Photosensitive composition, photosensitive laminate, and wiring board

Abstract

The invention provides a photosensitive composition, a photosensitive laminate and a circuit board. The photosensitive composition comprises the following components in parts by mass: 100 parts of alkali-soluble resin, 5-50 parts of a photopolymerization monomer, 0.1-10 parts of a photoinitiator and 0.01-30 parts of a light conversion agent, the absorption wavelength of the light conversion agent is greater than 390nm, and the emission wavelength of the light conversion agent is less than or equal to 390nm. The photosensitive composition provided by the invention is added with the light conversion agent, and the light conversion agent has an up-conversion function, can initiate an anti-Stokes phenomenon, absorbs long wavelength and low energy, and releases short wavelength and high energy, so that light with a relatively long wave band emitted by an exposure machine is converted into light with a relatively strong short wave band absorbed by the photoinitiator, and the exposure efficiency is improved. The high utilization rate of the light source is realized under the condition that the conventional photoinitiator is still used, so that the selectivity of the photoinitiator is expanded, and the photocuring speed and the photocuring effect are improved.

Description

Technical Field

[0001] The present invention relates to the technical field of photosensitive compositions, and in particular to a photosensitive composition, a photosensitive laminate and a circuit board. Background Art

[0002] Photoinitiators are key components of photocurable products, and often play a decisive role in the photocuring speed and photocuring effect of photocurable products. The speed of photocuring and the quality of photocuring effect are reflected in the resist as the length of exposure time (affecting production efficiency) and the quality of performance such as resolution, steepness, deep curing, and gold resistance. When selecting a photoinitiator, it is necessary to consider the matching of the absorption spectrum of the photoinitiator and the emission spectrum of the light source. Currently, the commonly used light sources of exposure machines are mainly high-pressure mercury lamps and LED lamps, with a wavelength range of generally 300-405nm and a peak of 365-405nm. The maximum absorption wavelength (maximum absorption wavelength refers to the maximum absorption value of a substance in the spectral wavelength, usually used to measure the absorption capacity of the substance to a certain wavelength of light) of commonly used photoinitiators is generally less than 390nm, and some are less than 370nm. Therefore, the utilization rate of light in the 370-405nm band is low.

[0003] In order to improve the utilization rate of light, a common practice is to mix photoinitiators with characteristic peaks at short wavelengths and long wavelengths (single-layer film CN112625149A), and further, to prepare a double-layer or multi-layer structure, with different photoinitiators selected for each layer (CN116300315A). However, although the mixing of different initiators improves the utilization rate of longer-wavelength light to a certain extent, most conventional photoinitiators are only "absorbed in longer-wavelength bands" rather than "characteristic peaks in longer-wavelength bands", and the utilization rate is limited; and the use of a double-layer or multi-layer structure with different initiators in different layers, in addition to the low utilization rate of the initiator, the preparation process is also cumbersome, which is not conducive to industrial application.

[0004] In view of this, the present invention is proposed. Summary of the invention

[0005] The main purpose of the present invention is to provide a photosensitive composition, a photosensitive laminate and a circuit board to solve the problem in the prior art that the utilization rate of longer wavelength light is low when mixing photoinitiators of different wavelengths or using different initiators in different layers of a double-layer or multi-layer structure.

[0006] In order to achieve the above-mentioned object, according to one aspect of the present invention, a photosensitive composition is provided, which comprises 100 parts of alkali-soluble resin, 5 to 50 parts of photopolymerizable monomers, 0.1 to 10 parts of photoinitiators and 0.01 to 30 parts of photoconverters, wherein the absorption wavelength of the photoconverter is greater than 390 nm and the emission wavelength is less than or equal to 390 nm.

[0007] In some embodiments, the photosensitive composition includes 0.01 to 10 parts of a light conversion agent by mass, and the light conversion agent is selected from at least one of NaLuF4, NaGdF4, NaYbF4, NaYF4, NaYGd, NaYLu, NaYNd, NaGd(WO4)2, LiErF4, BaYF5, BaLuF5, BaGdF5, BaYb2F8, CaS, LiLa(MoO4)2, Gd2O3, GdF3, ZrYO, YAIO, CaWO4, and a light conversion material composed of any of the above materials doped with rare earths, or a light conversion material composed of a derivative of any of the above materials, and the rare earth element includes at least one of Yb, Er, Tm, Eu, Sm, Bi, and Ho.

[0008] Furthermore, the light conversion agent is selected from at least one of NaGdF4, NaYF4, NaYGd, GdF3, and light conversion materials consisting of any of the above materials doped with rare earth, and light conversion materials consisting of derivatives of any of the above materials.

[0009] In some embodiments, the photosensitive composition includes 1 to 30 parts by weight of a light conversion agent, the light conversion agent includes a donor and an acceptor, the donor is selected from at least one of the compounds represented by formulas (I) to (III), and the acceptor is selected from at least one of the compounds represented by formulas (IV) to (VI);

[0010] Preferably, when the donor is selected from the compound represented by formula (I), the acceptor is selected from at least one of the compounds represented by formula (IV) to (VI); and / or, when the donor is selected from at least one of the compounds represented by formula (II) to (III), the acceptor is selected from the compound represented by formula (VI);

[0011]

[0012] In some embodiments, the photosensitive composition includes 0.01 to 10 parts of a light converter, measured by weight, and the light converter is selected from a metal halide perovskite light converter, the metal halide perovskite light converter is composed of alkaline earth metal cations, transition metal cations and halogens, and the metal halide perovskite light converter has a perovskite structure, wherein the alkaline earth metal includes at least one of beryllium, magnesium, calcium, strontium, barium, and francium, and the transition metal includes at least one of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, and zinc.

[0013] Further, the metal halide perovskite light conversion agent is CsPbX3; X is Cl, Br or I;

[0014] Furthermore, the metal halide perovskite light converter is formed by dispersing CsPbBr3 in Cs4PbBr6 crystals, and has a CsPbBr3 / Cs4PbBr6 doping structure.

[0015] Furthermore, the mass ratio of the light conversion agent to the photoinitiator is (0.5-8):1.

[0016] Furthermore, the acid value of the alkali-soluble resin is 10 to 200 KOH / g, and the weight-average molecular weight is 2000 to 15000; and / or, the photopolymerizable monomer is a monomer containing an ethylenically unsaturated group, including at least one of a monofunctional (meth)acrylate compound, a difunctional acrylate compound, a trifunctional acrylate compound or a multifunctional (meth)acrylate compound.

[0017] Further, the photoinitiator includes at least one of a titanocene compound, an acetophenone compound, an oxime ester compound, a phosphine oxide compound, an anthrone compound, a benzoin ether compound, a benzophenone compound, a phenylacetone compound, a butanone compound, an anthraquinone compound, a thioxanthone compound, a hexaarylbisimidazole compound, an acridine compound, a benzyl compound, and a benzoin compound; preferably, the photoinitiator is selected from 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 1-hydroxycyclohexylphenyl ketone , 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphonic acid ethyl ester, 2-methyl-1-(4-methylthiophenyl)-2-morphinyl-1-propanone, 2-isopropylthioxanthone, 4-p-toluenethiobenzophenone, benzophenone, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone, 4,4`-bis(dimethylamino)benzophenone, α,α`-dimethylbenzil ketal, α,α`-diethoxyacetophenone.

[0018] Furthermore, the photosensitive composition further comprises a thermal curing agent, the amount of the thermal curing agent is 5 to 20 parts by weight, and the thermal curing agent comprises at least one of epoxy resin, isocyanate, isocyanurate compound or triazine compound.

[0019] Furthermore, the epoxy resin includes at least one of bisphenol A epoxy resin, linked epoxy resin, novolac epoxy resin, epoxy resin containing naphthalene ring or alicyclic epoxy resin; wherein the bisphenol epoxy resin is selected from at least one of bisphenol A epoxy resin, bisphenol F epoxy resin or bisphenol S epoxy resin; the novolac epoxy resin is selected from at least one of phenol novolac epoxy resin or novolac epoxy resin; the phenolic resin is selected from at least one of phenol novolac epoxy resin or novolac epoxy resin.

[0020] Furthermore, the epoxy equivalent of the epoxy resin is 50 to 350 g / eq, and the softening point is 40 to 150°C.

[0021] In order to achieve the above object, according to another aspect of the present invention, a photosensitive layer stack is provided, which includes a support layer, a photosensitive layer and a protective layer stacked in sequence, and the material of the photosensitive layer is the photosensitive composition provided in the first aspect.

[0022] According to a third aspect of the present invention, there is provided a circuit board, the circuit board comprising a cured film, the cured film being formed by curing the photosensitive layer provided by the second aspect.

[0023] By applying the technical solution of the present application, the photosensitive composition provided by the present application is added with a light-conversion agent, which has an "up-conversion function" and can induce the "anti-Stokes" phenomenon, absorb long wavelength, low energy, and release short wavelength, high energy, thereby converting the longer wavelength light emitted by the exposure machine into shorter wavelength light that is more strongly absorbed by the photoinitiator, thereby achieving high utilization of the light source while still using conventional photoinitiators, thereby expanding the selectivity of the photoinitiator and improving the photocuring speed and photocuring effect. DETAILED DESCRIPTION

[0024] It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application can be combined with each other. The present invention will be described in detail below in conjunction with the embodiments.

[0025] As analyzed in the background technology of this application, photoinitiator is a key component of photocurable products, and the maximum absorption wavelength of commonly used photoinitiators is generally less than 390nm, and some are less than 370nm, so the utilization rate of light in the 370-405nm band is low. In the prior art, the use of photoinitiators of different wavelengths mixed or the use of different initiators in different layers of a double-layer or multi-layer structure to improve the utilization rate of light in the high-wavelength band still has the problem of low utilization rate of light in the longer-wavelength band. In order to solve this problem, the present application provides a photosensitive composition, a photosensitive laminate and a circuit board.

[0026] In a first typical embodiment of the present application, a photosensitive composition is provided, which comprises, by weight, 100 parts of an alkali-soluble resin, 5 to 50 parts of a photopolymerizable monomer, 0.1 to 10 parts of a photoinitiator, and 0.01 to 30 parts of a photoconverter, wherein the absorption wavelength of the photoconverter is greater than 390 nm and the emission wavelength is less than or equal to 390 nm.

[0027] The photosensitive composition provided in the present application is added with a photoconverter, which has an "up-conversion function" and can trigger the "anti-Stokes" phenomenon, absorb long wavelength, low energy, and release short wavelength, high energy, thereby converting the longer wavelength light emitted by the exposure machine into shorter wavelength light that is more strongly absorbed by the photoinitiator, thereby achieving high utilization of the light source while still using conventional photoinitiators, thereby expanding the selectivity of the photoinitiator and improving the photocuring speed and photocuring effect.

[0028] Typically but not limitatively, in the photosensitive composition provided in the present application, based on 100 parts by mass of the alkali-soluble resin, the amount of the photopolymerizable monomer is 5 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts or a range consisting of any two numerical values; the amount of the photoinitiator is 0.1 parts, 0.5 parts, 0.8 parts, 1 parts, 2 parts, 3 parts, 5 parts, 8 parts, 10 parts or a range consisting of any two numerical values; the amount of the light conversion agent is 0.01 parts, 0.05 parts, 0.08 parts, 0.1 parts, 0.2 parts, 0.5 parts, 1 parts, 1.5 parts, 2 parts, 5 parts, 8 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts or a range consisting of any two numerical values.

[0029] [Light conversion agent]

[0030] In the present application, any light conversion material that can satisfy the absorption wavelength>390nm and the emission wavelength≤390nm can be used as the light conversion agent of the present application. Specifically, in the present application, the light conversion agent includes at least four categories, wherein the first category of light conversion agents can be selected from NaLuF4, NaGdF4, NaYbF4, NaYF4, NaYGd, NaYLu, NaYNd, NaGd(WO4)2, LiErF4, BaYF5, BaLuF5, BaGdF5, BaYb2F8, CaS, LiLa(MoO 4)2. Gd2O3, GdF3, ZrYO, YAIO, CaWO4 and at least one of the light-conversion materials composed of any of the above materials doped with rare earth elements, and the light-conversion materials composed of derivatives of any of the above materials, wherein the above rare earth elements include at least one of Yb, Er, Tm, Eu, Sm, Bi, and Ho; preferably, the light-conversion agent is selected from NaGdF4, NaYF4, NaYGd, GdF3 and at least one of the light-conversion materials composed of any of the above materials doped with rare earth elements, and the light-conversion materials composed of derivatives of any of the above materials.

[0031] When the above-mentioned first light conversion agent is used, preferably in the photosensitizer composition, the amount of the above-mentioned first type of light conversion agent is 0.01 to 10 parts.

[0032] The second type of light conversion agent can also be selected from at least one of 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile, triphenylamine derivatives, and light conversion materials composed of any of the above materials doped with rare earths, and light conversion materials composed of derivatives of any of the above materials, and the above rare earth elements include at least one of Yb, Er, Tm, Eu, Sm, Bi, and Ho.

[0033] When the second light conversion agent is used, preferably in the photosensitizer composition, the amount of the second light conversion agent is 1 to 30 parts.

[0034] The third type of light conversion agent can also be selected from donor-acceptor complex type light conversion agents, including a donor and an acceptor, the donor is selected from at least one of the compounds represented by formulas (I) to (III), and the acceptor is selected from at least one of the compounds represented by formulas (IV) to (VI); when the donor is selected from the compound represented by formula (I), the acceptor is selected from at least one of the compounds represented by formulas (IV) to (VI); when the donor is selected from at least one of the compounds represented by formulas (II) to (III), the acceptor is selected from the compound represented by formula (VI);

[0035]

[0036]

[0037] When the third light conversion agent is used, preferably in the photosensitizer composition, the amount of the third light conversion agent is 1 to 30 parts.

[0038] The fourth type of light conversion agent can also be selected from metal halide perovskite light conversion agents, which are composed of alkaline earth metal cations, transition metal cations and halogens, and have a perovskite structure; wherein the alkaline earth metal includes at least one of beryllium, magnesium, calcium, strontium, barium, and francium, and the transition metal includes at least one of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, and zinc; preferably, the metal halide perovskite light conversion agent is CsPbX3; X is Cl, Br or I; further preferably, the metal halide perovskite light conversion agent is formed by CsPbBr3 dispersed in Cs4PbBr6 crystals, and has a CsPbBr3 / Cs4PbBr6 doping structure.

[0039] When the fourth type of light conversion agent is used, preferably in the photosensitizer composition, the amount of the fourth type of light conversion agent is 0.01 to 10 parts.

[0040] The mass fraction of the light converter in the photosensitive composition is 0.01-30 parts. Too much light converter may cause light scattering, affecting the accuracy of the exposure pattern position; on the other hand, it may cause agglomeration and sedimentation, affecting the dispersibility and compatibility. In addition, the light converter is generally solid and has a certain particle size range, which may affect the resolution and flexibility. The particle size of the light converter is preferably 1-1000nm, more preferably 30-500nm, 50-250nm, which is more conducive to improving the resolution and flexibility of the photosensitive film formed by the photosensitive composition.

[0041] [Alkali soluble resin]

[0042] In the present application, the alkali-soluble resin is a commonly used alkali-soluble resin in the art, and preferably has an acid value of 10 to 200 KOH / g and a weight average molecular weight of 2000 to 150000.

[0043] Typically but not limitatively, the acid value of the alkali-soluble resin is 10KOH / g, 20KOH / g, 50KOH / g, 80KOH / g, 100KOH / g, 150KOH / g, 200KOH / g or a range consisting of any two values; the weight-average molecular weight is 2000, 5000, 8000, 10000, 20000, 50000, 80000, 100000, 120000, 150000 or a range consisting of any two values.

[0044] In some embodiments, the alkali-soluble resin includes at least one of an acrylate resin and / or an alkali-soluble polyimide resin; wherein the monomers of the acrylate resin include but are not limited to itaconic acid, crotonic acid, acrylic acid, methacrylic acid, maleic acid half ester, maleic acid, fumaric acid, vinyl acetic acid and its anhydride, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, octadecyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxypropyl (meth)acrylate, At least one of -hydroxybutyl ester, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, (meth)acrylonitrile, glycidyl (meth)acrylate, N,N-dimethyl (meth)acrylate ethyl, N,N-diethyl (meth)acrylate ethyl, N,N-dimethyl (meth)acrylate propyl, N,N-diethyl (meth)acrylate propyl, N,N-dimethyl (meth)acrylate butyl, N,N-diethyl (meth)acrylate butyl, (meth)acrylamide, N-hydroxymethyl-acrylamide, N-butoxymethyl-acrylamide, styrene, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, (alkoxylated) nonylphenol (meth)acrylate. Methyl (meth)acrylate refers to methyl substituted or unsubstituted methyl acrylate, i.e. methyl acrylate or methyl methacrylate. Other similar expressions in this application, such as ethyl (meth)acrylate and monofunctional (meth)acrylate substances, have the same meaning.

[0045] [Photopolymerizable monomer]

[0046] In the present application, the photopolymerizable monomer may be a monomer containing an ethylenically unsaturated group, or may be selected from conventional photopolymerizable monomers, including but not limited to monofunctional (meth)acrylates, difunctional (meth)acrylates, trifunctional (meth)acrylates, or multifunctional (meth)acrylates, specifically, (ethoxy)phenol (meth)acrylate, stearic acid acrylate, ethoxy (propoxy) nonylphenol (meth)acrylate, ethoxy (propoxy) tetrahydrofurfuryl (meth)acrylate, Any one or more of 1,6-hexanediol diacrylate, tricyclohexanedimethanol diacrylate, dioxanediol diacrylate, ethoxylated (propoxylated) bisphenol A di(meth)acrylate, polyethylene glycol (400) diacrylate, polypropylene glycol (600) diacrylate, ethoxylated (propoxylated) trimethylolpropane tri(meth)acrylate, pentaerythritol triacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, dipentaerythritol hexaacrylate, ethoxylated pentaerythritol tetraacrylate, and dipentaerythritol hexaacrylate.

[0047] [Photoinitiator]

[0048] In the present application, the photoinitiator is selected from conventional photoinitiators, such as titanocene compounds, acetophenone compounds, oxime ester compounds, phosphine oxide compounds, phenylacetone compounds, butanone compounds, anthrone compounds, benzoin ether compounds, benzophenone compounds, anthraquinone compounds, thioxanthone compounds, hexaarylbisimidazole compounds, acridine compounds, benzyl compounds, benzoin compounds, etc., including but not limited to 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(acetoxyiminomethyl)thioxanthene-9-one, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone 1-(O-acetyl oxime), 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-[4-(2-hydroxy)-phenyl ]-3-hydroxy-2-methyl-1-propanone-1-one, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphonate, 2-methyl-1-(4-methylthiophenyl)-2-morphinyl-1-propanone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone , diethyl 2,4-oxalate, 2,4-diethylthiazolone, 2-isopropylthioxanthone, 2-ethylanthraquinone, 2,4-diethylthioxanthone, 4-p-toluenemercaptobenzophenone, benzophenone, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone, 4,4`-bis(dimethylamino)benzophenone, α,α`-dimethylbenzil ketal, α,α`-diethoxyacetophenone or more. Preferably, the photoinitiator is selected from at least one of 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphonic acid ethyl ester, 2-methyl-1-(4-methylthiophenyl)-2-morphinyl-1-propanone, 2-isopropylthioxanthone, 4-tolylthiobenzophenone, benzophenone, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone, 4,4'-bis(dimethylamino)benzophenone, α,α'-dimethylbenzil ketal, and α,α'-diethoxyacetophenone, and the above-mentioned preferred photoinitiator has a characteristic absorption peak in a band less than 390nm.

[0049] [Thermosetting agent]

[0050] In some embodiments of the present application, the photosensitive resin composition further comprises a thermal curing agent, and the laminate formed by the photosensitive resin composition has a solder resist function and can be used as a solder resist film or an interlayer insulating film. Based on 100 parts by mass of the alkali-soluble resin, the mass fraction of the thermal curing agent is preferably 5-20 parts.

[0051] Specifically, the thermal curing agent is selected from one or more of epoxy resins, isocyanates or isocyanurate compounds or triazine compounds; wherein the epoxy resins include but are not limited to bisphenol epoxy resins, biphenyl epoxy resins, novolac epoxy resins, epoxy resins containing naphthalene rings, and alicyclic epoxy resins; bisphenol epoxy resins such as bisphenol A epoxy resins, bisphenol F epoxy resins, and bisphenol S epoxy resins; novolac epoxy resins such as phenol novolac epoxy resins and novolac epoxy resins. Preferably, the epoxy equivalent of the epoxy resin is 50 to 350 g / eq. (e.g., 50 g / eq., 80 g / eq., 100 g / eq., 150 g / eq., 200 g / eq., 250 g / eq., 300 g / eq., 350 g / eq.) and the softening point is 40 to 150°C (e.g., 40°C, 50°C, 80°C, 100°C, 120°C, 150°C).

[0052] [Other components]

[0053] In some embodiments of the present application, the photosensitive resin composition further includes 20 to 150 parts of a colorant or filler, 2 to 10 parts of an auxiliary agent, and 30 parts of a solvent.

[0054] The colorant or filler includes pigments and dyes that can make the photosensitive composition present specific color effects and optical effects, and also includes physical fillers that make the photosensitive composition have certain mechanical properties or thermal properties. Specifically, the colorant or filler is selected from at least one of silicon dioxide, titanium dioxide, barium sulfate, calcium carbonate, aluminum hydroxide, kaolin, talc, titanium oxide, aluminum oxide, silicon nitride, aluminum nitride, carbon black, indigo blue, indigo green, toluidine red, and chrome yellow. Other common colorants or fillers on the market can also be selected according to actual needs.

[0055] The auxiliary agent includes a color developer, a plasticizer, a defoamer, an inhibitor, an antioxidant and a leveling agent; the color developer is selected from at least one of amyl bromide, ethylene dibromide, benzyl bromide, dibromomethane, tribromomethylphenyl sulfone, trichloroacetamide, amyl iodide and dichloroethane; the plasticizer is selected from phthalic acid compounds or sulfonamide compounds; preferably, the plasticizer is selected from at least one of diethyl phthalate, diphenyl phthalate and p-toluenesulfonamide; the defoamer is selected from non-silicon type defoamers At least one of a foaming agent, a polyether defoamer, a silicone defoamer, and a polyether-modified silicone defoamer; the inhibitor is selected from at least one of p-methoxyphenol, hydroquinone, pyrogallol, tert-butylcatechol, and N-nitrosophenylhydroxylamine aluminum salt; the antioxidant is selected from at least one of an amine antioxidant, a phenolic antioxidant, a thioester auxiliary antioxidant, a phosphite auxiliary antioxidant, and a thioether auxiliary antioxidant; the leveling agent is selected from at least one of a modified polysiloxane and a long-chain resin.

[0056] The addition of solvent helps to promote the full mixing of the components of the photosensitive resin composition. The solvent can be a conventional organic solvent that can effectively dissolve the components. Preferably, γ-butyrolactone is used.

[0057] In a second typical embodiment of the present application, a photosensitive laminate is further provided, which includes a support layer, a photosensitive layer and a protective layer stacked in sequence, wherein the material of the photosensitive layer is the photosensitive composition provided in the above-mentioned first typical embodiment.

[0058] In some embodiments, the photosensitive layer is formed by removing a solvent from a photosensitive composition.

[0059] In some embodiments, the substrate layer and the protective layer are respectively selected from at least one of a PET film, a PP film, a PE film, a PEN film, a PI film, and a release paper.

[0060] The photosensitive laminate provided in the present application can convert the longer-wavelength light emitted by the exposure machine into shorter-wavelength light that is more strongly absorbed by the photoinitiator by introducing a photoconverter into the photosensitive layer, thereby achieving high utilization of the light source while still using conventional photoinitiators, thereby expanding the selectivity of the photoinitiator and improving the photocuring speed and photocuring effect.

[0061] In a third typical embodiment of the present application, a cured film is further provided. The cured film is formed by photocuring the photosensitive layer provided in the second typical embodiment.

[0062] In a fourth typical embodiment of the present application, a circuit board is further provided. The circuit board includes the cured film provided in the third typical embodiment.

[0063] In a fifth typical embodiment of the present application, an electronic device is further provided. The electronic device includes the circuit board provided in the fourth typical embodiment.

[0064] The beneficial effects of the present application will be further illustrated below in combination with embodiments and comparative examples.

[0065] [Raw material selection]

[0066] Alkali soluble resin (A)

[0067] A-1: acid-modified epoxy acrylate resin (Nippon Kayaku ZFR-1401H, bisphenol F type, acid value 98 mgKOH / g, molecular weight 25000);

[0068] A-2: acrylate resin (Daichol CYCLOMER P (ACA) Z250, acid value 70 mgKOH / g, molecular weight 18000); photopolymerizable monomer (B)

[0069] B-1: poly(propylene glycol) diacrylate;

[0070] B-2: propoxylated triethylolpropane tri(propyl)acrylate;

[0071] Photoinitiator (C)

[0072] C-1: 2,4,6-trimethylbenzoyldiphenylphosphine oxide (characteristic absorption peak: 299 / 366nm);

[0073] C-2: 1-Hydroxycyclohexylphenyl ketone (characteristic absorption peak: 246 / 333nm);

[0074] C-3: 2-methyl-1-(4-methylthiophenyl)-2-morpholinyl-1-propanone (characteristic absorption peak: 231 / 307nm);

[0075] C-4: bis(1-(2,4-difluorophenyl)-3-pyrrolyl)titanocene (characteristic absorption peaks: 333 / 396 / 407nm);

[0076] Light conversion agent (D)

[0077] D-1: NaYGd:Er;

[0078] D-2: NaYbF4:Yb;

[0079] D-3: NaGdF4:Eu;

[0080] D-4: 2.45.6-Tetrakis(9-carbazolyl)-isophthalonitrile;

[0081] D-5: donor formula (I) + acceptor formula (IV) (molar ratio 1:1);

[0082] D-6: donor formula (I) + acceptor formula (V) (molar ratio 1:1);

[0083] D-7: donor formula (II) + acceptor formula (VI) (molar ratio 1:1);

[0084] D-8: CsPbBr3 / Cs4PbBr6;

[0085] Thermal curing agent (E)

[0086] E-1: cresol novolac epoxy resin (DIC EPICLON N-660, epoxy equivalent 202-212 g / eq); E-2: bisphenol A epoxy resin (Japanese Epoxy Resin jER828, epoxy equivalent 184-194 g / eq). The specific raw material amounts of the examples and comparative examples are shown in Tables 1 to 4 below.

[0087] Table 1

[0088]

[0089] Table 2

[0090]

[0091]

[0092] Table 3

[0093]

[0094]

[0095] Table 4

[0096]

[0097] Test example

[0098] The compositions provided in the above examples and comparative examples were prepared into optical laminates, and their performance was tested. The results are shown in Table 5 below.

[0099] [Preparation process]

[0100] According to the ingredient list, alkali-soluble resin, colorant or filler, and additives are added to the solvent and mixed evenly, and ground by a sand mill. Then, photopolymerization monomer, photoinitiator, thermal curing agent, and photoconversion agent are added in sequence and mixed evenly to obtain a photosensitive composition; the photosensitive composition is evenly coated on a PET support film by a coater, placed in an oven at 85°C for 30 minutes, taken out and covered with a PP protective film, to obtain a photosensitive laminate with a photosensitive layer thickness of 25 μm.

[0101] [Test method]

[0102] Hundred-grid method: Use a vacuum laminator to attach the above-mentioned photosensitive layer to a commercial copper-clad laminate. The pressure in the vacuum section is 6kgf, the vacuum time is 20s, the pressing time is 30s, and the temperature is 65℃; the pressure in the leveling section is 6kgf, the leveling time is 50s, and the temperature is 85℃. After the attachment is completed, the supporting layer film is torn off, and the standard test mask film is exposed at ST8 / 21 sensitivity energy. After thermal curing, use a hundred-grid knife to cut a hundred grids on the surface of the photosensitive layer, and then pull it up at 90° with 3M 600 tape to observe whether it falls off. Repeat 3 times, and replace new tape each time. Record the total number of squares that fall off in the 3 tests.

[0103] Sensitivity: The above-mentioned photosensitive layer is attached to the commercial copper-clad laminate using a vacuum laminating machine. The pressure of the vacuum section is 6kgf, the vacuum time is 20s, the pressing time is 30s, and the temperature is 65℃; the pressure of the leveling section is 6kgf, the leveling time is 50s, and the temperature is 85℃. After the attachment is completed, the supporting layer film is torn off, and the exposure is developed at the ST21 step exposure scale. The lowest energy that is not developed and completely exposed at the ST8 step is recorded as the sensitivity energy. The lower the sensitivity energy, the less energy is required to achieve a specific light reaction level, and the stronger the sensitivity.

[0104] Edge steepness and resolution: The above-mentioned photosensitive layer is attached to the commercial copper-clad laminate using a vacuum laminating machine. The pressure of the vacuum section is 6kgf, the vacuum time is 20s, the pressing time is 30s, and the temperature is 65°C; the pressure of the leveling section is 6kgf, the leveling time is 50s, and the temperature is 85°C. After the attachment is completed, the supporting layer film is torn off, and the standard test mask film is exposed at ST8 / 21 sensitivity energy, developed, and heat-cured. After slicing, observe and record the edge steepness and resolution under a metallographic microscope. The edge steepness indicates the width of the actual line side wall being overetched based on the ideal line side wall intersecting the substrate at a 90-degree angle. The smaller the side erosion, the weaker the edge inverted trapezoid, the closer the side edge is to the right angle edge, and the better the steepness. In the present invention, the smaller the side erosion number, the better the edge steepness.

[0105] Table 5

[0106]

[0107]

[0108] From the above description, it can be seen that the above-mentioned embodiments of the present invention achieve the following technical effects: the photosensitive composition provided by the present application is added with a photoconverter, which has an "up-conversion function" and can induce the "anti-Stokes" phenomenon, absorb long wavelength, low energy, and release short wavelength, high energy, thereby converting the longer wavelength light emitted by the exposure machine into a shorter wavelength light that is more strongly absorbed by the photoinitiator, thereby achieving high utilization of the light source while still using conventional photoinitiators, thereby expanding the selectivity of the photoinitiator and improving the photocuring speed and photocuring effect.

[0109] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A photosensitive composition, characterized in that: The photosensitive composition comprises, by weight, 100 parts of an alkali-soluble resin, 5 to 50 parts of a photopolymerizable monomer, 0.1 to 10 parts of a photoinitiator and 0.01 to 30 parts of a light-converting agent, wherein the absorption wavelength of the light-converting agent is greater than 390 nm and the emission wavelength is less than or equal to 390 nm.

2. The photosensitive composition according to claim 1, characterized in that: The photosensitive composition comprises 0.01 to 10 parts of the light conversion agent in parts by mass, and the light conversion agent is selected from at least one of NaLuF4, NaGdF4, NaYbF4, NaYF4, NaYGd, NaYLu, NaYNd, NaGd(WO4)2, LiErF4, BaYF5, BaLuF5, BaGdF5, BaYb2F8, CaS, LiLa(MoO4)2, Gd2O3, GdF3, ZrYO, YAIO, CaWO4, and a light conversion material composed of any of the above materials doped with rare earths, or a light conversion material composed of a derivative of any of the above materials, and the rare earth element comprises at least one of Yb, Er, Tm, Eu, Sm, Bi, and Ho; Preferably, the light conversion agent is selected from at least one of NaGdF4, NaYF4, NaYGd, GdF3, and light conversion materials consisting of any of the above materials doped with rare earth, and light conversion materials consisting of derivatives of any of the above materials.

3. The photosensitive composition according to claim 1, characterized in that The photosensitive composition comprises 0.1 to 20 parts of a light conversion agent in parts by mass, wherein the light conversion agent is selected from at least one of 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile, triphenylamine derivatives, and light conversion materials composed of any of the above materials doped with rare earths, and light conversion materials composed of derivatives of any of the above materials, and the rare earth element comprises at least one of Yb, Er, Tm, Eu, Sm, Bi, and Ho.

4. The photosensitive composition according to claim 1, characterized in that The photosensitive composition comprises 1 to 30 parts of the light conversion agent in parts by mass, wherein the light conversion agent comprises a donor and an acceptor, wherein the donor is selected from at least one of the compounds represented by formulas (I) to (III), and the acceptor is selected from at least one of the compounds represented by formulas (IV) to (VI); Preferably, when the donor is selected from the compound represented by formula (I), the acceptor is selected from at least one of the compounds represented by formulas (IV) to (VI); when the donor is selected from at least one of the compounds represented by formulas (II) to (III), the acceptor is selected from the compound represented by formula (VI); 5. The photosensitive composition according to claim 1, characterized in that The photosensitive composition comprises 0.01 to 10 parts of the light conversion agent in parts by mass, and the light conversion agent is selected from metal halide perovskite light conversion agents, the metal halide perovskite light conversion agent is composed of alkaline earth metal cations, transition metal cations and halogens, and the metal halide perovskite light conversion agent has a perovskite structure; wherein the alkaline earth metal comprises at least one of beryllium, magnesium, calcium, strontium, barium, and francium, and the transition metal comprises at least one of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, and zinc; Preferably, the metal halide perovskite light conversion agent is CsPbX3; X is Cl, Br or I; More preferably, the metal halide perovskite light conversion agent is formed by dispersing CsPbBr3 in Cs4PbBr6 crystals, and has a CsPbBr3 / Cs4PbBr6 doping structure.

6. The photosensitive composition according to any one of claims 1 to 5, characterized in that The mass ratio of the light conversion agent to the photoinitiator is (0.5-8):

1.

7. The photosensitive composition according to any one of claims 1 to 5, characterized in that The acid value of the alkali-soluble resin is 10 to 200 KOH / g, and the weight average molecular weight is 2000 to 150000; And / or, the photopolymerizable monomer is a monomer containing an ethylenically unsaturated group, including at least one of a monofunctional acrylate compound, a monofunctional methacrylate compound, a difunctional acrylate compound, a difunctional methacrylate compound, a trifunctional acrylate compound, a trifunctional methacrylate compound, a multifunctional acrylate compound or a multifunctional methacrylate compound; And / or, the photoinitiator includes at least one of a titanocene compound, an acetophenone compound, an oxime ester compound, a phosphine oxide compound, an anthrone compound, a benzoin ether compound, a benzophenone compound, a phenylacetone compound, a butanone compound, an anthraquinone compound, a thioxanthone compound, a hexaarylbisimidazole compound, an acridine compound, a benzyl compound, and a benzoin compound; preferably, the photoinitiator is selected from 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 1-hydroxycyclohexylphenyl ketone , 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphonic acid ethyl ester, 2-methyl-1-(4-methylthiophenyl)-2-morphinyl-1-propanone, 2-isopropylthioxanthone, 4-p-toluenethiobenzophenone, benzophenone, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone, 4,4`-bis(dimethylamino)benzophenone, α,α`-dimethylbenzil ketal, α,α`-diethoxyacetophenone.

8. The photosensitive composition according to any one of claims 1 to 6, characterized in that The photosensitive composition further comprises a heat curing agent, the amount of the heat curing agent is 5 to 20 parts by weight, and the heat curing agent comprises at least one of epoxy resin, isocyanate, isocyanurate compound or triazine compound; Preferably, the epoxy resin comprises at least one of bisphenol epoxy resin, biphenyl epoxy resin, novolac epoxy resin, epoxy resin containing naphthalene ring or alicyclic epoxy resin; wherein the bisphenol epoxy resin is selected from at least one of bisphenol A epoxy resin, bisphenol F epoxy resin or bisphenol S epoxy resin; the novolac epoxy resin is selected from at least one of phenol novolac epoxy resin or novolac epoxy resin; Preferably, the epoxy resin has an epoxy equivalent of 50 to 350 g / eq. and a softening point of 40 to 150°C.

9. A photosensitive laminate, characterized in that: The photosensitive laminate comprises a support layer, a photosensitive layer and a protective layer which are sequentially stacked, and the material of the photosensitive layer is the photosensitive composition according to any one of claims 1 to 8.

10. A circuit board, characterized in that: The circuit board includes a cured film, and the cured film is formed by photocuring the photosensitive layer described in claim 9.

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