Bipyrazoline structure sensitizer as well as preparation method and application thereof

Abstract

The invention relates to a double-pyrazoline structure sensitizer as well as a preparation method and application thereof. The double-pyrazoline structure sensitizer disclosed by the invention has a structure as shown in a formula (1). The bipyrazoline structure sensitizer has a wide UV absorption spectrum, and is strong in absorption, more excellent in photosensitive activity and good in solid form. Besides, the flexibility of the two pyrazoline groups is adjusted by introducing an ether bond and an additional alkoxy structure, so that on one hand, the designed molecular solid form is ensured to be good, and on the other hand, the compatibility in a photocuring system is ensured to be good. The photocuring composition containing the photocuring composition has excellent photosensitivity and developability, and the cured composition has good resolution and strong adhesive force.

Description

[0001] This invention relates to the field of photocuring technology, and in particular to a class of bispyrazoline sensitizers, their preparation methods and applications. Background Technology

[0002] Ultraviolet (UV) curing technology has been widely used due to its advantages such as fast curing speed and low environmental pollution. The photoinitiator plays a decisive role in the curing efficiency of the entire curing system. Most efficient free radical or cationic photoinitiators (such as traditional thioxanthones, benzophenones, iodonium salts, and thiodonium salts) have their maximum absorption peaks located in the mid-to-short wavelength UV region (250-350 nm). However, the main strong emission lines of commonly used, safer, and more penetrating medium-pressure mercury lamps in industry are around 365 nm, and LED UV light sources are mainly concentrated at 365 nm, 385 nm, 395 nm, and even 405 nm (visible light region). Traditional initiators have very low absorption efficiency for these long-wavelength UV / visible light, resulting in low curing efficiency, energy waste, and incomplete curing (especially in deep or colored systems).

[0003] To address the aforementioned challenges, photosensitizers have been introduced into UV curing systems. This overcomes the bottleneck of traditional photoinitiators' insufficient absorption of long-wavelength light (especially LED UV and visible light). By introducing photosensitizer molecules that efficiently absorb long-wavelength light, light energy is indirectly transferred to the initiator molecules via FRET (Follicular Unit Transfer) or electron transfer mechanisms, thereby activating the polymerization reaction. The development of this technology has directly promoted the widespread adoption of LED UV curing technology and the rise of cutting-edge applications such as visible light curing, and is one of the key technologies for improving UV curing efficiency and expanding its application range.

[0004] Currently, finding sensitizers that match the absorption wavelength of photoinitiators and have good compatibility has been a research hotspot in this field. Pyrazoline compounds are a very important class of sensitizers and have been widely used. However, existing pyrazoline compounds have drawbacks to varying degrees when used as sensitizers, such as unsatisfactory solubility and poor photosensitivity enhancement. Existing literature provides a macromolecular pyrazoline sensitizer that solves the problems of solubility and formulation compatibility, but in practical applications, it has been found that it has problems such as large addition amounts, insufficient sensitivity enhancement, and high viscosity, making it inconvenient to use. Therefore, further optimization is needed. Summary of the Invention

[0005] The main objective of this invention is to provide a class of bispyrazoline sensitizers to solve the problems of excessive dosage, insufficient sensitivity enhancement, and high viscosity in the prior art, which makes them inconvenient to use.

[0006] In a first aspect, the present invention provides a bispyrazoline compound represented by the following general formula (1):

[0007]

[0008] In this context, R1 and R2 each independently represent substituents that have a conjugated structure with the pyrazole ring;

[0009] R3 and R5 are each independently selected from hydrogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C14 cycloalkyl, C1-C10 alkylene, substituted or unsubstituted C3-C14 cycloalkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C4-C10 cyclodienyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C2-C30 heteroaryl.

[0010] R4 and R6 are each independently selected from hydrogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C14 cycloalkyl, C1-C10 alkylene, substituted or unsubstituted C3-C14 cycloalkyl, and substituted or unsubstituted C1-C20 alkoxy.

[0011] L represents -(L1-O) m -L2-、-CO(L1-O) m -L2CO-, -CO(L1-O) m -L2-、-(L1-O) m -L2CO-;

[0012] L1 and L2 are each independently selected from C1 to C10 alkylene groups;

[0013] m is independently selected from 1, 2, 3, 4, 5, 6, 7, 8, or 9;

[0014] p, q, s, and t are independently selected from 0, 1, 2, 3, or 4.

[0015] In one embodiment, R1 and R2 are each independently selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C2-C20 alkenyl, and substituted or unsubstituted C4-C10 cyclodiene.

[0016] In one embodiment, R1 and R2 are each independently selected from phenyl, naphthyl, biphenyl, pyrrolyl, imidazolyl, indolyl, thiophene, furanyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, carbazole, C2-C10 alkenyl, C6-C12 aryl, C2-C4 alkenylidel, and C4-C8 cyclodienyl; each group may be independently substituted by one or more of the following groups: C1-C10 alkyl, C2-C10 alkenyl, C3-C10 cycloalkyl, and C1-C6 alkenylidel. The aryl group can be a C3-C10 cycloalkyl group, a C6-C14 aryl group, a C6-C12 aryl C1-C2 alkylene group, a C6-C12 aryl C2-C4 alkenyl group, or a C2-C14 heteroaryl group. Furthermore, the C6-C14 aryl group in the C6-C14 aryl group, C2-C14 heteroaryl group, C6-C12 aryl C1-C2 alkylene group, and C6-C12 aryl C2-C4 alkenyl group can be mono- or poly-substituted with a C1-C10 alkyl group or a C1-C10 alkoxy group.

[0017] In one embodiment, the substituents in R1 and R2 are selected from: C1-C6 alkyl, C2-C6 alkenyl, C3-C8 cycloalkyl-C1-C4 alkylene, C3-C8 cycloalkyl, C6-C12 aryl, C6-C10 aryl-C1-C2 alkylene, C6-C10 aryl-C2 alkenyl, C1-C6 alkyl-substituted C6-C10 aryl-C2 alkenyl, C1-C6 alkoxy-substituted C6-C10 aryl-C2 alkenyl, and C2-C10 monocyclic or bicyclic heteroaryl (such as pyrroleyl, imidazolyl, carbazoleyl, indolyl, thiophenyl, furanyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl).

[0018] In one embodiment, R1 and R2 are each independently selected from phenyl, naphthyl, biphenyl, pyrrolyl, imidazolyl, indolyl, thiophene, furanyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, carbazoleyl substituted at the 9-position with a C1-C6 alkyl, vinyl, allyl, propenyl, phenyl, naphthyl, or biphenyl, aryl-C2 alkenyl-C6, alkenyl-C2, and cyclodienyl-C4; each group may be independently substituted by one or more of the following groups: C1-C6 alkyl, C3-C8 cyclodienyl. Alkyl C1-C2 alkylene, C3-C8 cycloalkyl, C6-C10 aryl, C6-C10 aryl C1-C2 alkylene, C6-C10 aryl C2-alkenyl, C1-C6 alkyl-substituted C6-C10 aryl C2-alkenyl, C1-C6 alkoxy-substituted C6-C10 aryl C2-alkenyl, C2-C10 monocyclic or bicyclic heteroaryl (such as pyrrole, imidazolyl, carbazole, indolyl, thiophene, furanyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl).

[0019] In one embodiment, R1 and R2 are each independently selected from the following groups:

[0020]

[0021] Among them, R 11 Each is independently selected from hydrogen, C1-C10 alkyl, C2-C10 alkenyl, C3-C10 cycloalkyl, C1-C6 alkylene, C3-C10 cycloalkyl, C6-C14 aryl, C6-C12 aryl, C1-C2 alkylene, C6-C12 aryl, C2-C4 alkenyl, and C2-C14 heteroaryl;

[0022] R 12 Each is independently selected from hydrogen, C1-C6 alkyl groups, and C1-C6 alkoxy groups;

[0023] M is selected from O, S, or NR. 13 ;

[0024] X is selected from CH or N;

[0025] R 13 Selected from hydrogen, C1-C10 alkyl, C2-C10 alkenyl, C3-C10 cycloalkyl, C1-C6 alkylene, C3-C10 cycloalkyl, C6-C14 aryl, C6-C12 aryl, C1-C2 alkylene, C6-C12 aryl, C2-C4 alkenyl, C2-C14 heteroaryl, and C1-C10 alkoxy.

[0026] a1 is selected from 0, 1, 2, 3, 4 or 5; a2 is selected from 0, 1, 2, 3, 4, 5, 6 or 7; a3 is selected from 0, 1, 2, 3 or 4; a4 is selected from 0, 1, 2 or 3; a5 is selected from 0, 1 or 2.

[0027] Preferably, R 11 Each is independently selected from hydrogen, C1-C6 alkyl, vinyl, allyl, propenyl, C3-C8 cycloalkyl, C1-C4 alkylene, C3-C8 cycloalkyl, C6-C12 aryl, C6-C10 aryl, C1-C2 alkylene, C6-C10 aryl, C2-C10 alkenyl, and C2-C10 monocyclic or bicyclic heteroaryl (such as pyrrole, imidazolyl, carbazole, indolyl, thiophene, furanyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl).

[0028] Preferably, R 13 The compound is selected from C1-C6 alkyl, C2-C6 alkenyl, C3-C8 cycloalkyl, C1-C4 alkylene, C3-C8 cycloalkyl, C6-C12 aryl, and C1-C6 straight alkoxy. More preferably, R13 Selected from C1 to C6 alkyl, allyl, propenyl, phenyl, naphthyl, and biphenyl.

[0029] In one embodiment, R1 and R2 are each independently selected from any one of the following groups:

[0030]

[0031] In one embodiment, R3 and R5 are each independently selected from hydrogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C8 cycloalkyl, C1-C4 alkylene, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C4-C8 cyclodienyl, substituted or unsubstituted C6-C14 aryl, and substituted or unsubstituted C2-C14 heteroaryl.

[0032] In one embodiment, R3 and R5 are each independently selected from hydrogen, C1-C6 alkyl, C3-C8 cycloalkyl, C2-C8 alkenyl, and C6-C10 aryl.

[0033] In one embodiment, R4 and R6 are each independently selected from hydrogen, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C8 cycloalkyl, C1-C4 alkylene, substituted or unsubstituted C3-C8 cycloalkyl, and substituted or unsubstituted C1-C10 alkoxy.

[0034] Preferably, R4 and R6 are each independently selected from hydrogen, C1-C6 alkyl groups, C3-C8 cycloalkyl groups, and C1-C6 alkoxy groups. More preferably, R4 and R6 are each independently selected from hydrogen and C1-C4 alkoxy groups.

[0035] In one embodiment, L1 and L2 are each independently selected from C1 to C6 alkylene groups.

[0036] Preferably, L1 and L2 are each independently selected from -(CR a R b ) n -, R a R bEach is independently selected from hydrogen, C1 to C2 alkyl groups, and n is selected from 1, 2, 3, 4, 5 or 6. More preferably, each of L1 and L2 is independently selected from -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2CH2-, -CH(CH3)-, -C(CH3)2-, -CH(CH3)CH2-, -C(CH3)2CH2-, -CH2CH(CH3)CH2-, -CH2C(CH3)2CH2-, -CH(CH3)CH2CH2-, -C(CH3)2CH2CH2-.

[0037] In one implementation, L is selected from:

[0038] -(CH2) 1-4 O(CH2) 1-4 -;

[0039] -(CH2) 1-4 O(CH2) 1-4 O(CH2) 1-4 -;

[0040] -(CH2) 1-4 O(CH2) 1-4 O(CH2) 1-4 O(CH2) 1-4 -;

[0041] -(CH2) 1-4 O(CH2) 1-4 O(CH2) 1-4 O(CH2) 1-4 O(CH2) 1-4 -;

[0042] -(CH2) 1-4 O(CH2) 1-4 O(CH2) 1-4 O(CH2) 1-4 O(CH2) 1-4 O(CH2) 1-4 -

[0043] Wherein, the -(CH2) 1-4 - Each is independently selected from -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-.

[0044] Preferably, L is selected from:

[0045] -CH2OCH2-;

[0046] -CH2OCH2OCH2-;

[0047] -CH2OCH2OCH2OCH2;

[0048] -CH2OCH2OCH2OCH2OCH2OCH2;

[0049] -CH2OCH2OCH2OCH2OCH2OCH2OCH2-;

[0050] -CH2CH2OCH2CH2-;

[0051] -CH2CH2OCH2CH2OCH2CH2-;

[0052] -CH2CH2OCH2CH2OCH2CH2OCH2CH2-;

[0053] -CH2CH2OCH2CH2OCH2CH2OCH2CH2OCH2CH2-;

[0054] -CH2CH2OCH2CH2OCH2CH2OCH2CH2OCH2CH2OCH2CH2-;

[0055] -CH2CH2CH2OCH2CH2CH2-;

[0056] -CH2CH2CH2OCH2CH2CH2OCH2CH2CH2-;

[0057] -CH2CH2CH2OCH2CH2CH2OCH2CH2CH2OCH2CH2CH2-;

[0058] -CH2CH2CH2OCH2CH2CH2OCH2CH2CH2OCH2CH2CH2OCH2CH2CH2-.

[0059] Preferably, the ratio of carbon atoms to oxygen atoms in L is not higher than 6, or not higher than 5, or not higher than 4, or not higher than 3.

[0060] In one embodiment, the pyrazoline compound has the structure shown in formula (II) or formula (III):

[0061]

[0062] In one embodiment, the pyrazoline compound is selected from:

[0063]

[0064]

[0065] The present invention also provides a method for synthesizing the pyrazoline compounds, wherein the method is selected from one of the following routes:

[0066] Route 1:

[0067] When R1 and R2 are the same, R4 and R6 are the same, R3 and R5, p and q are the same, and s and t are the same, the synthetic route of the pyrazoline compound includes:

[0068]

[0069] Route 2:

[0070] When R1 and R2 are different, and all other parameters are the same, the synthetic route for the pyrazoline compounds includes:

[0071] Route 3:

[0072] When R4 differs from R6, and at least one of p and q differs, and R1 is the same as R2, the synthetic route for the pyrazoline compound includes:

[0073]

[0074] Route 4:

[0075] The synthetic routes for the pyrazoline compounds include:

[0076]

[0077] Wherein, Lg represents a leaving group, such as Ts (4-methylbenzenesulfonyl), Tf (trifluoromethanesulfonyl), Tfa (trifluoroacetyl); X represents hydrogen, halogen (such as chlorine, bromine), -OLg.

[0078] In a second aspect, the present invention also provides a photosensitizer containing at least one of the pyrazoline compounds described in the present invention.

[0079] Preferably, the photosensitizer uses the pyrazoline compounds described in this invention as the active ingredient.

[0080] In a third aspect, the present invention also provides a photosensitizing composition comprising at least one of the pyrazoline compounds described in the present invention, a photoinitiator, and a polymeric compound having an olefinic unsaturated bond.

[0081] Preferably, the content of the pyrazoline compound of the present invention in the photosensitive composition is 0.01-10%. More preferably, the content is 0.01%, 0.05%, 0.08%, 0.1%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, or any two of these values.

[0082] Preferably, the photosensitive composition further contains an inorganic compound.

[0083] In a fourth aspect, the present invention also provides an alkaline-developable photosensitive resin composition comprising at least one of the pyrazoline compounds described in the present invention, a photoinitiator, and an alkaline-developable compound having an alkene-type unsaturated bond.

[0084] Preferably, the content of the pyrazoline compound of the present invention in the alkaline-developable photosensitive resin composition is 0.01-10%. More preferably, the content is 0.01%, 0.05%, 0.08%, 0.1%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, or any two of these values.

[0085] In a fifth aspect, the present invention also provides a coloring alkali-developable photosensitive resin composition comprising the alkali-developable photosensitive resin composition and pigment described herein.

[0086] In a sixth aspect, the present invention also provides a chemical for the electronics industry, comprising the photosensitive composition described herein.

[0087] Preferably, the chemicals used in the electronics industry are resist inks, solder resist inks, printing inks, inkjet inks, coatings, or adhesives.

[0088] In a seventh aspect, the present invention also provides a photoresist containing at least one of the photosensitizers described in the present invention.

[0089] Preferably, the content of the pyrazoline compound of the present invention in the photoresist is 0.01-10%. More preferably, the content is 0.01%, 0.05%, 0.08%, 0.1%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, or any two of these values.

[0090] Preferably, the photoresist further comprises a photoinitiator, a multifunctional acrylate monomer, an alkali-soluble resin, additives, a colorant, and a solvent.

[0091] In an eighth aspect, the present invention also provides an article obtained by using either the electronic industry chemicals described in the present invention or the photoresist of the present invention as a raw material.

[0092] Preferably, the article is a printed circuit board, an LCD display, an OLED display, a solar panel, a consumer electronics product, or a semiconductor device; more preferably, the consumer electronics product is a mobile phone, a television, or a computer.

[0093] In the compounds of the present invention, any atom not specified as a particular isotope is included as any stable isotope of that atom, and includes atoms at both their natural and non-natural isotopic abundances.

[0094] In this invention, the term "alkyl" refers to a straight-chain or branched saturated aliphatic hydrocarbon group containing, for example, 1 to 20 carbon atoms, preferably containing 1 to 15 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms. Examples include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, etc.

[0095] In this invention, the term "alkoxy" refers to -O-alkyl, wherein the alkyl group has the meaning as described above. Examples include, but are not limited to, methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, etc.

[0096] In this invention, the term "cycloalkyl" refers to a saturated cyclic aliphatic hydrocarbon group having a specific number of carbon atoms, preferably containing 3 to 14 carbon atoms, more preferably containing 3 to 10 carbon atoms or 3 to 8 carbon atoms. Examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl, norbornel, etc.

[0097] In this invention, the term "cycloalkyl alkylene" refers to a group in which a cycloalkyl group is attached to an alkyl group, wherein the alkyl group serves as the linking site. The cycloalkyl group and the alkyl group have the meanings described above. Examples of cycloalkyl alkylenes include, for example, C3-14 cycloalkyl C1-10 cycloalkylenes, C3-10 cycloalkyl C1-6 cycloalkylenes, and C3-8 cycloalkyl C1-4 cycloalkylenes. Examples include, but are not limited to, cyclopropylmethylene, cyclobutylmethylene, cyclopentylmethylene, cyclohexylmethylene, cycloheptylmethylene, cyclopropylethylene, cyclobutylethylene, cyclopentylethylene, cyclohexylethylene, and cycloheptylethylene.

[0098] In this invention, the term "alkenyl" refers to a straight-chain or branched aliphatic hydrocarbon group containing 2 to 20 carbon atoms and comprising at least one (e.g., one, two, three, or more) carbon-carbon double bond, preferably containing 2 to 15, 2 to 10, 2 to 6, or 2 to 4 carbon atoms. When the number of carbon-carbon double bonds is two or more, the carbon-carbon double bonds can be conjugated or non-conjugated. Examples include, but are not limited to, vinyl, propenyl, and allyl. The linkage site of the alkenyl group can be sp... 2On hybridized carbon atoms, sp... 3 On hybridized carbon atoms.

[0099] In this invention, the term "cyclodienyl" refers to a cyclic aliphatic hydrocarbon group containing two carbon-carbon double bonds, preferably containing 4 to 10 carbon atoms, 4 to 8 carbon atoms, or 5 to 8 carbon atoms.

[0100] In this invention, the term "aryl" or "aromatic ring group" refers to an aromatic carbocyclic system containing 6 to 30 carbon atoms, or 6 to 25 carbon atoms, or 6 to 14 carbon atoms, or 6 to 12 carbon atoms, or 6 to 10 carbon atoms, and the term "aryl" may be used interchangeably with the term "aromatic ring". Examples of aryl groups include, but are not limited to, phenyl, biphenyl, terphenyl, tetraphenyl, 1-phenylnaphthyl, 2-phenylnaphthyl, naphthyl, anthraceneyl, phenanthrene, triphenylene, pyrene, perylene, fluoranyl, benzo[a]fluorenyl, spirofluorenyl, spirodifluorenyl, etc.

[0101] In this invention, the term "arylalkylene" refers to a group in which an aryl group is attached to an alkyl group, wherein the alkyl group serves as the linking site to other segments of the compound. The aryl group and the alkyl group have the meanings described above. Examples of arylalkylene groups include, for example, C6-20 aryl-C1-C10 arylalkylene groups, C6-14 aryl-C1-C6 arylalkylene groups, C6-10 aryl-C1-C4 arylalkylene groups, and C6-10 aryl-C1-C2 arylalkylene groups. Examples of arylalkylene groups include, but are not limited to, benzyl, phenylethylene, naphthylmethylene, and naphthylethylene.

[0102] In this invention, the term "aryl-alkylene group" refers to a group in which an aryl group is attached to an alkenyl group, wherein the alkenyl group serves as the linking site to other segments of the compound. The aryl group and the alkenyl group have the meanings described above. Examples of arylalkylene groups include, for example, C6-20 aryl-C2-C10 arylalkylene groups, C6-14 aryl-C2-C6 arylalkylene groups, C6-10 aryl-C2-C4 arylalkylene groups, and C6-10 aryl-C2 arylalkylene groups. Examples of arylalkylene groups include, but are not limited to, phenylvinylene (i.e., 2-phenyl-vinylene) and naphthylvinylene (i.e., 2-naphthyl-vinylene).

[0103] In this invention, the term "heteroaryl" or "heteroarylcycloyl" refers to a monocyclic, bicyclic, polycyclic, or fused-ring cyclic system containing 2 to 30 carbon atoms, 2 to 25 carbon atoms, 2 to 14 carbon atoms, 2 to 12 carbon atoms, or 3 to 10 carbon atoms, wherein one, two, three, or more ring atoms are heteroatoms and the remaining atoms are carbon atoms, and the heteroatoms are independently selected from oxygen, sulfur, nitrogen, silicon, selenium, or phosphorus atoms. Examples of heteroaryl groups include, but are not limited to, pyrroleyl, furanyl, thiopheneyl, oxazolyl, thiazolyl, imidazolyl, pyridyl, pyrazinyl, pyridazinyl, triazinyl, bipyridyl, bipyrimidinyl, phenylpyridyl, phenylpyrimidinyl, spirofluorenoxazanyl, spirofluorenthionanyl, acridineyl, 9,10-dihydroacridyl, naphridyl, indolyl, phenoxazinyl, phenthiazinyl, phenoxthiazinyl, quinolinyl, and isoquinolinyl. Benzoquinolinyl, benzoisoquinolinyl, quinazolinyl, benzoquinazolinyl, quinoxolinyl, benzoquinoxolinyl, o-phenanthrolinel, benzofuranyl, dibenzofuranyl, naphthobenzofuranyl, benzothiopheneyl, benzothiazolyl, dibenzothiapheneyl, naphthobenzothiapheneyl, benzooxazolyl, naphthooxazolyl, benzoimidazolyl, naphthoimidazolyl, benzothiazolyl, naphthothiazolyl, carbazole, benzocarbazole, etc.

[0104] In this invention, the term "halogen" or "halogenated" refers to F, Cl, Br, and I.

[0105] Unless otherwise indicated, the structural formulas described in this invention include all isomers (e.g., enantiomers, diastereomers, and geometric isomers (or conformational isomers)): for example, R and S configurations containing an asymmetric center, (Z) and (E) isomers of double bonds, and (Z) and (E) conformational isomers. Therefore, any single stereochemical isomer of the compounds of this invention, or its enantiomers, diastereomers, or mixtures of geometric isomers (or conformational isomers), is within the scope of this invention.

[0106] In this invention, the term "substitution" refers to the replacement of a hydrogen atom in a certain functional group by another atom or functional group (i.e., a substituent), and the position of substitution is not limited, as long as the position is where the hydrogen atom is substituted, and when two or more are substituted, the two or more substituents can be the same or different from each other.

[0107] In this invention, the term "substituted or unsubstituted" means unsubstituted or substituted by one or more substituents selected from the group consisting of: deuterium, tritium, halogen, cyano, nitro, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C3-14 cycloalkyl C1-C10 alkylene, substituted or unsubstituted C3-C14 cycloalkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C6-C12 aryl C1-C4 alkylene, substituted or unsubstituted C6-C12 aryl C2-C4 alkenyl, substituted or unsubstituted C2-C20 heteroaryl, substituted or unsubstituted C1-C20 alkoxy, and substituted or unsubstituted amino. Preferably, "substituted or unsubstituted" means unsubstituted or substituted by one or more substituents selected from the group consisting of: deuterium, tritium, halogen, cyano, nitro, C1-C10 alkyl, C2-C10 alkenyl, C3-C10 cycloalkyl, C3-10 cycloalkyl, C1-C4 alkylene, C6-C20 aryl, C6-C12 aryl, C1-C2 alkylene, C6-C12 aryl, C2 alkenyl, C2-C20 heteroaryl, C1-C10 alkoxy, and C1-C10 alkylamine. Most preferably, the term "substituted or unsubstituted" means unsubstituted or substituted with one or more substituents selected from the group consisting of: deuterium, tritium, fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, trifluoromethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, phenyl, naphthyl, anthracene, phenanthrene, triphenylene, pyrene, benzyl, benzene Vinyl, pyrrolo, imidazolyl, thiophene, furanyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, carbazole, indolyl, pyridyl, pyrimidinyl, triazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxolinyl, N-methylcarbazole, N-ethylcarbazole, benzofuranyl, benzothiophene, benzooxazolyl, benzothiazolyl, where the substituents are the same as or different from each other when substituted by multiple substituents.

[0108] In this invention, when the substituent or linking site on the ring is not indicated as fixed, it means that the substituent or linking site is connected to any one of the corresponding optional sites on the ring.

[0109] The effects of the invention:

[0110] The bispyrazoline sensitizer of this invention exhibits a broad UV absorption spectrum, strong absorption, superior photosensitivity, and good solid form. This invention adjusts the flexibility of the two pyrazoline groups by introducing ether bonds and additional alkoxy structures, and by setting asymmetric spatial structures in some molecules. This ensures both good solid form of the designed molecule and good compatibility in photocuring systems. Photocurable compositions containing the aforementioned bispyrazoline sensitizer exhibit excellent photosensitivity and developability, while the cured composition shows good resolution and strong adhesion. Detailed Implementation

[0111] The present invention will be described in more detail below by way of examples, but the present invention is not limited to these examples.

[0112] Example 1

[0113] Synthesis of Compound 2

[0114] The synthesis route is shown below:

[0115]

[0116] Step 1: Dissolve reactant 1, namely triethylene glycol (50 g, 332.95 mmol) and 4-methylbenzenesulfonyl chloride (139.64 g, 732.48 mmol), in 250 mL of dichloromethane. Cool to 0 °C, and add triethylamine (101 g, 998.84 mmol) dropwise. Maintain the temperature and stir for 1 h, then return to room temperature and continue stirring. After the reaction is complete as monitored by TLC, dilute the reaction system with dichloromethane (220 mL). Wash the organic phase three times with water (300 mL × 3). Concentrate the organic phase under low temperature and reduced pressure, then add n-hexane and slurry to obtain the product of Step 1: 130 g, yield: 85.15%. MS-ESI calculated value [M+H] + 459.54, the actual measured value is 459.58.

[0117] Step 2: In a single-necked flask, the product from Step 1 (130 g, 283.51 mmol), reactant 2 (69.94 g, 573.69 mmol) and potassium carbonate (117.55 g, 58 mmol) were added to 500 mL of acetonitrile. The mixture was stirred in an 80 °C oil bath. After the starting materials disappeared (as monitored by TCL), the acetonitrile was concentrated under reduced pressure. 300 mL of ethyl acetate was added to the system, and the mixture was stirred at room temperature. The mixture was filtered to obtain a filtrate. The filtrate was concentrated to dryness, stirred with n-hexane, and filtered to obtain a filter cake, which was the product of Step 2: 90 g, yield: 88.58%. MS-ESI calculated value [M+H] + 359.3, the actual measured value is 359.42.

[0118] Step 3: Dissolve the product from Step 2 (90 g, 251.12 mmol) and reactant 3, biphenyl acetone (99.06 g, 504.76 mmol), in 600 ml of anhydrous ethanol. After dispersing with stirring at room temperature, slowly add a 3M sodium hydroxide solution (25.11 g, 627.81 mmol) dropwise to the reaction system. After the addition is complete, continue the reaction at room temperature. Monitor the reaction progress using TLC. Once the reaction is complete, filter directly to obtain the filter cake. Wash with 30 ml of ethanol:water (3:1) solution and dry to obtain 150 g of product from Step 3, yield: 83.56%. MS-ESI calculated value [M+H] + 715.86, the actual measured value is 715.89.

[0119] Step 4: The product from Step 3 (150 g, 209.83 mmol), reactant 4 (phenylhydrazine, 46.52 g, 430.16 mmol), and sodium hydroxide (25.18 g, 524.58 mmol) were added to 540 mL of anhydrous ethanol and heated to 85 °C. After the reaction was complete as monitored by TLC, the mixture was cooled and filtered. The filter cake was recrystallized from methanol to give compound 2: 160 g, yield: 83.56%. MS-ESI calculated value [MH]. + 896.41, the actual measured value is 896.45.

[0120] Examples 2-6

[0121] Referring to the synthetic route in Example 1, and selecting the corresponding reactants 1-4, a series of specific compounds of the present invention were prepared (see Table 1).

[0122] Table 1

[0123]

[0124]

[0125] Table 2

[0126] Example 7

[0127] Synthesis of Compound 23

[0128]

[0129] Step 1: Dissolve reactant 1, namely triethylene glycol (50 g, 332.95 mmol) and 4-methylbenzenesulfonyl chloride (63.47 g, 332.95 mmol), in 250 mL of dichloromethane. Cool to 0 °C, and add triethylamine (40.43 g, 399.54 mmol) dropwise. Maintain the temperature and stir for 1 h, then return to room temperature and continue stirring. After the reaction is complete as monitored by TLC, dilute the reaction system with dichloromethane (220 mL), wash the organic phase three times with water (300 mL × 3), and concentrate the organic phase under low temperature and reduced pressure to obtain the product of Step 1: 98.32 g, yield: 97.02%. MS-ESI calculated value [M+H] + 305.36, the actual measured value is 305.41.

[0130] Step 2: In a single-necked flask, the product from Step 1 (98.32 g, 323.04 mmol), reactant 2 (p-hydroxybenzaldehyde, 37.48 g, 306.89 mmol), and potassium carbonate (58.04 g, 419.95 mmol) were added to 500 mL of acetonitrile. The mixture was stirred at 80 °C. After the starting materials disappeared under TCL monitoring, the acetonitrile was concentrated under reduced pressure. 300 mL of ethyl acetate was added to the system, and the mixture was stirred at room temperature. The mixture was filtered to obtain the filtrate, which was then concentrated to dryness to obtain the Step 2 product: 78.6 g, yield: 95.69%. MS-ESI calculated value [M+H] + 255.28, the actual measured value is 255.32.

[0131] Step 3: Dissolve the Step 2 product (78.6 g, 309.11 mmol) and 4-methylbenzenesulfonyl chloride (70.71 g, 370.93 mmol) in 350 mL of dichloromethane. Cool to 0 °C, then add triethylamine (46.92 g, 463.66 mmol) dropwise. Maintain the temperature and stir for 1 h, then return to room temperature and continue stirring. After the reaction is complete as monitored by TLC, dilute the reaction system with dichloromethane (220 mL). Wash the organic phase three times with water (300 mL × 3). Concentrate the organic phase under reduced pressure at low temperature, add n-hexane, and slurry to obtain the Step 3 product: 95 g, yield: 75.24%. MS-ESI calculated value [M+H] + 409.46, the actual measured value is 409.49.

[0132] Step 4: In a single-necked flask, the product from Step 3 (95 g, 232.58 mmol), reactant 3 (syringaldehyde, 43.22 g, 237.33 mmol), and potassium carbonate (45 g, 325.61 mmol) were added to 500 mL of acetonitrile. The mixture was stirred in an 80°C oil bath. After the starting material disappeared under TCL monitoring, the acetonitrile was concentrated under reduced pressure. 300 mL of ethyl acetate was added to the system, and the mixture was stirred at room temperature. The mixture was filtered to obtain the filtrate, which was then concentrated to dryness to obtain the Step 4 product: 87.5 g, yield: 89.91%. MS-ESI calculated value [M+H] + 419.44, measured value is 419.48;

[0133] Step 5: Dissolve the product from Step 4 (87.5 g, 209.11 mmol) and reactant 4, biphenyl acetone (84.13 g, 428.67 mmol), in 680 ml of anhydrous ethanol. After dispersing with stirring at room temperature, slowly add a 3M sodium hydroxide solution (20.91 g, 522.77 mmol) dropwise to the reaction system. After the addition is complete, continue the reaction at room temperature. Monitor the reaction progress using TLC. Once the reaction is complete, filter directly to obtain the filter cake. Elute with 100 ml of ethanol:water (3:1) solution and dry to obtain the Step 5 product: 139.75 g, yield: 86.24%. MS-ESI calculated value [M+H] + 775.91, the actual measured value is 775.95.

[0134] Step 6: The product from Step 5 (139.75 g, 180.34 mmol), reactant 5 (phenylhydrazine, 20.48 g, 369.70 mmol), and sodium hydroxide (21.64 g, 541.03 mmol) were added to 560 mL of anhydrous ethanol and heated to 85 °C. After the reaction was completed as monitored by TLC, the mixture was cooled and filtered. The filter cake was recrystallized from methanol to give compound 23: 150 g, yield: 87.08%. MS-ESI calculated value [M+H] + 956.17, the actual measured value is 956.21.

[0135] Example 8

[0136] Synthesis of Compound 24

[0137]

[0138] Step 1-2 is prepared in the same manner as compound 2, yielding 90g of product step 2;

[0139] Step 3: Dissolve the product from Step 2 (90g, 251.12mmol) and reactant 3, biphenyl ethylphenidate (46.82g, 238.57mmol), in 400ml of anhydrous ethanol. After dispersing with stirring at room temperature, prepare a 3M sodium hydroxide solution (10.04g, 251.12mmol) and slowly add it dropwise to the reaction system. After the addition is complete, continue the reaction at room temperature. When the concentration of the raw materials no longer changes significantly as monitored by TLC, filter directly to obtain a filter cake. Recrystallize the filter cake with anhydrous ethanol and dry it to obtain 100g of the product from Step 3, with a yield of 74.21%. MS-ESI calculated value [M+H]+537.62, measured value 537.66.

[0140] Step 4: Dissolve the product from Step 3 (100 g, 186.35 mmol) and reactant 4, 1-naphthyl ethylone (31.72 g, 186.35 mmol), in 300 ml of anhydrous ethanol. After dispersing with stirring at room temperature, slowly add a 3M sodium hydroxide solution (8.94 g, 223.62 mmol) dropwise to the reaction system. After the addition is complete, continue the reaction at room temperature. Monitor the reaction progress using TLC. Once the reaction is complete, filter directly to obtain the filter cake. Elute with 100 ml of ethanol:water (3:1) and dry to obtain the product from Step 5: 106 g, yield: 82.58%. MS-ESI calculated value [M+H] + The actual value is 689.86, while the actual value is 689.82.

[0141] Step 5: The product from Step 4 (106 g, 153.89 mmol), reactant 5-phenylhydrazine (34.12 g, 315.47 mmol), and sodium hydroxide (18.46 g, 461.66 mmol) were added to 560 ml of anhydrous ethanol and heated to 85 °C. After the reaction was completed by TLC monitoring, the mixture was cooled and filtered. The filter cake was recrystallized from methanol to give compound 24: 115 g, yield: 85.99%. MS-ESI calculated value [M+H] +870.08, measured value 870.11.

[0142] Performance evaluation:

[0143] 1.1 Example 9: Modulation of the photosensitizing composition of the present invention

[0144] 60g of trimethylolpropane triacrylate, 5g of photoinitiator BCIM, 0.5g of compound 2 obtained in Example 1, and 25g of methyl ethyl ketone were added to 100g of acrylic copolymer and stirred thoroughly to obtain photosensitive composition 1.

[0145] In addition, the above-mentioned acrylic copolymer was 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 were dissolved in 300 parts by mass of methyl ethyl ketone, and 0.75 parts by mass of azobisisobutyronitrile were added under a nitrogen atmosphere and reacted at 70°C for 5 hours to obtain the above-mentioned acrylic copolymer (Mv = 15000).

[0146] 1.2 Examples 10-16: Modulation of photosensitizing compositions 2-8

[0147] Except that compound 2 obtained in Example 1 was replaced with the compounds shown in Table 3 below, photosensitive compositions 2-8 were obtained by the same method as in the Examples.

[0148] 1.3 Comparative Examples 1-3: Modulation of Comparative Photosensitive Compositions 1-3

[0149] Except that compound 2 obtained in Example 1 was replaced with the compounds shown in Table 3 below, comparative photosensitizing compositions 1-3 were obtained by the same method as in the Examples.

[0150] Table 3

[0151]

[0152] The structures of the compounds used as sensitizers in Examples 9-16 and Comparative Examples 1-3 are shown below. As control compounds, control compound 1 was synthesized according to the method reported in patent CN113527207B, control compound 2 was synthesized according to the method reported in patent TWI878162B, and control compound 3 was synthesized according to the method reported in patent CN104892512B.

[0153]

[0154] 1.3 Evaluation Content:

[0155] (1) Compatibility evaluation

[0156] The photosensitive resin composition was thoroughly stirred and mixed, and then uniformly coated onto the surface of a 19 μm thick polyethylene terephthalate film used as a support using a rod coater. The film was dried in a dryer at 90°C for 5 minutes to form a photosensitive resin layer. The surface of the coating was observed for any undissolved substances. If there were any undissolved substances, it indicated poor compatibility; if there were no undissolved substances, it indicated good compatibility. The test results are shown in Table 4.

[0157] (2) Evaluation of photosensitivity performance

[0158] The above photosensitive resin composition was stirred in the dark, and the mixture was applied to a PET template. A wire-coating method was used, and the solvent was removed by drying at 90°C for 5 minutes, resulting in a coating with a thickness of approximately 30±2 μm. After exposure and development, the sensitivity (21st order) across the entire wavelength range (365nm / 385nm / 405nm) was observed (energy level 60mJ / cm²). 2 The test results are shown in Table 5.

[0159] (3) Resolution evaluation

[0160] The laminated substrate is exposed for 15 minutes using a linear pattern mask with a 1:1 ratio of the exposed to the unexposed width. Then, it is developed for twice the minimum development time, with the minimum mask linewidth for normal formation of cured resist lines as the resolution value.

[0161] (4) Evaluation of radioactivity

[0162] The photosensitive resin laminate has a thickness of 30 μm and an area of ​​0.12 m². 2 The photosensitive layer (dry film resist layer) was dissolved in 1L of 1wt% Na2CO3 aqueous solution and sprayed for 5 hours using a circulating spray device at a spray pressure of 0.1MPa. Then, the developer was left to stand for 1 day, and the appearance of agglomerates was observed.

[0163] 〇 No clumps: The spraying device produces almost no clumps, and only a very small amount of clumps float in the developing solution; these can be easily rinsed away with water.

[0164] ▼Trace amounts of aggregates: The spray device contains trace amounts of aggregates that are visible to the naked eye, and trace amounts of aggregates float in the developer; these aggregates cannot be completely removed by water washing.

[0165] ▄Agglomerates are present: Agglomerates are visible throughout the spraying device, and they float in the developing solution; they cannot be completely washed away by water, and most of them remain.

[0166] (5) Adhesion evaluation

[0167] The laminated substrate is exposed for 15 minutes using a linear pattern mask with a width ratio of 1:100 between the exposed and unexposed portions. Then, it is developed using a development time twice the minimum development time, with the minimum mask linewidth for normal formation of cured resist lines used as the adhesion value.

[0168] 1.4 Evaluation Results:

[0169] (1) Compatibility:

[0170] Table 4

[0171]

[0172] As shown in Table 4, the pyrazoline sensitizer provided by the present invention has good compatibility with the components of the matrix resin, and no undissolved substances precipitate on the surface after drying and film formation.

[0173] (2) Sensitivity:

[0174] Table 5

[0175] Photosensitive composition 365nm (step) 385nm (level) 405nm (level) Full band (order) Example 9 15 15 11 15.5 Example 10 16 16 11.5 16 Example 11 17 17 12 17 Example 12 13 13 10.5 14 Example 13 17 17 12 18 Example 14 13 13 10.5 13.5 Example 15 15 15 11 15 Example 16 16 16 12 16 Comparative Example 1 8 8 5 9 Comparative Example 2 9 9 6 10 Comparative Example 3 8 8 5 9.5

[0176] As shown in Table 5, the pyrazoline sensitizers provided by this invention have better photosensitivity than comparative compounds 1-3. The photocurable systems under UV-LED light source irradiation can be cured smoothly, which indicates that the sensitizers of this invention have good applicability in UV-LED photocurable systems.

[0177] (3) Dry film performance evaluation:

[0178] Table 6

[0179]

[0180]

[0181] As shown in Table 6, compared with comparative compounds 1-3, the pyrazoline sensitizers provided by the present invention can effectively improve the performance of the cured product; the photosensitive resin composition containing the pyrazoline sensitizer has high resolution, excellent developability and high adhesion after curing; while the photosensitive resin composition containing the sensitizer with the structure shown in the comparative example has relatively poor resolution, developing effect and adhesion after curing.

[0182] In summary, the pyrazoline sensitizer provided by this invention employs a specific molecular structure design, resulting in photosensitive resin compositions containing it exhibiting good compatibility, high photosensitivity, high resolution, excellent developability, and high adhesion. It also demonstrates good hydrophilicity during development, significantly reducing the amount of sludge in the developer solution during recycling, allowing for repeated and effective use of the developer solution; thus improving the curing efficiency of the photocuring system.

[0183] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above descriptions are merely specific embodiments of the present invention and are 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 within the protection scope of the present invention.

Claims

1. A bispyrazoline compound represented by the following general formula (1): in, R1 and R2 each independently represent substituents that have a conjugated structure with the pyrazole ring; R3 and R5 are each independently selected from hydrogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C14 cycloalkyl, C1-C10 alkylene, substituted or unsubstituted C3-C14 cycloalkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C4-C10 cyclodienyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C2-C30 heteroaryl. R4 and R6 are each independently selected from hydrogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C14 cycloalkyl, C1-C10 alkylene, substituted or unsubstituted C3-C14 cycloalkyl, and substituted or unsubstituted C1-C20 alkoxy. L represents -(L1-O) m -L2-, -CO(L1-O) m -L2CO-, -CO(L1-O) m -L2-, -(L1-O) m -L2CO-; L1 and L2 are each independently selected from C1 to C10 alkylene groups; m is independently selected from 1, 2, 3, 4, 5, 6, 7, 8, or 9; p, q, s, and t are independently selected from 0, 1, 2, 3, or 4.

2. The bispyrazoline compound according to claim 1, characterized in that, R1 and R2 are each independently selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C2-C20 alkenyl, and substituted or unsubstituted C4-C10 cyclodienyl. Preferably, R1 and R2 are each independently selected from phenyl, naphthyl, biphenyl, pyrrolyl, imidazolyl, indolyl, thiophene, furanyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, carbazole, C2-C10 alkenyl, C6-C12 aryl, C2-C4 alkenylidel, and C4-C8 cyclodienyl; each group may be independently substituted by one or more of the following groups: C1-C10 alkyl, C2-C10 alkenyl, C3-C10 cycloalkyl, C1-C6 alkenylidel, C4-C8 cyclodienyl. The aryl group can be 3-C10 cycloalkyl, C6-C14 aryl, C6-C12 arylC1-C2 alkylene, C6-C12 arylC2-C4 alkenyl, or C2-C14 heteroaryl, and the C6-C14 aryl, C2-C14 heteroaryl, C6-C12 arylC1-C2 alkylene, and C6-C12 arylC2-C4 alkenyl can also be mono- or poly-substituted by C1-C10 alkyl or C1-C10 alkoxy groups; More preferably, the substituents in R1 and R2 are selected from: C1-C6 alkyl, C2-C6 alkenyl, C3-C8 cycloalkyl C1-C4 alkylene, C3-C8 cycloalkyl, C6-C12 aryl, C6-C10 aryl C1-C2 alkylene, C6-C10 aryl C2 alkenyl, C1-C6 alkyl-substituted C6-C10 aryl C2 alkenyl, C1-C6 alkoxy-substituted C6-C10 aryl C2 alkenyl, and C2-C10 monocyclic or bicyclic heteroaryl (such as pyrroleyl, imidazolyl, carbazoleyl, indolyl, thiophenyl, furanyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl). More preferably, R1 and R2 are each independently selected from the following groups: Among them, R 11 Each is independently selected from hydrogen, C1-C10 alkyl, C2-C10 alkenyl, C3-C10 cycloalkyl, C1-C6 alkylene, C3-C10 cycloalkyl, C6-C14 aryl, C6-C12 aryl, C1-C2 alkylene, C6-C12 aryl, C2-C4 alkenyl, and C2-C14 heteroaryl; R 12 Each is independently selected from hydrogen, C1-C6 alkyl groups, and C1-C6 alkoxy groups; M is selected from O, S, or NR. 13 ; X is selected from CH or N; R 13 Selected from hydrogen, C1-C10 alkyl, C2-C10 alkenyl, C3-C10 cycloalkyl, C1-C6 alkylene, C3-C10 cycloalkyl, C6-C14 aryl, C6-C12 aryl, C1-C2 alkylene, C6-C12 aryl, C2-C4 alkenyl, C2-C14 heteroaryl, and C1-C10 alkoxy. a1 is selected from 0, 1, 2, 3, 4 or 5; a2 is selected from 0, 1, 2, 3, 4, 5, 6 or 7; a3 is selected from 0, 1, 2, 3 or 4; a4 is selected from 0, 1, 2 or 3; a5 is selected from 0, 1 or 2.

3. The bispyrazoline compound according to claim 1, characterized in that, R3 and R5 are each independently selected from hydrogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C8 cycloalkyl, C1-C4 alkylene, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C4-C8 cyclodienyl, substituted or unsubstituted C6-C14 aryl, and substituted or unsubstituted C2-C14 heteroaryl; preferably, R3 and R5 are each independently selected from hydrogen, C1-C6 alkyl, C3-C8 cycloalkyl, C2-C8 alkenyl, and C6-C10 aryl. And / or, R4 and R6 are each independently selected from hydrogen, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C8 cycloalkyl, C1-C4 alkylene, substituted or unsubstituted C3-C8 cycloalkyl, and substituted or unsubstituted C1-C10 alkoxy; preferably, R4 and R6 are each independently selected from hydrogen, C1-C6 alkyl, C3-C8 cycloalkyl, and C1-C6 alkoxy; more preferably, R4 and R6 are each independently selected from hydrogen and C1-C4 alkoxy.

4. The bispyrazoline compound according to claim 1, characterized in that, L1 and L2 are each independently selected from C1 to C6 alkylene groups; preferably, L1 and L2 are each independently selected from -(CR) a R b ) n -, R a R b Each is independently selected from hydrogen, C1 to C2 alkyl groups, and n is selected from 1, 2, 3, 4, 5 or 6; more preferably, each of L1 and L2 is independently selected from -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2CH2-, -CH(CH3)-, -C(CH3)2-, -CH(CH3)CH2-, -C(CH3)2CH2-, -CH2CH(CH3)CH2-, -CH2C(CH3)2CH2-, -CH(CH3)CH2CH2-, -C(CH3)2CH2CH2-.

5. The bispyrazoline compound according to claim 1, characterized in that, The L is selected from: -(CH2) 1-4 O(CH2) 1-4 -; -(CH2) 1-4 O(CH2) 1-4 O(CH2) 1-4 -; -(CH2) 1-4 O(CH2) 1-4 O(CH2) 1-4 O(CH2) 1-4 -; -(CH2) 1-4 O(CH2) 1-4 O(CH2) 1-4 O(CH2) 1-4 O(CH2) 1-4 -; -(CH2) 1-4 O(CH2) 1-4 O(CH2) 1-4 O(CH2) 1-4 O(CH2) 1-4 O(CH2) 1-4 -; Preferably, L is selected from: -CH2OCH2-; -CH2OCH2OCH2-; -CH2OCH2OCH2OCH2; -CH2OCH2OCH2OCH2OCH2OCH2; -CH2OCH2OCH2OCH2OCH2OCH2OCH2-; -CH2CH2OCH2CH2-; -CH2CH2OCH2CH2OCH2CH2-; -CH2CH2OCH2CH2OCH2CH2OCH2CH2-; -CH2CH2OCH2CH2OCH2CH2OCH2CH2OCH2CH2-; -CH2CH2OCH2CH2OCH2CH2OCH2CH2OCH2CH2OCH2CH2-; -CH2CH2CH2OCH2CH2CH2-; -CH2CH2CH2OCH2CH2CH2OCH2CH2CH2-; -CH2CH2CH2OCH2CH2CH2OCH2CH2CH2OCH2CH2CH2-; -CH2CH2CH2OCH2CH2CH2OCH2CH2CH2OCH2CH2CH2OCH2CH2CH2-.

6. The bispyrazoline compound according to claim 1, characterized in that, The pyrazoline compounds have the structures shown in formula (II) or formula (III):

7. The bispyrazoline compound according to claim 1, characterized in that, The pyrazoline compounds are selected from:

8. The method for synthesizing pyrazoline compounds according to any one of claims 1-7, wherein the method is selected from one of the following routes: Route 1: When R1 and R2 are the same, R4 and R6 are the same, R3 and R5, p and q are the same, and s and t are the same, the synthetic route of the pyrazoline compound includes: Route 2: When R1 and R2 are different, and all other parameters are the same, the synthetic route for the pyrazoline compounds includes: Route 3: When R4 differs from R6, and at least one of p and q differs, and R1 is the same as R2, the synthetic route for the pyrazoline compound includes: Route 4: The synthetic routes for the pyrazoline compounds include: Wherein, Lg represents a leaving group, such as Ts (4-methylbenzenesulfonyl), Tf (trifluoromethanesulfonyl), Tfa (trifluoroacetyl); X represents hydrogen, halogen (such as chlorine, bromine), -OLg.

9. A photosensitizer comprising at least one of the pyrazoline compounds according to any one of claims 1-7.

10. A photosensitive composition comprising at least one of the pyrazoline compounds according to any one of claims 1-7, a photoinitiator, and a polymeric compound having an olefinic unsaturated bond.

11. An alkaline-developable photosensitive resin composition comprising at least one of the pyrazoline compounds according to any one of claims 1-7, a photoinitiator, and an alkaline-developable compound having an alkene-type unsaturated bond.

12. A coloring alkali-developable photosensitive resin composition comprising the alkali-developable photosensitive resin composition of claim 11 and a colorant.

13. A chemical for the electronics industry comprising the photosensitive composition of claim 10.

14. A photoresist containing at least one of the photosensitizers of claim 9.

15. An article obtained by using either the electronic industry chemical of claim 13 or the photoresist of claim 14 as a raw material.

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