Pyrazoline sensitizer, preparation method thereof, photosensitive resin composition containing pyrazoline sensitizer and application

Abstract

The invention provides a pyrazoline sensitizer, a preparation method of the pyrazoline sensitizer, a photosensitive resin composition containing the pyrazoline sensitizer and application of the photosensitive resin composition. The pyrazoline sensitizer has a structure as shown in a formula I; the pyrazoline sensitizer has an excellent sensitizing effect, and is good in compatibility with resin and the like, so that the photosensitive resin composition containing the sensitizer is short in curing time, the ultraviolet curing efficiency is remarkably improved, and the pyrazoline sensitizer is particularly suitable for a UV-LED light curing system.

Description

Technical Field

[0001] The invention belongs to the technical field of photocurable materials, and in particular relates to a pyrazoline sensitizer, a preparation method thereof, a photosensitive resin composition containing the pyrazoline sensitizer, 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 the disadvantages of 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 strong light intensity are considered to be good substitutes in the field of photocuring, and UV-LED light sources have the advantages of saving electricity and reducing thermal effects. However, the photoinitiators suitable for mainstream UV-LEDs in the field of photocuring generally have poor performance and have the disadvantages of weak light absorption ability of the initiator, which limits the application of UV-LED in photocuring.

[0003] Sensitizers are an effective way to solve the above problems. Under the premise of not changing the photocurable composition system, the purpose of continuously absorbing and transferring energy can be achieved by adding sensitizers, thereby improving the problem that the initiator has a weak direct absorption capacity for light, improving the utilization rate of light, reducing the curing time and cost, and improving the curing effect of UV-LED photocuring technology. Among them, pyrazoline compounds have an absorption band of 380 to 410 nm, which is particularly suitable for use as a sensitizer in the UV-LED photocuring system, but the existing pyrazoline sensitizers have poor sensitization effects and long curing times.

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

[0005] In view of the shortcomings of the prior art, the purpose of the present invention is to provide a pyrazoline sensitizer, a preparation method thereof, a photosensitive resin composition containing the pyrazoline sensitizer and an application thereof. The pyrazoline sensitizer has an excellent sensitizing effect and good compatibility with resins, etc., so that the photosensitive resin composition including the sensitizer has a short curing time, significantly improves the ultraviolet light curing efficiency, and is particularly suitable for UV-LED light curing systems.

[0006] To achieve this object, the present invention adopts the following technical solutions:

[0007] In a first aspect, the present invention provides a pyrazoline sensitizer, wherein the pyrazoline sensitizer has a structure shown in Formula I:

[0008]

[0009] Wherein, 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 can 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-, and -N(R)-; at least one -CH- in the C6-C20 aryl group may be substituted by at least one of -O-, -S-, and -N(R)-; the R, R 1 Each is independently selected from H, a C1-C6 alkyl group; at least one H in the C1-C20 straight or branched alkyl group, C1-C20 straight or branched alkenyl group, and C3-C10 cycloalkyl group can be independently substituted 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-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 is independently selected from H, C1-C6 alkyl, C3-C20 cycloalkyl, C1-C10 alkyl substituted with C3-C8 cycloalkyl, C3-C10 cycloalkyl substituted with C1-C20 alkyl; 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; 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 invention, the pyrazoline sensitizer is designed with a specific molecular structure, that is, a specific mother core structure is adopted, and a specific substituent is selected, so that the pyrazoline sensitizer can achieve 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 particular under a UV-LED light curing system.

[0012] Preferably, the R1 is selected from any one of H, amino, C2~C12 straight chain or branched alkyl or C6~C12 aryl; at least one -CH2- in the C2~C12 straight chain 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, 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 invention, the C1-C20 may be, for example, C1, C2, C4, C6, C8, C10, C12, C14, C16, C18, C20, etc. The C3-C10 may be, for example, C3, C4, C5, C6, C7, C8, C9, C10, etc. The C2-C8 may be, for example, C2, C3, C4, C5, C6, C7, C8, etc.; the C1-C6 may be, for example, C1, C2, C3, C4, C5, C6, etc.; the C2-C18 may be, for example, C2, C4, C6, C8, C10, C12, C14, C16, C18, etc.; the C2-C12 may be, for example, C2, C3, C4, C5, C6, C7, C8, C9, C10, C12, etc.; the C6-C20 may be, for example, C6, C8, C10, C12, C14, C16, C18, C20, etc.; the above all refer to the number of C in the group, and the same expressions below represent the same meaning and numerical range.

[0016] Preferably, R2 is selected from any one of H, halogen or C2-C12 straight or branched alkyl;

[0017] Preferably, at least one H in the C2-C12 straight-chain or branched alkyl group is substituted by F.

[0018] Preferably, R2 is selected from any one of H, trifluoromethyl or ethyl.

[0019] 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 oxygen, sulfur or imine.

[0020] Preferably, the R3 is selected from any one of the following groups:

[0021]

[0022] 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 (for example, C3, C4, C5, C6, C7, C8 cycloalkyl); Indicates the connection site.

[0023] 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.

[0024] Preferably, the pyrazoline sensitizer is selected from any one of the following compounds 1-13:

[0025]

[0026] In the present invention, the selection of R1, R2 and R3 groups is crucial for the compound to play a better role. The three not only affect the solubility of the compound in the system, but whether R2 and R3 can form a conjugated structure of N—N—C with the main structure of formula I is the key to whether the compound can produce a good sensitization effect.

[0027] In a second aspect, the present invention provides a method for preparing the pyrazoline sensitizer according to the first aspect, the preparation method comprising the following steps:

[0028] (1) reacting a compound of formula II with a compound of formula III to obtain an intermediate compound of formula IV;

[0029]

[0030] (2) reacting the intermediate compound obtained in step (1) with the compound of the structure represented by formula V to obtain the pyrazoline sensitizer;

[0031]

[0032] or,

[0033] The preparation method comprises the following steps:

[0034] (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;

[0035]

[0036] (12) reacting the intermediate compound obtained in step (11) with a compound of formula V to obtain the intermediate compound of formula I-1;

[0037]

[0038] (13) reacting the intermediate compound obtained in step (12) with R3-H to obtain the pyrazoline sensitizer;

[0039] R1, R2, and R3 are all selected from the same range as in Formula I.

[0040] 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, 1.5, etc.

[0041] Preferably, the reactions in step (1) and step (11) are each independently carried out in an organic solvent.

[0042] Preferably, the organic solvent includes any one of dichloromethane, dichloroethane, methanol, ethanol or toluene, or a combination of at least two thereof.

[0043] Preferably, the reactions in step (1) and step (11) are each independently carried out in the presence of an alkaline substance.

[0044] Preferably, the alkaline substance includes at least one of sodium hydroxide, sodium methoxide, potassium ethoxide, butyl lithium or phenyl lithium.

[0045] Preferably, the reaction temperature in 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, 30°C, etc.; the reaction time is independently 12 to 24h, for example, 12h, 14h, 16h, 18h, 20h, 22h, 24h, etc.

[0046] Preferably, the molar ratio of the intermediate compound in step (2) and step (12) to the compound of the structure represented by formula V is independently 1:(1 to 1.2).

[0047] Preferably, the reactions in step (2) and step (12) are each independently carried out in the presence of an acidic substance.

[0048] Preferably, the acidic substance includes any one or both of acetic acid and methanesulfonic acid.

[0049] 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 of them.

[0050] Preferably, the reaction temperature in step (2) and step (12) is independently 50-110°C, for example, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, etc.; the reaction time is independently 12-24h, for example, 12h, 14h, 16h, 18h, 20h, 22h, 24h, etc.

[0051] In the present invention, 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.

[0052] Preferably, the reaction in step (13) is carried out in the presence of a catalyst.

[0053] Preferably, the catalyst comprises Pd(dppf)Cl2.

[0054] Preferably, the reaction temperature in step (13) is 90-110°C, for example, it can be 90°C, 92°C, 94°C, 98°C, 100°C, 102°C, 104°C, 106°C, 108°C, 110°C, etc.; the reaction time is 6-8h, for example, it can be 6h, 7h, 8h, etc.

[0055] In the present invention, 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.

[0056] In a third aspect, the present invention provides a photosensitive resin composition, wherein the photosensitive resin composition comprises the pyrazoline sensitizer according to the first aspect.

[0057] Preferably, the photosensitive resin composition further comprises a base resin, a photoinitiator and a carbon-carbon double bond-containing compound, wherein, by mass 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%, 80%, etc.), 0.01-10% of the sensitizer (for example, 0.01%, 0.05%, 0.08%, 0.09%, 10.10%, 10.20%, 10.30%, 10.40%, 10.50%, 10.60%, 10.70%, 10.80%, 10.90%, 10.90%, 11.10%, 11.11%, 11.12%, 11.13%, 11.14%, 11.15%, 11.16%, 11.17%, 11.18%, 11.19%, 11.20%, 11.21%, 11.22%, 11.23%, 11.24%, 11.25%, 11.26%, 11.27%, 11.28%, 11.29%, 11.30%, 11.31%, 11.32%, 11.33%, 11.34%, 11.35%, .1%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, etc.), photoinitiator 0.1-20% (for example, it can be 0.3%, 1%, 3%, 5%, 8%, 10%, 13%, 15%, 18%, 20%, etc.) and carbon-carbon double bond-containing compound 10-50% (for example, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, etc.); the sensitizer includes the pyrazoline sensitizer as described in the first aspect.

[0058] In the present invention, the pyrazoline sensitizer is used in combination with a photoinitiator to significantly improve the photocuring efficiency and the performance of the cured product.

[0059] 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.

[0060] In the present invention, the acrylic polymer, aliphatic polyurethane acrylate polymer, and aromatic polyurethane acrylate polymer are not limited to acrylic acid and acrylate, but refer to acrylic acid, acrylate and their derivatives, such as methacrylic acid polymer, aliphatic polyurethane methacrylate polymer, aromatic polyurethane methacrylate, etc.

[0061] 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 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.

[0062] Preferably, the photoinitiator includes at least one of a bisimidazole compound, an acridine compound, an aromatic ketone compound, anthraquinone compound, benzoin, benzoin alkyl ether compound, oxime ester compound, triazine compound, pyridine compound or thioxanthone compound.

[0063] 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.

[0064] Preferably, the photosensitive resin composition further includes other additives in an amount of 0.01-10% by mass, for example, 0.01%, 0.05%, 0.08%, 0.1%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, etc.

[0065] In the present invention, the auxiliary agent includes a pigment, a solvent, etc. 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 indoleanthrone pigment, an indole pigment, an indole pigment, a pyrroledione pigment, etc. The above pigments can be used alone or in combination, depending on the specific application requirements of the product.

[0066] The solvent includes ketones, such as methyl ethyl ketone, butanone, cyclohexanone, heptanone, 3-heptanone, etc.; cyclic ethers, such as tetrahydrofuran and pyran, etc.; cyclic esters, such as γ-butyrolactone, etc.; (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, tripropylene glycol monoethyl ether, etc.; aromatic hydrocarbons, such as toluene, xylene, trimethylbenzene, etc. These solvents may be used alone or in combination of two or more.

[0067] In a fourth aspect, the present invention 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.

[0068] Preferably, the photocurable product comprises a dry film or a resin laminate prepared by photocuring.

[0069] The numerical range described in the present invention not only includes the point values ​​listed above, but also includes any point values ​​between the above numerical ranges that are not listed. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0070] Compared with the prior art, the present invention has the following beneficial effects:

[0071] In the present invention, the pyrazoline sensitizer is designed through a specific molecular structure, that is, a specific mother core structure is adopted, and a specific substituent is selected, 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 particular under a UV-LED light curing system. DETAILED DESCRIPTION

[0072] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0073] The raw materials used in the examples and comparative examples of the present invention can be obtained from commercial sources or prepared by conventional methods in the prior art.

[0074] Example 1

[0075] This embodiment provides a pyrazoline sensitizer, wherein the pyrazoline sensitizer is compound 1; and the preparation method of the pyrazoline sensitizer is as follows:

[0076] (1) Preparation of intermediate 1a

[0077] At room temperature, 17.7 g of N,N-diethyl-4-aminobenzaldehyde, 19.9 g of 4-bromoacetophenone and 100 g of methanol were added to a 250 mL four-necked flask and stirred until completely dissolved; 3.24 g of sodium methoxide was added and the addition was completed in about half an hour; the mixture was stirred at 25°C for 8 h, and the reaction progress was tracked by HPLC and TLC synchronously (EA:Hex=1:10). The product gradually precipitated, and the reaction was stopped when the raw material was <1%; the filter cake was collected by suction and dried to obtain 31.9 g of intermediate 1a (HPLC: 99.0%, yield 89%).

[0078] use 1 The structure of intermediate 1a was characterized by H-NMR, and the results are as follows.

[0079] 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).

[0080] (2) Preparation of intermediate 1b

[0081] At room temperature, 35.8 g of intermediate 1a, 35 g of acetic acid and 150 g of methanol were added to a 500 mL four-necked flask, stirred evenly and then heated to 55° C.; 11.35 g of phenylhydrazine was added dropwise over half an hour, and after the addition was completed, the mixture was kept at 55° C. for 24 hours. The reaction was tracked synchronously by HPLC and TLC (EA: Hex = 1:10). When the 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%).

[0082] use 1 The structure of intermediate 1b was characterized by H-NMR, and the results are as follows:

[0083] 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).

[0084] (3) Preparation of Compound 1

[0085] At room temperature, 4.5 g of intermediate 1b, 1.6 g of p-tert-butylstyrene and 50 mL of DMF were added to a dry 100 mL four-necked flask and stirred until the solution was clear; Pd(dppf)Cl2 was added under nitrogen protection, and then the temperature was raised to 100°C and the reaction was kept warm for 8 hours. The reaction was tracked synchronously by HPLC and TLC (EA:Hex=1:10). When the mass content of the raw material was ≤1%, the reaction was stopped; DMF was removed by concentration under reduced pressure to obtain a crude product, 100 ml of ethyl acetate was added, and the product was washed with water twice (50 mL each time); and then subjected to column chromatography to obtain 3.3 g of a bright yellow solid with a melting point of 97.4-98.5°C (HPLC 99.6%, yield 62.6%).

[0086] use 1 The structure of compound 1 was characterized by H-NMR, and the results are as follows:

[0087] 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).

[0088] The synthetic route of compound 1 is as follows:

[0089]

[0090] Embodiments 2 to 11

[0091] Embodiments 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 Embodiment 1, except that the raw material 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.

[0092] use 1 The structure of compound 2-11 was characterized by H-NMR, and the results are as follows:

[0093] Compound 2: 1 H-NMR (d6-DMSO, 500MHz): 1.0237-1.0636 (6H, t), 1.3010 (9), 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), 7.1464-7.15 77 (2H, t), 7.4564-7.5276 (4H, m), 7.5754-7.5954 (2H, d), 7.7625-7.7825 (2H, d).

[0094] 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).

[0095] 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).

[0096] 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).

[0097] Compound 6: 1 H-NMR (d6-DMSO, 500MHz):

[0098] 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), 6.8127 (2H, d), 6.9 418-7.0232(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).

[0099] 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).

[0100] 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).

[0101] 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).

[0102] 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), 6.9246-7.0 681 (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).

[0103] Compound 11: 1 H-NMR (d6-DMSO, 500MHz):

[0104] 3.6324-3.6624(2H,m),5.2365-5.2796(1H,m),6.8027-6.8120(2H,m),6.9216-7.1236(7H,m),7.1424-7.1 908 (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).

[0105] Comparative Examples 1 to 5

[0106] Comparative Examples 1 to 5 provide a sensitizer, respectively, wherein the sensitizer is comparative compound 1 Comparative Compound 2 Comparative Compound 3 Comparative Compound 4 Comparative Compound 5

[0107] Application Examples

[0108] This application example provides a photosensitive resin composition, which includes, 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=10000) 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 used in combination with ethoxylated trimethylolpropane triacrylate and ethoxylated bisphenol A dimethacrylate in a mass ratio of 1:5.

[0109] Blank example

[0110] The resin composition without adding sensitizer was used as a blank example, and the other components and amounts were the same as those in the application example.

[0111] Performance Testing

[0112] (1) Compatibility: The photosensitive resin composition was fully stirred and mixed, and evenly coated on the surface of a 19 μm thick polyethylene terephthalate film as a support using a rod coater. The film was dried in a dryer at 95° C. for 4 min to form a photosensitive resin layer. The coating surface was observed to see whether there was precipitation of undissolved matter. If there was precipitation, it indicated poor compatibility; if there was no precipitation, it indicated good compatibility. The test results are shown in Table 1.

[0113] (2) Photosensitivity performance evaluation

[0114] Sensitivity performance test under UV-LED

[0115] The photosensitive resin composition was stirred in the dark, and the material was taken on a PET template, and a film was coated using a wire rod, and dried at 80°C for 3 minutes to remove the solvent to form a coating film with a thickness of about 38±2μm. After exposure and development, the sensitivity of the full band / 365nm / 385nm / 405nm (21 steps) (energy level 100mJ.cm 2 ); the test results are shown in Table 2.

[0116] (3) Resolution evaluation

[0117] The laminated substrate was exposed for 15 minutes through a line pattern mask with a ratio of 1:1 between the width of the exposed part and the unexposed part, and then developed for twice the minimum development time, with the minimum mask line width for normally forming a cured resist line as the resolution value.

[0118] ○: The resolution value is 30 μm or less.

[0119] ◎: Resolution value is 30μm-50μm (excluding end value).

[0120] ●: Resolution value is above 50μm.

[0121] The test results are shown in Table 3.

[0122] (4) Evaluation of developing properties

[0123] The photosensitive resin laminate has a thickness of 40 μm and an area of ​​0.16 m 2 The photosensitive layer (resist layer) was dissolved in 200 mL of 1 wt.% Na2CO3 aqueous solution and sprayed for 3 hours using a circulating spray device at a spray pressure of 0.1 MPa. Then, the developer was left for 1 day to observe the appearance of aggregates.

[0124] ○: No agglutinate: There is almost no agglutinate in the spray device, and a very small amount of agglutinate floats in the developer; it can be easily washed away by water.

[0125] ◎: Trace agglutination: Trace to small amount of agglutination is visible in the spray device, and trace to small amount of agglutination is floating in the developer; it cannot be completely washed away by water.

[0126] ●: Agglutination: Agglutination is visible on the entire spray device and floating in the developer. It cannot be completely washed away with water and most of it remains.

[0127] The test results are shown in Table 3.

[0128] (5) Adhesion evaluation

[0129] The laminated substrate was exposed for 15 min through a line pattern mask with a ratio of 1:100 between the width of the exposed part and the unexposed part, and then developed for a development time twice the minimum development time, with the minimum mask line width for normally forming a cured resist line being taken as the adhesion value.

[0130] ○: Adhesion value is 30 μm or less.

[0131] ◎: Adhesion value is 30 μm-50 μm (excluding end value).

[0132] ●: Adhesion value is 50μm or more.

[0133] The test results are shown in Table 3.

[0134] Table 1

[0135]

[0136] It can be seen from Table 1 that the pyrazoline sensitizer provided by the present invention has good compatibility with the components of the matrix resin, and no undissolved matter is precipitated on the surface after drying and film formation.

[0137] Table 2

[0138]

[0139]

[0140] As can be seen from Table 2, the pyrazoline sensitizer provided by the present invention has a better photosensitizing effect than the control group, and the photocuring system under the irradiation of the UV-LED light source can be successfully cured, which shows that the sensitizer of the present invention has good applicability under the UV-LED photocuring system.

[0141] Table 3

[0142]

[0143]

[0144] It can be seen from Table 3 that, compared with Comparative Examples 1-5, the pyrazoline sensitizer provided by the present invention can effectively improve the performance of the cured product; after the photosensitive resin composition including the pyrazoline sensitizer is cured, it has high resolution, excellent developability and high adhesion; while for the sensitizer of the structure shown in the comparative example, after the photosensitive resin composition is cured, the resolution, developing effect and adhesion are all deteriorated.

[0145] In summary, the pyrazoline sensitizer provided by the present invention adopts a specific molecular structure design, so that the photosensitive resin combination including the pyrazoline sensitizer has good compatibility, high sensitivity, high resolution, excellent developability, high adhesion, good hydrophilicity during development, and can significantly reduce the amount of sludge in the developer during recycling, so that the developer can be reused and effectively used multiple times; the curing efficiency of the UV-LED light curing system is improved, and the photosensitive resin combination including the pyrazoline sensitizer has good applicability under the UV-LED light curing system.

[0146] The specific embodiments described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A pyrazoline sensitizer, characterized in that: The pyrazoline sensitizer has a structure shown in Formula I: Wherein, 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-, and -N(R)-; at least one -CH- in the C6-C20 aryl group may be substituted by at least one of -O-, -S-, and -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 is independently selected from H, C1-C6 alkyl, C3-C20 cycloalkyl, C1-C10 alkyl substituted with C3-C8 cycloalkyl, C3-C10 cycloalkyl substituted with C1-C20 alkyl; 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 groups; 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, characterized in that 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, characterized in that 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, characterized in that 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, characterized in that The pyrazoline sensitizer is selected from any one of the following compounds 1-13:

6. A method for preparing a pyrazoline sensitizer according to any one of claims 1 to 5, characterized in that: The preparation method comprises 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, characterized in that: 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 at least one of sodium hydroxide, sodium methoxide, potassium ethoxide, butyl lithium or phenyl lithium; 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 used in the reactions of step (2) and step (12) 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, characterized in that The photosensitive resin composition comprises the pyrazoline sensitizer according to any one of claims 1 to 5.

9. A photosensitive resin composition as claimed in claim 8, characterized in that: 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, 0.01-10% of the sensitizer, 0.1-20% of the photoinitiator and 10-50% of the 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 comprises 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; 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.

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