Pyrazoline-based compound and photocurable composition containing same

Abstract

To provide a pyrazoline-based compound and a photocurable composition containing the same.SOLUTION: The pyrazoline compound has a structure represented by formula (I). The photocurable composition contains an alkali-soluble polymer (A), a monomer or oligomer (B) having a double bond, a photoinitiator (C), and a sensitizer (D) containing the pyrazoline-based compound. Since the pyrazoline-based compound has an absorption wavelength that can match the photoinitiator, the photosensitivity of the photocurable composition can be improved.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a pyrazoline compound, and more particularly to a pyrazoline compound and a photocurable composition containing the same. [Background technology]

[0002] UV curing technology has a wide range of applications due to its advantages of fast curing speed and low environmental pollution. In recent years, laser equipment has been continuously applied in fields such as printed circuit boards, biomedicine, military, and optical communication industries due to its high efficiency, small volume, long lifespan, and low energy consumption. Among them, UV laser equipment with a wavelength of 355nm to 405nm is the mainstream, and laser equipment with a wavelength of 405nm is particularly mainstream. Summary of the Invention [Problem to be solved by the invention]

[0003] In photocurable compositions, photoinitiators and sensitizers are key to the curing speed. In practical applications, some commercially available photoinitiators cannot induce good polymerization due to limitations in their absorption wavelength, so a sensitizer must be added to improve polymerization efficiency. In other words, a sensitizer acts similarly to a catalyst in a photochemical reaction, converting absorbed wavelength energy and transferring it to the photoinitiator. However, sensitizers have limitations in their application due to factors such as absorption wavelength and solubility.

[0004] In view of this, it is urgent to provide a sensitizer that can be mutually combined with the absorption wavelength of the photoinitiator and has good solubility. [Means for solving the problem]

[0005] According to one aspect of the present invention, there is provided a pyrazoline compound having a specific structure, an absorption wavelength that can match with a photoinitiator, and good solubility in a solvent.

[0006] According to another aspect of the present invention, there is provided a photocurable composition comprising a sensitizer having a pyrazoline-based compound of the above formula embodiment to improve the photosensitivity of the photocurable composition.

[0007] According to one aspect of the present invention, there is provided a pyrazoline compound having the structure shown in formula (I): [ka] In formula (I), R1 represents a linear alkylene group having 1 to 14 carbon atoms, an alkylene group substituted with a cycloalkyl group, an alkylene group substituted with an aromatic group, or a divalent organic group containing a carbonyl group or an alkenylene group, providing a pyrazoline-based compound.

[0008] According to one embodiment of the present invention, R1 is selected from the group consisting of structures represented by formula (I-1) to formula (I-29). [ka] [ka] [ka]

[0009] According to another aspect of the present invention, there is provided a photocurable composition comprising an alkali-soluble polymer (A), a monomer or oligomer (B) having a double bond, a photoinitiator (C), and a sensitizer (D) containing the pyrazoline-based compound.

[0010] According to one embodiment of the present invention, the content of the alkali-soluble polymer (A) is 20 to 70 parts by weight, based on 100 parts by weight of the photocurable composition.

[0011] According to one embodiment of the present invention, the content of the monomer or oligomer (B) having a double bond is 20 to 50 parts by weight, based on 100 parts by weight of the photocurable composition.

[0012] According to one embodiment of the present invention, the content of the photoinitiator (C) is 0.01 to 10 parts by weight, based on 100 parts by weight of the photocurable composition.

[0013] According to one embodiment of the present invention, the content of the sensitizer (D) is 0.001 to 10 parts by weight, based on 100 parts by weight of the photocurable composition.

[0014] According to one embodiment of the present invention, the alkali-soluble polymer (A) is at least one selected from the group consisting of acrylic acid polymers, methacrylic acid polymers, copolymers of acrylic acid and acrylate, copolymers of methacrylic acid, methyl methacrylate, n-butyl acrylate and styrene, styrene polymers, epoxy resin polymers, aliphatic polyurethane acrylate polymers, aromatic polyurethane acrylate polymers, amide polymers, amide epoxy resin polymers, alkyd resin polymers, and phenolic resin polymers.

[0015] According to one embodiment of the present invention, the monomer or oligomer (B) having a double bond is at least one selected from the group consisting of acrylates or methacrylates having at least one double bond, acrylates or methacrylates having a bisphenol A functional group, acrylates or methacrylates having a polyethylene glycol and / or polypropylene glycol functional group, acrylates or methacrylates having a glycidyl group, acrylates or methacrylates having a polyurethane group, acrylates or methacrylates having an aromatic ring functional group, alkyl acrylates, and alkyl methacrylates.

[0016] According to one embodiment of the present invention, the photocurable composition further comprises an auxiliary (E), which is at least one selected from the group consisting of a compound capable of providing hydrogen ions, a dye, a pigment, a photocoloring agent, a stabilizer, an adhesion promoter, a defoaming auxiliary, and a release promoter.

[0017] By using the pyrazoline compound and the photocurable composition containing the same of the present invention, the sensitizer containing the pyrazoline compound can have an absorption wavelength that matches that of the photoinitiator, good solubility in solvents, and further improve the photosensitivity of the photocurable composition. [Brief description of the drawing] (No) DETAILED DESCRIPTION OF THE INVENTION

[0018] The making and using of embodiments of the present invention are discussed in detail below. However, it will be understood that the embodiments provide many applicable inventive concepts that can be implemented in a variety of specific contexts. The specific embodiments discussed are for illustrative purposes only and are not intended to limit the scope of the present invention.

[0019] As used herein, "around," "about," "approximately," or "substantially" generally refers to within 20 percent, or within 10 percent, or within 5 percent of the value or range.

[0020] Pyrazoline compounds are widely used sensitizers, but when commercially available pyrazoline compound sensitizers are used in photocurable compositions, they do not provide a satisfactory effect on improving photosensitivity and have poor solubility in solvents. While some literature suggests that large-molecule pyrazoline compound sensitizers can partially solve the compatibility and solubility problems of formulations, in actual applications, the required amount is large, resulting in insufficient improvement in photosensitivity. Therefore, as described above, the present invention provides a pyrazoline compound and a photocurable composition containing the same. The pyrazoline compound sensitizer has an absorption wavelength that matches the absorption wavelength of a photoinitiator, good solubility in solvents, and can further improve the photosensitivity of the photocurable composition.

[0021] The present invention provides a pyrazoline compound having the structure shown in formula (I): [ka] In formula (I), R1 represents a linear alkylene group having 1 to 14 carbon atoms, an alkylene group substituted with a cycloalkyl group, an alkylene group substituted with an aromatic group, or a divalent organic group containing a carbonyl group or an alkenylene group.

[0022] According to one embodiment of the present invention, the above R1 represents a linear alkylene group having 1 to 14 carbon atoms, for example, but not limited to, the following: [ka]

[0023] According to one embodiment of the present invention, R1 represents an alkylene group substituted with a cycloalkyl group, such as, but not limited to, the following: [ka]

[0024] According to one embodiment of the present invention, R1 represents an alkylene group substituted with an aromatic group, for example, but not limited to, the following: [ka]

[0025] According to one embodiment of the present invention, R1 represents a divalent organic group containing a carbonyl group, such as, but not limited to, the following: [ka] [ka]

[0026] According to one embodiment of the present invention, R1 represents a divalent organic group containing an alkenylene group, such as, but not limited to, the following: [ka]

[0027] In some embodiments, the pyrazoline compounds of the present invention may be prepared by first synthesizing a compound having a pyrazoline structure as a main structural monomer, and then linking the main structural monomer via R1 to obtain the structure of Formula (I). For example, the following reaction scheme (1) may be used to synthesize a main structural monomer D1 having a pyrazoline structure, and the following reaction scheme (2) may be used to synthesize a pyrazoline compound having the structure of Formula (I). It should be understood that the reaction scheme (1) for synthesizing the main structural monomer D1 is based on Taiwan Patent Publication No. TW I766645B and China Patent Publication No. CN 113527207A, the entire contents of which are incorporated herein by reference. In practice, those skilled in the art should understand that the following reaction scheme (1) is a basic process for organic chemical synthesis, and its process parameters can be easily understood and implemented by those skilled in the art. Therefore, the detailed process flow and process conditions will not be repeated in this specification. [ka]

[0028] The solvent used in the synthesis of Reaction Scheme (2) above is not particularly limited, as long as it can dissolve the reactants and does not cause other side reactions or produce other undesirable by-products. In some embodiments, the solvent may be acetonitrile, acetone, butanone, N,N-dimethylformamide, N,N-diethylformamide, or the like. To facilitate the reaction, an alkaline solution must be added. In some embodiments, the alkaline solution may be sodium carbonate, potassium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, sodium methoxide, pyridine, triethylamine, or the like. In some embodiments, the reaction temperature for this reaction may be about 50°C to about 130°C, and the reaction time may be about 6 hours to about 16 hours.

[0029] The pyrazoline compound of the present invention having the structure of formula (I) has an ultraviolet-visible light absorption wavelength of 350 nm to 440 nm, and therefore can be applied to the photocuring field, particularly to systems using bisimidazole photoinitiators. Furthermore, the pyrazoline compound of the present invention is solid, making it easy to use. Furthermore, the pyrazoline compound of the present invention has good solubility in solvents and can have excellent compatibility with each component of the photocurable composition. Therefore, the pyrazoline compound of the present invention has a significant effect on improving the photosensitivity of the photocurable composition.

[0030] The present invention further provides a photocurable composition comprising an alkali-soluble polymer (A), a monomer or oligomer (B) having a double bond, a photoinitiator (C), and a sensitizer (D) including a pyrazoline-based compound having the structure shown in formula (I) above.

[0031] Alkali-soluble polymer (A)

[0032] The alkali-soluble polymer (A) can provide the photocurable composition with a film-forming function, and any alkali-soluble polymer having this function can be used without any particular limitation. In some embodiments, the alkali-soluble polymer (A) may be an acrylic acid polymer, a methacrylic acid polymer, a copolymer of acrylic acid and acrylate, a copolymer of methacrylic acid, methyl methacrylate, n-butyl acrylate, and styrene, a styrene polymer, an epoxy resin polymer, an aliphatic polyurethane acrylate polymer, an aromatic polyurethane acrylate polymer, an amide polymer, an amide epoxy resin polymer, an alkyd resin polymer, a phenolic resin polymer, or any combination thereof.

[0033] The alkali-soluble polymer (A) may be obtained by polymerizing a polymerizable monomer. In some embodiments, the polymerizable monomer may be a styrene derivative having a substituted functional group on an aromatic ring, such as styrene, vinyltoluene, o-methylstyrene, p-methylstyrene, p-ethylstyrene, or p-chlorostyrene, an acrylamide derivative, such as acrylamide or diacetone acrylamide, a vinyl derivative, such as acrylonitrile or vinyl-n-butyl ether, an acrylic acid or methacrylic acid derivative, such as α-bromoacrylic acid, α-bromomethacrylic acid, α-chloroacrylic acid, α-chloromethacrylic acid, β-furanylacrylic acid, β-furanylmethacrylic acid, β-styrylacrylic acid, or β-styrylmethacrylic acid, an alkyl acrylate, an alkyl methacrylate, benzyl acrylate, benzyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, tetrahydrofurfuryl acrylate, or tetrahydrofurfuryl The polymerizable monomer may include, but is not limited to, acrylate or methacrylate derivatives such as methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl acrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl acrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate, as well as maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, and monopropyl maleate. The polymerizable monomer may be used alone or in combination of two or more.

[0034] The content of the alkali-soluble polymer (A) is about 20 to about 70 parts by weight, preferably about 30 to about 60 parts by weight, based on 100 parts by weight of the photocurable composition. When the content of the alkali-soluble polymer (A) is within this range, it is possible to ensure that the photocurable composition has excellent chemical resistance to electroplating and / or etching processes, which is advantageous in improving the resolution ability of the photocurable composition.

[0035] The weight-average molecular weight of the alkali-soluble polymer (A) is not particularly limited and may be adjusted according to specific application needs. To improve the alkaline developability of the alkali-soluble polymer (A), in some embodiments, the weight-average molecular weight of the alkali-soluble polymer (A) may be about 15,000 to about 200,000, preferably about 25,000 to about 120,000. When the weight-average molecular weight of the alkali-soluble polymer (A) is within the above range, the photocurable composition exhibits excellent resistance to alkaline developers after exposure, a moderate development time, and excellent compatibility with the photoinitiator (C) or other components. The weight-average molecular weight of the alkali-soluble polymer (A) may be determined by gel permeation chromatography (GPC) and converted using a calibration curve using polystyrene.

[0036] In some embodiments, the molecular weight distribution (or dispersity index, i.e., weight average molecular weight (M w ) and number average molecular weight (M n ) is about 1.5 to about 6.0, and preferably about 1.8 to about 3.7. When the molecular weight distribution of the alkali-soluble polymer (A) is within the above range, the photocurable composition has excellent developability.

[0037] Regarding developability, in some embodiments, the acid value of the alkali-soluble polymer (A) may be about 50 mg KOH / g to about 300 mg KOH / mg, and preferably about 100 mg KOH / g to about 250 mg KOH / mg. When the acid value of the alkali-soluble polymer (A) is within the above range, the photocurable composition can have a high development speed and good adhesion, thereby avoiding the problem of reduced stability of the photocurable composition after development.

[0038] The alkali-soluble polymer (A) may be used alone or in combination of two or more kinds, and the alkali-soluble polymer (A) used in combination of two or more kinds may be composed of alkali-soluble polymers (A) having different copolymerization components, different weight-average molecular weights, or different molecular weight distributions.

[0039] Monomer or oligomer having a double bond (B)

[0040] The double bond-containing monomer or oligomer (B) can be used to form a film by polymerizing a photocurable composition through light irradiation in the presence of a photoinitiator. The double bond-containing monomer or oligomer (B) of the present invention is not particularly limited as long as it is a photopolymerizable compound having at least one double bond in the molecule. In some embodiments, the double bond-containing monomer or oligomer (B) may be an acrylate / methacrylate having at least one double bond, an acrylate / methacrylate having a bisphenol A functional group, an acrylate / methacrylate having a polyethylene glycol or polypropylene glycol functional group, an acrylate / methacrylate having a glycidyl group, an acrylate / methacrylate having a polyurethane group, an acrylate / methacrylate having an aromatic ring functional group, or an alkyl acrylate / alkyl methacrylate.

[0041] In some specific examples, the monomer or oligomer (B) having a double bond is polyethylene glycol diacrylate / polyethylene glycol dimethacrylate having 2 to 14 ethylene glycol groups, polypropylene glycol diacrylate / polypropylene glycol dimethacrylate having 2 to 14 propylene glycol groups, polyethylene glycol propylene glycol diacrylate / polyethylene glycol propylene glycol dimethacrylate having 2 to 14 ethylene glycol groups and 2 to 14 propylene glycol groups, trimethylolpropane diacrylate / trimethylolpropane dimethacrylate, trimethylolpropane triacrylate / trimethylolpropane trimethacrylate, trimethylolpropane triacrylate modified with an ethylene glycol group / trimethylolpropane trimethacrylate, or trimethylolpropane triacrylate modified with a propylene glycol group. The polymerizable monomers may include, but are not limited to, ethylene glycol / trimethylolpropane trimethacrylate, trimethylolpropane triacrylate / trimethylolpropane trimethacrylate modified with ethylene glycol groups and propylene glycol groups, tetrahydroxymethylmethane triacrylate / tetrahydroxymethylmethane trimethacrylate, tetrahydroxymethylmethane tetraacrylate / tetrahydroxymethylmethane tetramethacrylate, dipentaerythritol pentaacrylate / dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate / dipentaerythritol hexamethacrylate, polypropylene glycol monoacrylate / polypropylene glycol monomethacrylate, polyethylene glycol monoacrylate / polyethylene glycol monomethacrylate, tripropylene glycol diacrylate / tripropylene glycol dimethacrylate, or any combination thereof.

[0042] In some specific examples, the acrylate / methacrylate having a bisphenol A functional group is 2,2-bis(4-(acryloxypolyethoxy)phenylpropane / 2,2-bis(4-(methacryloyloxypolyethoxy)phenylpropane, 2,2-bis(4-(acryloxypolypropoxy)phenylpropane / 2,2-bis(4-(methacryloyloxypolypropoxy)phenylpropane, 2,2-bis(4-(acryloxypolybutoxy)phenylpropane), The copolymers may include, but are not limited to, 2,2-bis(4-(methacryloyloxypolybutoxy)phenylpropane, 2,2-bis(4-(acryloxypolyethoxypolypropoxy)phenylpropane / 2,2-bis(4-(methacryloyloxypolyethoxypolypropoxy)phenylpropane, or any combination thereof. Among them, 2,2-bis(4-(acryloxypolyethoxy)phenylpropane / 2,2-bis(4-(methacryloyloxypolyethoxy)phenylpropane The number of ethoxy groups in each molecule of 2,2-bis(4-(acryloxypolypropoxy)phenylpropane is preferably 2 to 20, more preferably 2 to 6, and the number of propoxy groups in each molecule of 2,2-bis(4-(methacryloyloxypolypropoxy)phenylpropane is preferably 4 to 20, more preferably 8 to 15. The number of butoxy groups in each molecule of 2,2-bis(4-(acryloxypolyethoxypolypropoxy)phenylpropane) is preferably 2 to 15, and more preferably 3 to 10. The number of ethoxy groups and propoxy groups in each molecule of 2,2-bis(4-(acryloxypolyethoxypolypropoxy)phenylpropane) / 2,2-bis(4-(methacryloyloxypolyethoxypolypropoxy)phenylpropane) is preferably 4 to 20, and more preferably 8 to 15.

[0043] In some specific examples, the acrylate / methacrylate having a polyurethane group may include, but is not limited to, tri(acryloxytetraethylene glycol isocyanate)hexamethylene isocyanurate / tri(methacryloyloxytetraethylene glycol isocyanate)hexamethylene isocyanurate, urethane diacrylate / urethane dimethacrylate modified with an ethylene glycol group, urethane diacrylate / urethane dimethacrylate modified with a propylene glycol group, urethane diacrylate / urethane dimethacrylate modified with an ethylene glycol group and a propylene glycol group, and an addition reaction product of an acrylic acid / methacrylic acid monomer having a hydroxy group at the β-position with a diisocyanate (for example, when the diisocyanate is 1,6-hexamethylene diisocyanate, the product is an aminoacrylate polymer). Among these, the diisocyanate may include, but is not limited to, isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, 1,6-hexamethylene diisocyanate, and any combination thereof.

[0044] In some specific examples, the alkyl acrylate / alkyl methacrylate is methyl acrylate / methyl methacrylate, ethyl acrylate / ethyl methacrylate, n-propyl acrylate / n-propyl methacrylate, isopropyl acrylate / isopropyl methacrylate, n-butyl acrylate / n-butyl methacrylate, sec-butyl acrylate / sec-butyl methacrylate, t-butyl acrylate / t-butyl methacrylate, 2-ethylhexyl acrylate / 2-ethylhexyl methacrylate, phenyl acrylate / phenyl methacrylate, isobornyl acrylate / isobornyl methacrylate, hydroxymethyl acrylate / hydroxymethyl methacrylate, hydroxyethyl acrylate / hydroxyethyl methacrylate, hydroxypropyl acrylate / hydroxypropyl methacrylate, 2-hydroxyethyl acrylate / 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate / 2-hydroxypropyl ... The acrylic acid esters may include, but are not limited to, propyl methacrylate, benzyl acrylate / benzyl methacrylate, pentyl acrylate / pentyl methacrylate, tetrahydrofurfuryl acrylate / tetrahydrofurfuryl methacrylate, isooctyl acrylate / isooctyl methacrylate, nonylphenol ethoxylate acrylate / nonylphenol ethoxylate methacrylate, propylene glycol polypropylene ether diacrylate / propylene glycol polypropylene ether dimethacrylate, 1,9-nonanediol diacrylate / 1,9-nonanediol dimethacrylate, 1,10-decanediol diacrylate / 1,10-decanediol dimethacrylate, ethoxylated polytetramethylene ether glycol diacrylate / ethoxylated polytetramethylene ether glycol dimethacrylate, ethoxylated polypropylene glycol diacrylate / ethoxylated polypropylene glycol dimethacrylate, or any combination thereof.

[0045] Based on the improvement of the resolution, adhesion and electroplating resistance of the photocured composition, the monomer or oligomer (B) having a double bond is preferably an acrylate / methacrylate having a bisphenol A functional group, an acrylate / methacrylate having a polyurethane group, or a combination of both.

[0046] The monomer or oligomer (B) having a double bond is preferably an acrylate / methacrylate having a bisphenol A functional group, based on which the resolution and photosensitivity of the photocurable composition are improved.

[0047] The content of the double bond-containing monomer or oligomer (B) is about 20 to about 50 parts by weight, preferably about 25 to about 45 parts by weight, based on 100 parts by weight of the photocurable composition. When the content of the double bond-containing monomer or oligomer (B) is within this range, the photocurable composition can be ensured to have excellent photosensitivity and resolution, can be more easily thinned, and can further improve etching resistance.

[0048] Photoinitiator (C)

[0049] In some embodiments, the photoinitiator (C) may include, but is not limited to, bisimidazole-based compounds, acridine-based compounds, aromatic ketone-based compounds, anthraquinone-based compounds, benzoin and benzoin alkyl ether-based compounds, oxime ester-based compounds, triazine-based compounds, coumarin-based compounds, thioxanthone-based compounds, or any combination thereof.

[0050] In some embodiments, the bisimidazole compound is 2,2'-di(o-chlorophenyl)-4,4',5,5'-tetraphenyl-bisimidazole, 2,2',5-tri(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-bisimidazole, 2,2',5-tri(o-fluorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-bisimidazole, 2,2 '-Di(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-bisimidazole, 2,2'-di(o-fluorophenyl)-4-(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-bisimidazole, 2,2'-di(o-fluorophenyl)-4,4',5,5'-tetraphenyl-bisimidazole, 2,2'-di(o-methoxyphenyl)-4,4',5,5'-tetraphenyl-bisimidazole Phenyl-bisimidazole, 2,2'-di(2-chloro-5-nitrophenyl)-4,4'-di(3,4-dimethoxyphenyl)-5,5'-di(o-fluorophenyl)-bisimidazole, 2,2'-di(2-chloro-5-nitrophenyl)-4-(3,4-dimethoxyphenyl)-5-(o-fluorophenyl)-4',5'-diphenyl-bisimidazole, 2,2'-di(2,4-dichlorophenyl)-4,4'-di(3 ,4-dimethoxyphenyl)-5,5'-di(o-fluorophenyl)-bisimidazole, 2-(2,4-dichlorophenyl)-4-(3,4-dimethoxyphenyl)-2',5-di(o-chlorophenyl)-4',5'-diphenyl-bisimidazole, 2,2'-di(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-bisimidazole, or any combination thereof.

[0051] In some specific examples, the acridine-based compound may include, but is not limited to, 9-phenylacridine, 9-o-methylphenylacridine, 9-m-methylphenylacridine, 9-p-methylphenylacridine, 9-o-fluorophenylacridine, 9-ethylacridine, 9-(4-bromophenyl)acridine, 9-(3-chlorophenyl)acridine, 1,7-bis(9-acridinyl)heptane, 1,5-bis(9-acridinyl)pentane, 1,3-bis(9-acridinyl)propane, or any combination thereof.

[0052] In some specific examples, the aromatic ketone compound is acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, benzophenone, 4-benzoyldiphenylsulfide, 4-benzoyl-4'-methyldiphenylsulfide, 4-benzoyl-4'-ethyldiphenylsulfide, 4-benzoyl-4'-propyldiphenylsulfide, 4,4'-bis(diethylamino)benzophenone, 4-p-toluenemercaptobenzophenone, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(methylethylamino)benzophenone, acetophenone dimethyl ketal, benzil dimethyl ketal, α,α'-dimethylbenzyl ketal, α,α'-diethoxyacetophenone, 2-hydroxy-2-methyl- The hydroxyl groups may include, but are not limited to, 1-phenylacetone, 1-hydroxycyclohexylbenzophenone, 2-hydroxy-2-methyl-1-p-hydroxyethyl ether phenylacetone, 2-methyl-1-(4-methylmercaptophenyl)-2-morpholino-1-acetone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, phenylbis(2,4,6-trimethylformyl)phosphine oxide, 2,4,6-(trimethylformyl)-diphenylphosphine oxide, 2-hydroxy-1-(1-(4-(2-hydroxy-2-methyl-propionyl)-phenyl)-1,3,3-trimethyl-inden-5-yl)-2-methylacetone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl-(2-hydroxy-2-propyl)ketone, or any combination thereof.

[0053] In some specific examples, the anthraquinone-based compound may include, but is not limited to, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 2,3-dimethylanthraquinone, 2-ethylanthracene-9,10-diethyl ester, 1,2,3-trimethylanthracene-9,10-dioctyl ester, 2-ethylanthracene-9,10-di(4-chlorobutyric acid methyl ester), 2-(3-((3-ethyloxetan-3-yl)methoxy)-3-oxopropyl)anthracene, 9,10-di(2-hydroxyethylmercapto)anthracene, 9,10-di(3-hydroxy-1-propylmercapto)anthracene, or any combination thereof.

[0054] In some embodiments, benzoin and benzoin alkyl ether compounds may include, but are not limited to, benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, or any combination thereof.

[0055] In some specific examples, the oxime ester compound is 1-(4-phenylthiophenyl)-n-octane-1,2-dione-2-benzoic acid oxime ester, 1-(6-(2-methylbenzoyl)-9-ethylcarbazol-3-yl)-ethan-1-one-acetic acid oxime ester, 1-(6-(2-methylbenzoyl)-9-ethylcarbazol-3-yl)-propan-1-one-acetic acid oxime ester, 1-(6-(2-methylbenzoyl)-9-ethylcarbazol-3-yl)-but ... 1-(6-(2-methylbenzoyl)-9-ethylcarbazol-3-yl)-1-cyclohexyl-methane-1-one-acetic acid oxime ester, 1-(6-(2-methylbenzoyl)-9-ethylcarbazol-3-yl)-(3-cyclopentyl)-propan-1-one-acetic acid oxime ester, 1-(4-phenylthiophenyl)-(3-cyclopentyl)propane-1,2-dione-2-benzoic acid oxime ester, 1-(4-phenylthiophenyl)-(3-cyclohexyl)-propane-1,2-dione-2-benzoic acid oxime ester, 1-(4-phenylthiophenyl)-(3-cyclohexyl)-propane-1,2-dione-2-benzoic acid oxime ester 1-(6-(2-methylbenzoyl)-9-ethylcarbazol-3-yl)-(3-cyclopentyl)-propane-1,2-dione-2-acetic acid oxime ester, 1-(6-o-methylbenzoyl)-9-ethylcarbazol-3-yl)-(3-cyclopentyl)-propane-1,2-dione-2-benzoic acid oxime ester, 1-(4-benzoyldiphenylsulfide)-(3-cyclopentylacetone)-1-oxime acetone tate, 1-(6-o-methylbenzoyl)-9-ethylcarbazol-3-yl)-(3-cyclopentylacetone)-1-oxime cyclohexyl acetate, 1-(4-benzoyldiphenylsulfide)-(3-cyclopentylacetone)-1-oxime cyclohexylcarboxylate, 1-(6-o-methylbenzoyl)-9-ethylcarbazol-3-yl)-(3-cyclopentyl)-propane-1,2-dione-2-o-methylbenzoic acid oxime ester, 1-(4-benzoylphenyl)-(3-cyclopentyl)-propane-1,2-Dione-2-cyclohexylcarboxylic acid oxime ester, 1-(4-thienoyl-diphenylsulfide-4'-yl)-(3-cyclopentyl)-propan-1-one-acetic acid oxime ester, 1-(4-benzoyldiphenylsulfide)-(3-cyclopentyl)-propane-1,2-dione-2-oxime acetate, 1-(6-nitro-9-carbazol-3-yl)-3-cyclohexyl-propan-1-one-acetic acid oxime ester, 1-(6-o-methylbenzoyl)-9-ethylcarbazol-3-yl)-(3-cyclo 1-(6-furanylfurfurylformyl-9-ethylcarbazol-3-yl)-(3-cyclohexylacetone)-1-oxime acetate, 1-(6-furanylfurfurylformyl-9-ethylcarbazol-3-yl)-(3-cyclohexylacetone)-1-oxime acetate, 1,4-diphenylpropane-1,3-dione-2-acetic acid oxime ester, 1-(6-furoyl-9-ethylcarbazol-3-yl)-(3-cyclohexyl)-propane-1,2-dione-2-acetic acid oxime ester ter, 1-(4-phenylthiophenyl)-(3-cyclohexyl)-propane-1,2-dione-2-oxime acetate, 1-(4-phenylthiophenyl)-(3-cyclohexyl)-propane-1,2-dione-3-benzoic acid oxime ester, 1-(6-thienoyl-9-ethylcarbazol-3-yl)-(3-cyclohexyl)-propane-1,2-dione-2-acetic acid oxime ester, 2-((benzoyloxy)imino)-1-phenylpropan-1-one, 1-phenyl-1,2-propanedione-2-(oxoacetyl)oxime Shim, 1-(4-phenylthiophenyl)-2-(2-methylphenyl)-ethane-1,2-dione-2-acetic acid oxime ester, 1-(9,9-dibutyl-7-nitro-2-yl)-(3-cyclohexyl)-propan-1-one-2-acetic acid oxime ester, 1-(4-(4-(thienyl-2-formyl)phenylthiophenyl)-3-cyclopentylpropane-1,2-dione-2-acetic acid oxime ester, 1-(9,9-dibutyl-2-yl)-3-cyclohexylpropylpropane-1,2-dione-2-acetic acid oxime ester, 1-(9,9-Dibutyl-2-yl)-3-cyclohexylpropylpropane-1,2-dione-2-acetic acid oxime ester, 1-(6-(2-benzoyloxyimino)-3-cyclohexylpropyl-9-ethylcarbazol-3-yl)octane-1,2-dione-2-benzoic acid oxime ester, 1-(7-nitro-9,9-diallylfluoren-2-yl)-1-(2-methylphenyl)methanone-acetic acid oxime ester, 1-(6-(2-methylbenzoyl)-9-ethylcarbazol-3-yl)- The oxime esters may include, but are not limited to, (3-cyclopentyl)-propan-1-one-2-benzoic acid oxime ester, 1-(7-(2-methylbenzoyl)-9,9-dibutylfluoren-2-yl)-(3-cyclohexyl)-propane-1,2-dione-2-acetic acid oxime ester, 1-(6-(furanyl-2-formyl)-9-ethylcarbazol-3-yl)-(3-cyclohexyl)-propane-1,2-dione-2-ethoxycarbonyl oxime ester, or any combination thereof.

[0056] In some specific examples, the triazine-based compound is 2-(4-ethylbiphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4-methyleneoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 3-(4-(2,4-bis(trichloromethyl)-s-triazin-6-yl)phenylthio)propionic acid, 1,1,1,3,3,3-hexafluoroisopropyl-3-(4-(2,4-bis(trichloromethyl)-s-triazin-6-yl)phenylthio)propiolate, ethyl-2-(4-(2,4-bis(trichloromethyl)-s-triazin-6-yl)phenylthio)acetate, cyclohexyl-2-(4-(2,4-bis(trichloromethyl)-s-triazin-6-yl)phenyl The methylamino-4-amino-(6-p-methoxystyryl)-s-triazine may include, but are not limited to, 2-ethoxyethyl-2-(4-(2,4-bis(trichloromethyl)-s-triazin-6-yl)phenylthio)acetate, 2-ethoxyethyl-2-(4-(2,4-bis(trichloromethyl)-s-triazin-6-yl)phenylthio)acetate, benzyl-2-(4-(2,4-bis(trichloromethyl)-s-triazin-6-yl)phenylthio)acetate, 3-(chloro-4-(2,4-bis(trichloromethyl)-s-triazin-6-yl)phenylthio)propionic acid, 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazine, 2,4-bis(trichloromethyl)-6-(1-p-dimethylaminophenyl)-1,3-butadienyl-s-triazine, 2-(trichloromethyl)-4-amino-(6-p-methoxystyryl)-s-triazine, or any combination thereof.

[0057] In some specific examples, the coumarin-based compounds may include, but are not limited to, 3,3′-carbonylbis(7-diethylaminocoumarin), 3-benzoyl-7-diethylaminocoumarin, 3,3′-carbonylbis(7-methoxycoumarin), 7-diethylamino-4-methylcoumarin, 3-(2-benzothiazole)-7-(diethylamino)coumarin, 7-(diethylamino)-4-methyl-2H-1-benzopyran-2-one (7-(diethylamino)-4-methylcoumarin), 3-benzoyl-7-methoxycoumarin, or any combination thereof.

[0058] In some specific examples, the thioxanthone-based compound may include, but is not limited to, thioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, diisopropylthioxanthone, or any combination thereof.

[0059] The content of the photoinitiator (C) is about 0.01 to about 10 parts by weight, based on 100 parts by weight of the photocurable composition. When the content of the photoinitiator (C) is within this range, the photocurable composition can have excellent solubility and photosensitivity, and can exhibit excellent exposure effects.

[0060] Sensitizer (D)

[0061] The sensitizer (D) of the present invention comprises one or more pyrazoline compounds having the structure shown in formula (I) above. To improve the sensitization of the photocurable composition, the content of sensitizer (D) is about 0.001 to about 10 parts by weight (e.g., about 0.001, about 0.005, about 0.01, about 0.1, about 0.17, about 0.3, about 0.5, about 1, about 2, about 5, about 7, or about 10 parts by weight), preferably about 0.005 to about 5 parts by weight, based on 100 parts by weight of the photocurable composition. When the content of sensitizer (D) is within the above range, photosensitivity and resolution can be improved, i.e., the drawback of broadened photocurable patterns can be reduced.

[0062] Auxiliary Agent (E)

[0063] To improve the properties of the photocurable composition of the present invention, the photocurable composition further comprises an auxiliary agent (E).

[0064] The auxiliary (E) according to the present invention may include, but is not limited to, a compound capable of donating hydrogen ions, a dye, a pigment, a photocolorant, a stabilizer, an adhesion promoter, a defoaming auxiliary, a release promoter, or a combination thereof.

[0065] The type of compound capable of providing hydrogen ions is not particularly limited, and in some specific examples, the compound capable of providing hydrogen ions may include, but is not limited to, triethanolamine, methyl 4-dimethylaminobenzoate, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, dimethylphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, dodecyl mercaptan, ethylene glycol bis(3-mercaptobutyrate), or any combination thereof.

[0066] In some embodiments, the dyes, pigments, and photochromic agents are selected from the group consisting of tris(4-dimethylaminophenyl)methane (LCV), tris(4-dimethylamino-2-methylphenyl)methane, fluoran dyes, toluenesulfonic acid hydrate, basic fuchsin, phthalocyanine green / phthalocyanine blue, auramine base, parafuchsin, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green, diamond green, basic blue 20, brilliant green, eosin, ethyl violet, erythrosin sodium salt B, methyl green, phenolphthalein, alizarin red S, thymolphthalein, methyl violet 2B, quinaldine red, rose bengal sodium agar, metanil yellow, thymo The dyes may include, but are not limited to, sulfophthalein, xylenol blue, methyl orange, orange IV, diphenylthiocarbazone, 2,7-dichlorofluorescein, paramethyl red, Congo red, benzopurpurin 4B, α-naphthyl red, phenacetin, methyl violet, Victoria Pure Blue BOH, rhodamine 6G, diphenylamine, dibenzylamine, triphenylamine, N,N-diethylaniline, di-p-diamine, p-toluidine, benzotriazole, methylbenzotriazole, 4,4'-biphenyldiamine, o-chloroaniline, leuco crystal violet, leucomalachite green, leucoaniline, leucomethyl violet, azo dyes, and titanium dioxide, or any combination thereof.

[0067] In some specific examples, the stabilizer may include, but is not limited to, hydroquinone, 1,4,4-trimethyl-diazobicyclo(3.2.2)-non-2-ene-2,3-dioxide, 1-phenyl-3-pyrazolidinone, p-methoxyphenol, 2,2'-methylenebis(6-t-butyl-4-ethylphenol), alkyl and aromatic substituted hydroquinones and quinones, t-butylcatechol, 1,2,3-benzenetriol, copper resinate, naphthylamine, β-naphthol, cuprous chloride, 2,6-di-t-butyl-p-cresol, phenothiazine, pyridine, nitrobenzene, dinitrobenzene, p-toluenequinone, benzenequinone, or any combination thereof.

[0068] In some embodiments, the coating aid may include, but is not limited to, acetone, methanol, ethanol, isopropanol, butanone, propylene glycol monomethyl ether acetate, ethyl acetate, cyclohexanone, gamma-butyrolactone, dichloromethane, or any combination thereof.

[0069] In some embodiments, the release promoter may include, but is not limited to, benzene sulfonic acid, toluene sulfonic acid, xylene sulfonic acid, phenol sulfonic acid, alkyl benzene sulfonic acids such as methyl / propyl / heptyl / octyl / decyl / dodecyl, or any combination thereof.

[0070] The content of the other auxiliary (E) is not particularly limited and may be adjusted according to application needs. Generally, the content of the other auxiliary (E) is about 1 part by weight to about 10 parts by weight based on 100 parts by weight of the photocurable composition.

[0071] The photocurable composition of the present invention uses a pyrazoline compound having the structure of formula (I) as a sensitizer, thereby imparting to the photocurable composition the properties of good compatibility, high photosensitivity, and good resolution and adhesion.

[0072] The photocurable composition of the present invention can be manufactured into a dry film, i.e., a photosensitive resin laminate, and can be used in processes such as printed circuit boards, protective images, conductor images, lead wires, and semiconductor packaging, and can form required images on various substrates through different processes.

[0073] The dry film includes a photosensitive resin layer formed from a photocurable composition, a support supporting the photosensitive resin layer, and a coating film. Generally, dry film fabrication involves applying a photocurable composition to a support, drying the support to form a photosensitive resin layer, and optionally laminating the resulting layer to a coating film serving as a protective layer. In some embodiments, the drying temperature is about 80°C to about 120°C, and the drying time is about 1 minute to about 10 minutes. In some embodiments, the thickness of the photosensitive resin layer is about 5 μm to about 120 μm, preferably about 15 μm to about 40 μm.

[0074] In some embodiments, the support may be any of various types of plastic films, such as polyethylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, cellulose acetate, polymethyl methacrylate, methacrylate copolymers, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, vinyl chloride copolymers, polyamide, polyimide, ethylene chloride-vinyl acetate copolymers, polytrichloroethylene, polytetrafluoroethylene, or composite materials of any of the above, preferably polyethylene terephthalate, which has excellent optical transparency. In such embodiments, the thickness of the support is about 5 μm to about 150 μm, preferably about 10 μm to about 50 μm.

[0075] The method for applying the photocurable composition is not particularly limited, and may be spray coating, roller coating, spin coating, slit coating, compression coating, curtain coating, or the like.

[0076] In some embodiments where the dry film is used in the manufacture of printed circuit boards, the process includes: (1) a film lamination process in which a photosensitive resin layer is laminated onto a substrate (e.g., a copper-clad laminate or a flexible substrate); (2) an exposure process in which the photosensitive resin layer is exposed to ultraviolet light using an image template to cause a photo-curing reaction in the exposed areas; (3) a development process in which the unexposed areas of the photosensitive resin layer are removed with a developer to form the desired protected image areas; (4) an etching or electroplating process in which the unprotected image areas on the surface of the copper-clad laminate or flexible substrate are etched or electroplated to form a conductor image; and (5) a peeling process in which the protected image areas are peeled off from the copper-clad laminate or flexible substrate.

[0077] In the above exposure process, exposure is performed by employing a mask exposure method, a projection exposure method, or a direct writing exposure method such as a laser direct imaging exposure method or a digital optical processing exposure method, and actinic rays are irradiated in an imagewise manner. The light source of the actinic rays may be a common light source, such as a carbon arc lamp, a mercury vapor arc lamp, an ultra-high pressure indicator lamp, a high pressure indicator lamp, a xenon lamp, a gas laser such as argon, a solid laser such as a YAG laser, a semiconductor laser, or a gallium nitride blue-violet laser, which effectively emits ultraviolet light. In the photocurable composition of the present invention, the type of actinic rays source is not particularly limited, and the exposure energy is preferably 10 mJ / cm. 2 ~1000mJ / cm 2 is.

[0078] In the development process, the unexposed portions of the photosensitive resin layer are removed with a developer. The developer may be an alkaline aqueous solution. In some specific examples, the alkaline aqueous solution may include, but is not limited to, a 0.1 to 5 weight percent sodium carbonate solution, a 0.1 to 5 weight percent potassium carbonate solution, and a 0.1 to 5 weight percent sodium hydroxide solution, and has a pH value of 9 to 11. The alkaline aqueous solution further includes a surfactant, an antifoaming agent, and one or more organic solvents. In some specific examples, the development method may include, but is not limited to, common development methods such as immersion, spraying, or brushing.

[0079] In the etching process, the protective image formed on the substrate is used as a mask region template to etch the unprotected region to form the conductor image. The etching method can be selected according to the conductor layer to be removed, and the etching solution can be, for example, a cuprous oxide solution, an iron oxide solution, an alkaline etching solution, or a hydrogen peroxide-based etching solution.

[0080] In the electroplating process, the protective image formed on the substrate is used as a mask area template, metal plating is performed on the uncovered areas, and the photosensitive resin layer of the protective image is removed after the electroplating process to obtain the desired conductor image. In some embodiments, the electroplating process can be, but is not limited to, an electroplating method or an electroless plating method.

[0081] The stripping process may be carried out using an alkaline aqueous solution stronger than the alkaline aqueous solution used in the development process, such as a 1 to 10 weight percent sodium hydroxide aqueous solution or a 1 to 10 weight percent potassium hydroxide aqueous solution.

[0082] The following provides some examples to illustrate the application of the present invention, but they are not used to limit the present invention, and those skilled in the art can make various modifications and improvements without departing from the spirit and scope of the present invention. Preparation of pyrazoline sensitizers

[0083] I. Preparation of pyrazoline compound D1

[0084] I.1 Preparation of compound c [ka]

[0085] (a) 25.20 g (0.21 mole) of 4-hydroxybenzaldehyde, 0.688 g (2.75 mmole) of pyridinium 4-toluene-sulfonate, and 60 mL of dichloromethane were placed in a 250 mL two-neck flask.

[0086] (b) At a temperature of 50±2°C and in a nitrogen gas atmosphere, 17.49 g (0.21 mole) of 3,4-dihydro-2H-pyran was added dropwise to the two-neck flask from step (a) over 10 minutes, and after the addition was completed, the mixture was stirred while keeping the temperature constant.

[0087] (c) After reacting for 45 hours, the reaction mixture was monitored on a thin layer chromatography (TLC) sheet to confirm that no 4-hydroxybenzaldehyde remained, and then the temperature was lowered to room temperature.

[0088] (d) After the mixture from step (c) was repeatedly washed three times with deionized water (40 mL), the solution was dried over anhydrous magnesium sulfate, filtered, and then directly concentrated on a rotary evaporator to give 39.16 g of an orange liquid (compound c) in a 92.0% yield.

[0089] I.2 Preparation of compound d [ka]

[0090] (a) 39.16 g (0.190 mole) of compound c, 36.0 g (0.18 mole) of 4-acetylbiphenyl, and 80 mL of methanol were placed in a 250 mL two-neck flask.

[0091] (b) At a temperature of 25±2°C, 16.0 g of 40% NaOH was slowly added dropwise to the two-necked flask from step (a) over 10 minutes, and after the addition was completed, the mixture was stirred while keeping the temperature for 24 hours.

[0092] (c) The remaining 4-acetylbiphenyl was monitored on a TLC sheet. When the reaction was complete (i.e., when no 4-acetylbiphenyl remained), the temperature was lowered to 20±2°C, and the solid was filtered, washed with a small amount of methanol, and dried to obtain 60.68 g of a goose-yellow product (compound d) in a yield of 86.0%.

[0093] I.3 Preparation of compound e [ka]

[0094] (a) 28.63 g (74.47 mmole) of compound d, 12.2 g of 37% HCl, and 130 mL of dichloromethane were placed in a 250 mL two-neck flask.

[0095] (b) The two-necked flask from step (a) was stirred at a temperature of 25±2° C. for 20 hours, during which the solution went from cloudy to clear and then gradually became cloudy again.

[0096] (c) Upon completion of the reaction, the temperature was lowered to 20±2°C, and the solid was filtered, washed with a small amount of dichloromethane, and dried to give 14.1 g of a yellow-green solid (compound e) in a yield of 63.2%.

[0097] I.4 Preparation of Compound D1 [ka]

[0098] (a) 11.84 g (39.4 mmole) of compound e and 120 mL of glacial acetic acid were placed in a 250 mL two-neck flask.

[0099] (b) To the two-neck flask from step (a), 11.55 g (106.8 mmole) of phenyl hydrazone was added dropwise over 0.5 hours at room temperature with stirring. After the addition was complete, the mixture was heated to 50±2°C and stirred for 17 hours while maintaining the temperature.

[0100] (c) The remaining compound e was monitored on a TLC sheet, and when the reaction was completed, the temperature was lowered to 10±2°C.

[0101] (d) The mixture from step (c) was filtered, rinsed with deionized water and dried to give 11.97 g of a light yellow solid (compound D1) in 77.8% yield.

[0102] II. Preparation of pyrazoline sensitizers

[0103] II.1 Preparation of Compound D2 [ka]

[0104] (a) 3.9056 g (10.00 mmole) of compound D1, 4.8854 g (15.00 mmole) of cesium carbonate (Cs2CO3), 30 mL of N,N-dimethylformamide (DMF), and 0.8289 g (5.00 mmole) of 1,5-dibromopentane were placed in a 100 mL single-neck flask.

[0105] (b) The mixture of step (a) was heated to 60±2°C with stirring and kept at that temperature for 2 hours. The remaining compound D1 was monitored on a TLC sheet, and when the reaction was completed, the temperature of the single-neck flask was lowered to room temperature.

[0106] (c) 50 mL of ethyl acetate and 30 mL of deionized water were added to the mixture from step (b), stirred for 10 minutes, and the organic layer was separated and washed twice with 50 mL of saturated brine. The organic layer was dried over anhydrous magnesium sulfate, directly concentrated on a rotary evaporator, and recrystallized from dichloromethane to give 3.476 g of a yellow solid (Compound D2) in 82.1% yield.

[0107] The resulting products were 1 1 H NMR and mass spectrometry were performed. 1The H NMR (400 MHz, acetone-d6) analysis results were 7.89 (d, 4H), 7.75-7.71 (m, 8H), 7.50 (dd, 4H), 7.39 (t, 2H), 7.28 (d, 4H), 7.16 (d, 4H), 7.14 (d, 4H), 6.91 (d, 4H), 6.74 (t, 2H), 5.44 (dd, 2H), 4.01-3.95 (m, 6H), 3.18 (dd, 2H), 1.84-1.82 (m, 4H), and 1.65-1.63 (m, 2H). The molecular weight of the product was 860, and mass spectrometry revealed peak signals for molecular fragments 861 and 862.

[0108] II.2 Preparation of compound D3 [ka]

[0109] (a) 2.3424 g (6.00 mmole) of compound D1 was dissolved in 30 mL of dichloromethane and placed in a 100 mL two-necked reaction flask.

[0110] (b) 0.5209 g (3.08 mmole) of glutaryl chloride was dissolved in 5 mL of dichloromethane.

[0111] (c) The solution from step (a) was stirred at a temperature of 0° C., and the solution from step (b) was slowly added dropwise to the reaction flask over a period of 5 minutes.

[0112] (d) Then, 6 mL of triethylamine was slowly added dropwise to the reaction flask over 5 minutes, and the solution turned from cloudy to clear.

[0113] (e) After the addition of triethylamine was completed, the reaction flask was heated to 25±2°C and stirring was continued for 20 hours.

[0114] (f) The remaining compound D1 was monitored by TLC. Upon completion of the reaction, the reaction mixture was washed twice with 20 mL of deionized water, dried over anhydrous magnesium sulfate, filtered, and then directly concentrated on a rotary evaporator to obtain an orange solid. The solid was then washed with a 2:1 mixture of methanol and ethyl acetate and filtered to obtain 2.32 g of a pale yellow solid in an 87.2% yield.

[0115] The resulting products were 1 1 H NMR and mass spectrometry were performed. 1 The H NMR (400 MHz, acetone-d6) analysis results were 7.89 (d, 4H), 7.74-7.70 (m, 8H), 7.48 (dd, 4H), 7.41-7.38 (m, 6H), 7.16 (d, 4H), 7.14-7.10 (m, 8H), 6.74 (t, 2H), 5.51 (dd, 2H), 4.02 (dd, 2H), 3.27 (dd, 2H), 2.73 (t, 4H), and 2.10 (m, 2H). The molecular weight of the product was 888, and mass spectrometry revealed peak signals for molecular fragments of 889 and 890.

[0116] II.3 Preparation of compound D4 [ka]

[0117] (a) 3.9252 g (10.00 mmole) of compound D1, 4.9161 g (15.09 mmole) of cesium carbonate (Cs2CO3), 40 mL of butanone, and 1.3196 g (5.00 mmole) of α,α'-dibromo-p-xylene were placed in a 100 mL single-neck flask.

[0118] (b) The mixture of step (a) was heated to 60±2°C with stirring and kept at that temperature for 23 hours. The remaining compound D1 was monitored on a TLC sheet, and upon completion of the reaction, the temperature of the single-neck flask was lowered to room temperature.

[0119] (c) 50 mL of ethyl acetate and 30 mL of deionized water were added to the mixture from step (b), stirred for 10 minutes, and the organic layer was separated and washed twice with 50 mL of saturated brine. The organic layer was dried over anhydrous magnesium sulfate, directly concentrated on a rotary evaporator, and recrystallized from dichloromethane to give 3.192 g of a yellow solid (Compound D4) in 72.3% yield.

[0120] The resulting products were 1 1 H NMR and mass spectrometry were performed. 1 The H NMR (400 MHz, dichloromethane-d2) analysis results were 7.82 (d, 4H), 7.67-7.65 (m, 8H), 7.47 (dd, 4H), 7.44 (s, 4H), 7.37 (t, 2H), 7.26 (d, 4H), 7.18 (dd, 4H), 7.09 (d, 4H), 6.95 (d, 4H), 6.78 (t, 2H), 5.31 (dd, 2H), 5.05 (s, 4H), 3.88 (dd, 2H), and 3.16 (dd, 2H). The molecular weight of the product was 882, and mass spectrometry revealed peak signals for molecular fragments 883 and 884.

[0121] II.4 Preparation of compound D5 [ka]

[0122] Compound D5 (1-phenyl-3-biphenyl-5-(4-triglycolmethyletherphenyl)pyrazoline) was purchased from Changzhou Power Electronic New Materials Co., Ltd. Its synthesis method can be found in Taiwan Patent Publication No. TWI766645B and / or China Patent Publication No. CN113527207B. Preparation of photocurable compositions

[0123] The above pyrazoline sensitizers (compounds D1 to D5, among which compounds D2, D3, and D4 are pyrazoline compounds having the structure of formula (I) above), alkali-soluble polymers (A1 to A3), double bond-containing monomers or oligomers (B1 to B5), photoinitiators (C1 to C2), and auxiliary agents (E1 to E5) were uniformly mixed in the ratios shown in Table 1 below to prepare photocurable compositions of Examples 1 to 5 and Comparative Examples 1 to 4. The components represented by the respective component symbols are as shown in Table 2.

[0124] [Table 1]

[0125] [Table 2] Characterization

[0126] I. Production of evaluation samples

[0127] I.1 Dry film production

[0128] The photocurable composition was thoroughly stirred, and then uniformly coated on the surface of a 16 μm-thick polyethylene terephthalate support using a coater. The composition was then dried in an oven at 90°C for 3 minutes to form a 30 μm-thick photosensitive resin layer. A 20 μm-thick polyethylene film was then attached to the surface of the photosensitive resin layer as a protective layer to obtain a dry film.

[0129] I.2 Substrate surface treatment

[0130] The photosensitive resin layer was bonded to a copper foil substrate with a copper foil thickness of 35 μm and a substrate thickness of 1.6 mm. Before bonding, the surface of the copper foil substrate was first polished once with a wet polishing roller (manufactured by 3M Co.) using HD#800 and 1000 mesh sizes, respectively.

[0131] I.3 Film lamination

[0132] The protective layer of the dry film was peeled off, and film lamination was performed using a hot roller film laminator (manufactured by Zhisheng Technology Co., Ltd., model number CSL-M25E). The film lamination conditions were a preheating temperature of 60°C, a film lamination temperature of 110°C, a film lamination pressure of 0.3 MPa, and a film lamination speed of 1.5 m / min.

[0133] I.4 Exposure

[0134] After laminating the film, the photosensitive resin layer was exposed to light using a laser direct imaging exposure device (LDI, manufactured by ADTEC Engineering Co., Ltd., model number IP-4UH) at different energy settings.

[0135] I.5 Development

[0136] After peeling off the polyethylene terephthalate from the exposed sample, the sample was developed using a developing machine (manufactured by Azhi System Technology Co., Ltd., model number 410MP) under conditions of 0.85% aqueous sodium carbonate solution, temperature 28°C, and upper / lower spray pressures of 0.16 / 0.18 MPa. The development time was twice the shortest time required to completely dissolve the unexposed photosensitive resin layer.

[0137] II Evaluation Contents

[0138] II.1 Compatibility evaluation

[0139] After thoroughly stirring and mixing the photocurable compositions of Examples 1 to 5 and Comparative Examples 1 to 4, the photocurable composition solution was uniformly applied to the surface of a 16 μm-thick polyethylene terephthalate thin film support, and dried in an oven at 90°C for 3 minutes to form a 30 μm-thick photosensitive resin layer. The surface on which the photosensitive resin layer was applied was observed, and classification was confirmed as follows. √: The coating surface is uniform and free of insoluble matter. X: Insoluble matter is found on the coating film surface.

[0140] II.2 Photosensitivity evaluation

[0141] The photosensitivity of the photocurable composition was evaluated by placing the film on the laminated sample plate and then exposing and developing it using a 21 / 41 level energy level chart (manufactured by Stouffer), which has a brightness change of 21 / 41 levels from clear to black. After exposure, the sample plate was left for approximately 10 to 20 minutes, i.e., developed for twice the shortest time required to completely dissolve the unexposed photosensitive resin layer. The remaining resist film on the sample plate was classified as follows based on the exposure energy of the 21 / 41 level exposure chart, which has a level of 7 / 19. ○: Exposure energy is 17 mJ / cm 2 The following is the result. △: Exposure energy is 17 mJ / cm 2 Greater than 25mJ / cm 2 is smaller than. ●: Exposure energy is 25mJ / cm 2 That's all.

[0142] II.3 Development evaluation

[0143] Thickness 30μm, area 0.24m 2 The photosensitive resin layer was coated, dissolved in 1 L of 0.85% sodium carbonate aqueous solution, and sprayed using a circulating sprayer at a spray pressure of 0.1 MPa for 8 hours. The sprayed developer solution was then left for one day, and the presence of aggregated precipitate powder and / or oily substances on the bottom, sidewall, or solution surface of the sprayer was observed. The following classification was performed. Good: No agglomerated precipitate powder and / or oily material is present on the bottom, sidewalls or solution surface of the jetting device, and a small amount of observable agglomerated precipitate is observed floating in the developer, but can be easily washed away with a small amount of water. △: Aggregated precipitate powder and / or oily substance was observed on the bottom or side wall of the sprayer or part of the solution surface, and was difficult to wash away completely when washed with water. ●: Agglomerated powdery precipitate and / or oily substances were clearly observed on the bottom or sidewall of the sprayer or on the surface of the solution. When washed with water, they could not be completely washed away, and residue remained.

[0144] II.4 Resolution evaluation

[0145] Using a linear image protection film with a width ratio of exposed to unexposed areas of 1:1, the sample plate after film lamination was exposed to light with an energy of 7 / 19 levels on a 21 / 41 level exposure table, and then developed for twice the shortest time required for complete dissolution of the unexposed photosensitive resin layer. Resolution was evaluated based on the minimum coated line width that successfully formed a hardened photosensitive resin layer. The following classification was performed. ◯: The minimum resolution is 25 μm or less. △: The minimum resolution value is greater than 25 μm and smaller than 40 μm. ●: The minimum resolution is 40 μm or more.

[0146] II.5 Adhesion evaluation

[0147] Using a linear image protection film with a width ratio of exposed to unexposed areas of 1:1, the sample plate after film lamination was exposed to energy at 7 / 19 levels on a 21 / 41 level exposure table, and then developed for twice the shortest time required for complete dissolution of the unexposed photosensitive resin layer. Adhesion evaluation was performed using the minimum coating line width that successfully formed a hardened photosensitive resin layer. The following classification was performed. ◯: The minimum adhesion value is 24 μm or less. △: The minimum adhesion value is greater than 24 μm and less than 40 μm. ●: The minimum adhesion value is 40 μm or more.

[0148] III. Evaluation Results

[0149] The evaluation results of Examples 1 to 5 and Comparative Examples 1 to 4 are shown in Table 3.

[0150] [Table 3]

[0151] Based on the above examples, when a pyrazoline compound having the structure of formula (I) is used as a sensitizer in the present invention, the photocurable composition prepared has excellent compatibility with each component and exhibits excellent photosensitivity, developability, resolution, and adhesion. Furthermore, when a specific amount of pyrazoline sensitizer having the structure of formula (I) is used, the photocurable composition prepared exhibits excellent photosensitivity and resolution. Therefore, the photocurable composition of the present invention can be used in the form of a dry film in processes such as the manufacture of printed circuit boards, protective images, conductor images, lead wires, and semiconductor packaging.

[0152] As described above, the pyrazoline compound and the photocurable composition containing the same according to the present invention can be produced by a simple synthesis process, and the pyrazoline compound contains a sensitizer that provides excellent compatibility with various components in the photocurable composition, an absorption wavelength (e.g., 350 nm to 440 nm) that matches that of the photoinitiator, and good solubility in solvents, and further improves the photosensitivity, resolution, and adhesion of the photocurable composition.

[0153] Although the present invention has been disclosed as described above in several embodiments, it is not used to limit the present invention, and a person skilled in the art can make various modifications and improvements without departing from the spirit and scope of the present invention, so the protection scope of the present invention is subject to that defined by the appended claims.

Claims

1. A pyrazoline compound having the structure shown in formula (I): 【Chemistry 1】 In formula (I), R １ represents a linear alkylene group having 1 to 14 carbon atoms, an alkylene group substituted with a cycloalkyl group, an alkylene group substituted with an aromatic group, or a divalent organic group containing a carbonyl group or an alkenylene group.

2. The R １ is selected from the group consisting of structures represented by formula (I-1) to formula (I-29): 【Chemistry 2(1)】 【Chemistry 2(2)】 【Chemistry 2(3)】 The pyrazoline compound according to claim 1.

3. 1. A photocurable composition comprising: an alkali-soluble polymer (A), (B) a monomer or oligomer having a double bond; a photoinitiator (C), and A photocurable composition comprising a sensitizer (D) containing the pyrazoline compound according to claim 1 or 2.

4. 4. The photocurable composition according to claim 3, wherein the content of the alkali-soluble polymer (A) is 20 to 70 parts by weight, based on 100 parts by weight of the photocurable composition.

5. 4. The photocurable composition according to claim 3, wherein the content of the monomer or oligomer (B) having a double bond is 20 to 50 parts by weight, based on 100 parts by weight of the photocurable composition.

6. 4. The photocurable composition according to claim 3, wherein the content of the photoinitiator (C) is 0.01 to 10 parts by weight, based on 100 parts by weight of the photocurable composition.

7. 4. The photocurable composition according to claim 3, wherein the content of the sensitizer (D) is 0.001 to 10 parts by weight, based on 100 parts by weight of the photocurable composition.

8. 4. The photocurable composition according to claim 3, wherein the alkali-soluble polymer (A) is at least one selected from the group consisting of acrylic acid polymers, methacrylic acid polymers, copolymers of acrylic acid and acrylate, copolymers of methacrylic acid, methyl methacrylate, n-butyl acrylate, and styrene, styrene polymers, epoxy resin polymers, aliphatic polyurethane acrylate polymers, aromatic polyurethane acrylate polymers, amide polymers, amide epoxy resin polymers, alkyd resin polymers, and phenolic resin polymers.

9. 4. The photocurable composition according to claim 3, wherein the monomer or oligomer (B) having a double bond is at least one selected from the group consisting of an acrylate or methacrylate having at least one double bond, an acrylate or methacrylate having a bisphenol A functional group, an acrylate or methacrylate having a polyethylene glycol and / or polypropylene glycol functional group, an acrylate or methacrylate having a glycidyl group, an acrylate or methacrylate having a polyurethane group, an acrylate or methacrylate having an aromatic ring functional group, an alkyl acrylate, and an alkyl methacrylate.

10. 4. The photocurable composition according to claim 3, further comprising an auxiliary (E) which is at least one selected from the group consisting of a compound capable of providing a hydrogen ion, a dye, a pigment, a photocoloring agent, a stabilizer, an adhesion promoter, a defoaming auxiliary, and a release promoter.

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