyphenylethynyl, or 4-cyclohexylphenylene group.

5. The pyrazoline sensitizer according to any one of claims 1 to 4, wherein The pyrazoline sensitizer is selected from any one of the following compounds 1-13:

6. A method for preparing the pyrazoline sensitizer according to any one of claims 1 to 5, comprising the following steps: (1) reacting a compound of formula II with a compound of formula III to obtain an intermediate compound of formula IV; (2) reacting the intermediate compound obtained in step (1) with the compound of the structure represented by formula V to obtain the pyrazoline sensitizer; or, The preparation method comprises the following steps: (11) reacting the compound represented by formula II with the compound represented by formula III-1 to obtain an intermediate compound represented by formula IV-1; (12) reacting the intermediate compound obtained in step (11) with a compound of formula V to obtain the intermediate compound of formula I-1; (13) reacting the intermediate compound obtained in step (12) with R3-H to obtain the pyrazoline sensitizer; R1, R2 and R3 are all selected from the same range as in Formula I.

7. The preparation method according to claim 6, wherein: The molar ratio of the compound of formula II to the compound of formula III in step (1), and the molar ratio of the compound of formula II to the compound of formula III-1 in step (11) are each independently 1:(0.5-1.5); Preferably, the reactions in step (1) and step (11) are each independently carried out in an organic solvent; Preferably, the organic solvent comprises any one of dichloromethane, dichloroethane, methanol, ethanol or toluene, or a combination of at least two thereof; Preferably, the reactions in step (1) and step (11) are each independently carried out in the presence of an alkaline substance; Preferably, the alkaline substance comprises sodium hydroxide, sodium methoxide, potassium ethoxide, butyl lithium or phenyl lithium. At least one of; Preferably, the reaction temperature in step (1) and step (11) is independently 10 to 30° C., and the reaction time is independently 12 to 24 h. Preferably, the molar ratio of the intermediate compound in step (2) and step (12) to the compound of formula V is independently 1:(1-1.2); Preferably, the reactions in step (2) and step (12) are each independently carried out in the presence of an acidic substance; Preferably, the acidic substance includes any one or both of acetic acid or methanesulfonic acid; Preferably, the solvents for the reactions in step (2) and step (12) each independently include any one of dichloroethane, methanol, ethanol or toluene, or a combination of at least two thereof; Preferably, the reaction temperature in step (2) and step (12) is independently 50 to 110° C., and the reaction time is independently 12 to 24 h. Preferably, the reaction in step (13) is carried out in the presence of a catalyst; Preferably, the catalyst comprises Pd(dppf)Cl2; Preferably, the reaction temperature in step (13) is 90-110° C., and the reaction time is 6-8 h. 8 . A photosensitive resin composition comprising the pyrazoline sensitizer according to claim 1 .

9. A photosensitive resin composition as claimed in claim 8, further comprising a base resin, a photoinitiator and a compound containing a carbon-carbon double bond, wherein: The photosensitive resin composition comprises, by weight percentage, 10-80% of a base resin, 0.01-10% of a sensitizer, 0.1-20% of a photoinitiator, and 10-50% of a carbon-carbon double bond-containing compound; the sensitizer is the pyrazoline sensitizer according to any one of claims 1 to 5; Preferably, the matrix resin includes acrylic polymers, styrene polymers, epoxy polymers, aliphatic polyurethane acrylate polymers, aromatic polyurethane acrylate polymers, amide polymers, At least one of resin, amide epoxy resin, alkyd resin or phenolic resin; Preferably, the carbon-carbon double bond-containing compound includes any one or a combination of at least two of a compound obtained by reacting an α,β-unsaturated carboxylic acid with a polyol, a bisphenol A (meth)acrylate compound, a compound obtained by reacting an α,β-unsaturated carboxylic acid with a glycidyl-containing compound, a (meth)acrylate compound having an urethane bond in the molecule, nonylphenoxy polyvinyloxy acrylate, γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl-phthalate, β-hydroxyethyl-β'-(meth)acryloyloxyethyl-phthalate, β-hydroxypropyl-β'-(meth)acryloyloxyethyl-phthalate, phthalic acid compounds or (meth)acrylate alkyl esters; further preferred is any one or a combination of at least two of a bisphenol A (meth)acrylate compound or a (meth)acrylate compound having an urethane bond in the molecule; Preferably, the photoinitiator includes at least one of a bisimidazole compound, an acridine compound, an aromatic ketone compound, an anthraquinone compound, benzoin, a benzoin alkyl ether compound, an oxime ester compound, a triazine compound, a pyridine compound or a thioxanthone compound; Preferably, the photosensitive resin composition further comprises other auxiliary agents in an amount of 0.01 to 10% by mass.

10. Use of the pyrazoline sensitizer according to any one of claims 1 to 5 or the photosensitive resin composition according to claims 8 to 9 in a photocurable product; Preferably, the photocurable product comprises a dry film or a resin laminate prepared by photocuring.

Images