Light-conversion photosensitive laminate, cured film, wiring board, and electronic device

Abstract

The invention provides a light-conversion photosensitive laminate, a cured film, a circuit board and an electronic device. The light-conversion photosensitive laminated body provided by the invention comprises a supporting layer, a photosensitive layer and an optional protective layer which are sequentially laminated, the light-conversion photosensitive laminated body contains 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 light conversion agent is added into the light conversion photosensitive laminated body provided by the invention, and the light conversion agent has an up-conversion function, can trigger an anti-Stokes phenomenon, absorbs long wavelength and low energy, and releases short wavelength and high energy, so that when the light conversion photosensitive laminated body is irradiated by an exposure machine, the light conversion effect is good, and the light conversion effect is good. According to the invention, long-wave-band light emitted by the exposure machine is absorbed and converted into short-wave-band light which can be absorbed by the photoinitiator by the light conversion agent, so that the high utilization rate of the light source is realized under the condition that the conventional photoinitiator is still used, the selectivity of the photoinitiator is expanded, and the photocuring speed and the photocuring effect of the photosensitive layer are improved.

Description

Technical Field

[0001] The present invention relates to the technical field of photosensitive laminates, and in particular to a light-converting photosensitive laminate, a cured film, a circuit board and an electronic device. Background Art

[0002] Photoinitiators are key components of photocurable products, and often play a decisive role in the photocuring speed and effect of photocurable products. The speed of photocuring and the quality of photocuring 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 resistance to gold. 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 of commonly used photoinitiators is generally less than 390nm, and some are less than 370nm (the maximum absorption wavelength refers to the maximum absorption value of a substance in the spectral wavelength, which is usually used to measure the absorption capacity of the substance to a certain wavelength of light). Therefore, the utilization rate of light in the 370-405nm band is relatively 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, 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. Some researchers have improved the utilization rate of light by adding a photoconverter to the photosensitive layer, but the photoconverter is mostly inorganic particles. On the one hand, the dispersibility is poor, which may affect the resolution and flexibility. On the other hand, it may cause the light to be scattered everywhere inside the film layer, causing the non-pattern part to undergo a photocuring reaction, affecting the accuracy of the pattern and not conducive to deep curing.

[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 laminate, a cured film, a circuit board and an electronic device to solve the problem in the prior art of low utilization of longer wavelength light by 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 purpose, according to one aspect of the present invention, a light-converting photosensitive laminate is provided, which includes a supporting layer, a photosensitive layer and an optional protective layer stacked in sequence, and the light-converting photosensitive laminate contains a light-converting agent, and the absorption wavelength of the light-converting agent is greater than 390nm and the emission wavelength is less than or equal to 390nm.

[0007] Furthermore, the support layer contains a light conversion agent. By weight, the material of the support layer includes 65-99 parts of the first resin, 0.1-15 parts of the light conversion agent, 0.9-30 parts of the first filler, 0.1-5 parts of the light conversion agent, 0.9-30 parts of the first filler, and 0.1-5 parts of the first auxiliary agent.

[0008] Furthermore, the first resin is selected from at least one of polyethylene terephthalate, polyethylene naphthalate, polyethylene, and polypropylene.

[0009] Furthermore, the first filler is selected from at least one of calcium titanate, calcium carbonate, titanium dioxide, zinc oxide, antimony trioxide, silicon oxide, hollow glass microspheres, and barium sulfate.

[0010] Furthermore, the first auxiliary agent is selected from at least one of ultraviolet absorbers, hindered amine light stabilizers, antioxidants, heat stabilizers, catalysts, hydrolysis stabilizers, nucleating and permeability enhancers, and toughening agents.

[0011] Furthermore, the light conversion photosensitive layer stack also includes a light conversion layer, which is arranged between the support layer and the photosensitive layer or on the side of the support layer away from the photosensitive layer, and contains a light conversion agent.

[0012] Furthermore, the light conversion layer includes, by weight, 60-90 parts of the second resin, 0.1-50 parts of the light conversion agent, 0-30 parts of the second filler, 0.001-20 parts of the curing agent, and 0.001-1 parts of the second auxiliary agent.

[0013] Furthermore, the second resin is selected from at least one of acrylic resin, fluorocarbon resin, polyester resin, epoxy resin, polyurethane resin and terpene resin.

[0014] Furthermore, the second filler is selected from at least one of calcium titanate, calcium carbonate, titanium dioxide, zinc oxide, antimony trioxide, silicon oxide, hollow glass balls, and barium sulfate.

[0015] Further, the curing agent is selected from at least one of hexamethylene diisocyanate trimer, hexamethylene diisocyanate prepolymer, isophorone diisocyanate trimer, isophorone diisocyanate prepolymer, hydrogenated xylylene isocyanate trimer, hydrogenated xylylene isocyanate prepolymer, methylated polymethylol melamine resin, butylated polymethylol melamine resin, mixed etherified polymethylol melamine resin, polyamide, polymethylene diamine, diethylenetriamine, pentamethyldiethylenetriamine, triethylenetetramine, diethylenetriamine, triethylenetetramine, and (2,3-dimethyl)dibutylenetriamine.

[0016] Furthermore, the second auxiliary agent is selected from at least one of ultraviolet absorbers, hindered amine light stabilizers, antioxidants, heat stabilizers, catalysts, hydrolysis stabilizers, nucleating and permeability enhancers, and toughening agents.

[0017] Furthermore, the photosensitive layer includes a first photosensitive layer and a second photosensitive layer which are stacked in sequence, the first photosensitive layer is arranged between the support layer and the second photosensitive layer, and the first photosensitive layer contains a light conversion agent.

[0018] Furthermore, the material of the first photosensitive layer includes, by mass, 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; and / or, the material of the second photosensitive layer includes 100 parts of a second alkali-soluble resin, 5 to 50 parts of a second photopolymerizable monomer, and 0.1 to 10 parts of a second photoinitiator.

[0019] Furthermore, the photosensitive layer contains a light conversion agent, which is distributed in a gradient manner in the photosensitive layer, and the content of the light conversion agent gradually decreases along the thickness direction away from the support layer.

[0020] Furthermore, the material of the photosensitive layer includes, by weight, 100 parts of a third alkali-soluble resin, 5 to 50 parts of a third photopolymerizable monomer, 0.1 to 10 parts of a third photoinitiator and 0.01 to 30 parts of a light conversion agent; the content of the light conversion agent decreases gradually along the thickness direction away from the support layer.

[0021] In order to achieve the above object, according to a second aspect of the present invention, there is provided a cured film, which is formed by photocuring or photothermal dual curing of the photosensitive layer provided by the first aspect.

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

[0023] According to a fourth aspect of the present invention, an electronic device is provided. The electronic device includes the cured film provided by the second aspect or the circuit board provided by the third aspect.

[0024] By applying the technical solution of the present application, a photoconversion agent is added to the photosensitive laminate provided by the present application. The photoconversion agent has an "up-conversion function" and can induce an "anti-Stokes" phenomenon, absorbing long wavelengths and low energy and releasing short wavelengths and high energy. Therefore, when an exposure machine irradiates the photosensitive laminate, the longer wavelength light emitted by the exposure machine is absorbed by the photoconversion agent and converted into shorter wavelength light that can be 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 of the photosensitive layer. DETAILED DESCRIPTION

[0025] 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.

[0026] As analyzed in the background technology of this application, the photoinitiator is a key component of the photocurable product, and the maximum absorption wavelength of the commonly used photoinitiators is generally less than 390nm, and some are less than 370nm (the molar extinction coefficient of a certain wavelength reflects the absorption intensity of the photoinitiator at this wavelength), so the utilization rate of light in the 370-405nm band is low. In the prior art, photoinitiators of different wavelengths are mixed or different initiators in different layers of a double-layer or multi-layer structure are used to improve the utilization rate of light in the high-wavelength band, but there is still a problem of low utilization rate of light in the longer-wavelength band. In order to solve this problem, the present application provides a light-converting photosensitive laminate, a cured film, a circuit board and an electronic device.

[0027] In a first typical embodiment of the present application, a light-converting photosensitive laminate is provided, which includes a supporting layer, a photosensitive layer and an optional protective layer stacked in sequence, and the light-converting photosensitive laminate contains a light-converting agent, the absorption wavelength of the light-converting agent is greater than 390nm, and the emission wavelength is less than or equal to 390nm.

[0028] By applying the technical solution of the present application, a photosensitive laminate provided by the present application is added with a photoconversion agent, which has an "up-conversion function" and can induce an "anti-Stokes" phenomenon, absorbing long wavelength, low energy and releasing short wavelength, high energy. Therefore, when an exposure machine irradiates the photosensitive laminate, the longer wavelength light emitted by the exposure machine is absorbed by the photoconversion agent and converted into shorter wavelength light that can be 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 of the photosensitive layer.

[0029] In the present application, any light conversion material that can satisfy the absorption wavelength ≥ 390 nm and the emission wavelength ≤ 390 nm can be used as the light conversion agent of the present application.

[0030] [Light conversion agent]

[0031] Specifically, in the present application, the above-mentioned light conversion agents include at least four categories, among which 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(MoO4)2, Gd2O3, GdF3, ZrYO, YAIO, CaWO4 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-mentioned 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 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.

[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] 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);

[0034]

[0035]

[0036] 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.

[0037] The light conversion photosensitive laminate provided in the present application contains a light conversion agent. Specifically, the light conversion photosensitive laminate has at least the following four embodiments.

[0038] [First Implementation Method]

[0039] In this embodiment, the support layer of the light-converting photosensitive stack contains a photoconverter. When the exposure machine irradiates the support layer, the photoconverter contained in the support layer absorbs the longer-wavelength light emitted by the exposure machine and converts it into shorter-wavelength light to irradiate the photosensitive layer, thereby improving the photocuring speed and photocuring effect of the photosensitive layer.

[0040] In some specific embodiments, the material of the support layer includes, by weight, 65-99 parts of the first resin, 0.1-15 parts of the light conversion agent, 0.9-30 parts of the first filler and 0.1-5 parts of the first auxiliary agent.

[0041] Typically but not limiting, in terms of parts by mass, in the material of the support layer, the amount of the first resin is 65 parts, 68 parts, 70 parts, 72 parts, 75 parts, 78 parts, 80 parts, 82 parts, 85 parts, 88 parts, 90 parts, 92 parts, 95 parts, 97 parts, 99 parts, or a range of any two values; the amount of the light-converting agent is 0.1 parts, 0.2 parts, 0.5 parts, 0.8 parts, 1 part, 2 parts, 5 parts, The amount of the first filler is 0.9 part, 1 part, 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; the amount of the first auxiliary agent is 0.1 part, 0.2 part, 0.5 part, 0.8 part, 1 part, 2 parts, 3 parts, 4 parts, 5 parts or a range consisting of any two numerical values.

[0042] The specific type of the first resin is not limited, including but not limited to any one or more of polyethylene terephthalate, polyethylene naphthalate, polyethylene, and polypropylene.

[0043] The first filler mentioned above is a commonly used filler in the art, including but not limited to any one or more of calcium titanate, calcium carbonate, titanium dioxide, zinc oxide, antimony trioxide, silicon oxide, hollow glass microspheres, and barium sulfate.

[0044] The specific type of the first auxiliary agent is not limited, including but not limited to any one or more of ultraviolet absorbers, hindered amine light stabilizers, antioxidants, heat stabilizers, catalysts, hydrolysis stabilizers, nucleating transmittance enhancers, and toughening agents. In this embodiment, the specific composition of the photosensitive layer is not particularly limited, and the photosensitive layer may contain a light conversion agent or may not contain a light conversion agent. In some specific embodiments, the material of the photosensitive layer includes 100 parts of alkali-soluble resin, 5 to 50 parts of photopolymerizable monomers, and 0.01 to 10 parts of photoinitiators by weight.

[0045] [Alkali soluble resin]

[0046] 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 2,000 to 150,000.

[0047] 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.

[0048] 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.

[0049] [Photopolymerizable monomer]

[0050] 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.

[0051] [Photoinitiator]

[0052] In the present application, the photoinitiator is selected from conventional photoinitiators, such as titanocene compounds, acetophenone compounds, oxime ester compounds, phosphine oxide compounds, anthrone compounds, benzoin ether compounds, benzophenone compounds, anthraquinone compounds, thioxanthone compounds, hexaarylbisimidazole compounds, acridine 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- One or more of 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, 2,4,6-trimethylbenzoylphenylphosphonic acid ethyl ester, 2-methyl-1-(4-methylthiophenyl)-2-morphinyl-1-propanone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone, 2,4-oxalic acid diethyl ester, 2,4-diethylthiazolone, 2-isopropylthioxanthone, 2-ethylanthraquinone, 2,4-diethylthioxanthone, and benzophenone.

[0053] [Thermosetting agent]

[0054] In some embodiments of the present application, the material of the photosensitive layer further includes a thermal curing agent. In this case, the laminate formed by the photosensitive material 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.

[0055] 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).

[0056] [Other components]

[0057] In some embodiments of the present application, the material of the photosensitive layer 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.

[0058] Colorants or fillers include pigments and dyes that can make the photosensitive layer present specific color effects and optical effects, and also include physical fillers that make the photosensitive layer have certain mechanical properties or thermal properties. Specifically, the colorant or filler is selected from at least one of silica, 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.

[0059] 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.

[0060] 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.

[0061] [Second embodiment mode]

[0062] In this embodiment, the light-converting photosensitive laminate further includes a light-converting layer, which is disposed between the support layer and the photosensitive layer or on the side of the support layer away from the photosensitive layer, and the light-converting agent is contained in the light-converting layer. When the exposure machine irradiates the light-converting photosensitive laminate, the light emitted by the exposure machine enters the light-converting layer through the support layer, and the light-converting agent contained in the light-converting layer absorbs the light of the longer wavelength band emitted by the exposure machine and converts it into light of the shorter wavelength band, and then the light of the shorter wavelength band irradiates the photosensitive layer, thereby improving the light-curing speed and light-curing effect of the photosensitive layer.

[0063] In some specific embodiments, the material of the light conversion layer includes, by weight, 60-90 parts of the second resin, 0.1-50 parts of the light conversion agent, 0-30 parts of the second filler, and 0.001-20 parts of the curing agent.

[0064] Typically but not limiting, in the material of the light conversion layer, the amount of the second resin is 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts, or a range consisting of any two values, in parts by mass; the amount of the light conversion agent is 0.1 parts, 0.2 parts, 0.5 parts, 1 parts, 2 parts, 5 parts, 10 parts, 20 parts, 30 parts, 40 parts, 50 parts, or a range consisting of any two values; the amount of the second filler is 0 parts, 1 parts, 2 parts, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, or a range consisting of any two values; the amount of the second auxiliary agent is 0.001 parts, 0.002 parts, 0.005 parts, 0.008 parts, 0.01 parts, 0.05 parts, 0.1 parts, 0.2 parts, 0.5 parts, 1 parts, or a range consisting of any two values.

[0065] The specific type of the second resin is not limited, including but not limited to any one or more of acrylic resin, fluorocarbon resin, polyester resin, epoxy resin, polyurethane resin, and terpene resin.

[0066] The specific types of the above-mentioned curing agent are not limited, including but not limited to any one or more of hexamethylene diisocyanate trimer, hexamethylene diisocyanate prepolymer, isophorone diisocyanate trimer, isophorone diisocyanate prepolymer, hydrogenated xylylene isocyanate trimer, hydrogenated xylylene isocyanate prepolymer, methylated polymethylol melamine resin, butylated polymethylol melamine resin, mixed etherified polymethylol melamine resin, polyamide, polymethylene diamine, diethylenetriamine, pentamethyldiethylenetriamine, triethylenetetramine, diethylenetriamine, triethylenetetramine, and (2,3-dimethyl)dibutylenetriamine.

[0067] The specific types of the second filler and the second auxiliary agent are the same as the first filler and the first auxiliary agent, and will not be described in detail here.

[0068] In some embodiments, the preparation method of the light conversion layer is: on at least one side of the support layer, the light conversion layer material is arranged on the support layer by one of the processes selected from the group consisting of anilox coating, mask coating, spraying, inkjet printing, screen printing or transfer printing at 60-200° C., and the light conversion layer is obtained after drying.

[0069] In this embodiment, the specific composition of the photosensitive layer is the same as the photosensitive layer in the first embodiment, and will not be repeated here.

[0070] In this embodiment, the specific composition of the support layer is not limited. The support layer may contain a light conversion agent or may not contain a light conversion agent. In some specific embodiments, the material of the support layer includes 65-99 parts of the first resin, 0.1-15 parts of the light conversion agent, 0.9-30 parts of the first filler and 0.1-5 parts of the first auxiliary agent by weight.

[0071] In this embodiment, the thickness of the light conversion layer is 1-30 μm.

[0072] [Third Implementation Method]

[0073] In this embodiment, the photosensitive layer contains a photoconverter, and the photosensitive layer includes a first photosensitive layer and a second photosensitive layer stacked in sequence, the first photosensitive layer is arranged between the support layer and the second photosensitive layer, and the photoconverter is contained in the first photosensitive layer. When the exposure machine irradiates the light-converting photosensitive stack, the light emitted by the exposure machine enters the first photosensitive layer through the support layer, and the photoconverter contained in the first photosensitive layer absorbs the longer-wavelength light emitted by the exposure machine and converts it into shorter-wavelength light, which irradiates the first photosensitive layer and the second photosensitive layer, thereby improving the photocuring speed and photocuring effect of the first photosensitive layer and the second photosensitive layer. Since the second photosensitive layer does not contain a photoconverter, it does not affect the deep curing property, and has little effect on the resolvability.

[0074] In some specific embodiments, the material of the first photosensitive layer includes 100 parts of a first alkali-soluble resin, 5 to 50 parts of a first photopolymerizable monomer, 0.1 to 10 parts of a first photoinitiator, and 0.01 to 30 parts of a photoconverter, by weight. Typically but not limiting, by weight, the material of the first photosensitive layer includes 100 parts of the first alkali-soluble resin, and the amount of the first photopolymerizable monomer is 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, or any combination of two values. The amount of the light conversion agent is 0.1 part, 0.2 part, 0.5 part, 0.8 part, 1.0 part, 2.0 part, 5.0 part, 8.0 part, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts or a range value composed of any two numerical values; the amount of the first initiator is 0.01 part, 0.02 part, 0.05 part, 0.08 part, 0.1 part, 0.2 part, 0.5 part, 0.8 part, 1.0 part, 2.0 part, 5.0 part, 8.0 part, 10 parts or a range value composed of any two numerical values.

[0075] The specific meanings of the first alkali-soluble resin, the first photopolymerizable monomer and the first photoinitiator are as described in the first embodiment above and will not be repeated here.

[0076] In this embodiment, the specific composition of the second photosensitive layer is not limited, and the specific composition of the photosensitive layer commonly used in the art can be any, and can be the same as or different from the first photosensitive layer. In some specific embodiments, the specific composition of the second photosensitive layer differs from that of the first photosensitive layer only in that the second photosensitive layer does not contain a photoconverter.

[0077] In this embodiment, the thickness of the first photosensitive layer is 5-20 μm, and the thickness of the second photosensitive layer is 5-55 μm.

[0078] In this embodiment, the specific composition of the support layer is not limited. The support layer may contain a light conversion agent or may not contain a light conversion agent.

[0079] [Fourth embodiment]

[0080] In this embodiment, the photosensitive layer contains a photoconverter, which is distributed in a gradient in the photosensitive layer, and the content of the photoconverter gradually decreases in the direction away from the support layer. When the exposure machine irradiates the photoconverting photosensitive laminate, the light emitted by the exposure machine enters the photosensitive layer through the support layer, and the photoconverter contained in the photosensitive layer absorbs the longer-wavelength light emitted by the exposure machine and converts it into shorter-wavelength light, which irradiates the photosensitive layer, and the content of the photoconverter gradually decreases in the direction away from the exposure machine, thereby avoiding excessive content of the photoconverter affecting the mechanical properties, deep curing properties and resolvability of the photosensitive layer, and at the same time improving the light curing speed and light curing effect of the photosensitive layer.

[0081] In some embodiments, the photosensitive layer includes at least two stacked photosensitive layers, and the content of the photoconverter in each photosensitive layer gradually decreases in the direction away from the support layer. For example, the photosensitive layer includes a first photosensitive layer, a second photosensitive layer, and a third photosensitive layer stacked in sequence, and the content of the photoconverter in the first photosensitive layer is greater than the content of the photoconverter in the second photosensitive layer and greater than the content of the photoconverter in the third photosensitive layer, and the third photosensitive layer is away from the support layer.

[0082] In some specific embodiments, the material of the photosensitive layer includes, by weight, 100 parts of a second alkali-soluble resin, 5 to 50 parts of a second photopolymerizable monomer, 0.01 to 10 parts of a second photoinitiator, and 0.01 to 30 parts of a light-converting agent, and the content of the light-converting agent decreases gradually along the thickness direction away from the support layer. Typically but not restrictively, in the material of the photosensitive layer, by weight, based on 100 parts of the second alkali-soluble resin, the amount of the second photopolymerizable monomer is 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, or a range consisting of any two values; the amount of the light-converting agent is 0.01 parts, 0.02 parts, 0.05 parts, 0.08 parts, 0.1 parts, 0.2 parts, 0.5 parts, or a range consisting of any two values. , 0.8 parts, 1.0 parts, 2.0 parts, 5.0 parts, 8.0 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts or a range consisting of any two numerical values; the amount of the second initiator is 0.01 parts, 0.02 parts, 0.05 parts, 0.08 parts, 0.1 parts, 0.2 parts, 0.5 parts, 0.8 parts, 1.0 parts, 2.0 parts, 5.0 parts, 8.0 parts, 10 parts or a range consisting of any two numerical values.

[0083] The specific meanings of the second alkali-soluble resin, the second photopolymerizable monomer and the photoinitiator are as described in the first embodiment above and will not be repeated here.

[0084] In this embodiment, the specific composition of the support layer is not limited. Its specific composition is the same as the support layer in the third embodiment, and will not be repeated here.

[0085] In some embodiments, the protective layer is selected from at least one of PET film, PP film, PE film, PEN film, PI film, and release paper. The thickness of the support layer and the protective layer is 5-50 μm, and the total thickness of the photosensitive layer is 10-60 μm.

[0086] In a second typical embodiment of the present application, a cured film is further provided. The cured film is formed by photocuring or photothermal dual curing of the photosensitive layer provided in the second typical embodiment.

[0087] 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.

[0088] In a fifth typical embodiment of the present application, an electronic device is further provided. The electronic device includes the cured film provided in the above third typical embodiment or the circuit board provided in the above fourth typical embodiment.

[0089] The beneficial effects of the present application will be further illustrated below in combination with embodiments and comparative examples.

[0090] Example 1-1

[0091] The present embodiment provides a light-converting photosensitive laminate, which includes a supporting layer, a photosensitive layer and a protective layer which are stacked in sequence, wherein the supporting layer contains a light-converting agent, and the protective layer is a PET film with a thickness of 15 μm.

[0092] The materials of the support layer include: 99 parts by weight of the first resin polyethylene terephthalate, 5 parts of the light conversion agent NaYGd:Er, 0.9 parts by weight of silicon oxide, 0.05 parts by weight of the hydrolysis stabilizer I powder (Rhein Chemie), 0.04 parts by weight of the antioxidant triethylene glycol ether-di(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, and 0.01 parts by weight of the heat stabilizer N-phenylmaleimide-styrene-methyl methacrylate. The support layer is prepared by a melt extrusion process and has a thickness of 25 μm.

[0093] The photosensitive layer material includes: 100 parts of alkali-soluble resin acid-modified epoxy acrylate resin (Nippon Kayaku ZFR-1401H, bisphenol F type, acid value 98 mgKOH / g, molecular weight 25000), 10 parts of photopolymerization monomer poly (propylene glycol) diacrylate, 3 parts of photoinitiator 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, and 15 parts of thermal curing agent cresol novolac type epoxy resin (DICEPICLON N-660, epoxy equivalent 202-212 g / eq). The mixture of the photosensitive layer materials is coated on the surface of the support layer with a coating thickness of 30 μm, and dried at 85° C. for 10 minutes to obtain a photosensitive layer.

[0094] Example 1-2

[0095] The difference from Example 1-1 is that the ratio of the light conversion agent NaYGd:Er in the support layer of this example is 15 parts.

[0096] Examples 1-3

[0097] The difference from Example 1-1 is that the ratio of the light conversion agent NaYGd:Er in the support layer of this example is 0.1 parts.

[0098] Examples 1-4

[0099] The difference from Example 1-1 is that the light conversion agent in the support layer of this example is 5 parts of 2.45.6-tetrakis(9-carbazolyl)-isophthalonitrile.

[0100] Examples 1-5

[0101] The difference from Example 1-1 is that the light conversion agent in the support layer of this example is 5 parts of donor formula (I) + acceptor formula (IV) (molar ratio 1:1).

[0102] Examples 1-6

[0103] The difference from Example 1-1 is that the light conversion agent in the support layer of this example is 5 parts of CsPbBr3 / Cs4PbBr6.

[0104] Examples 1-7

[0105] The difference from Example 1-1 is that the first resin in the support layer of this example is 99 parts by weight of polypropylene.

[0106] Examples 1-8

[0107] The difference from Example 1-1 is that the first resin in the support layer of this example is 65 parts by weight of polyethylene terephthalate.

[0108] Example 2-1

[0109] The present embodiment provides a light-converting photosensitive laminate, which includes a supporting layer, a light-converting layer, a photosensitive layer and a protective layer which are sequentially stacked, wherein the light-converting layer contains a light-converting agent, and the protective layer is a PET film with a thickness of 15 μm.

[0110] The materials of the support layer include: 99 parts by weight of polyethylene terephthalate, 0.9 parts by weight of silicon oxide, 0.05 parts by weight of hydrolysis stabilizer I powder (Rhein Chemie), 0.04 parts by weight of antioxidant triethylene glycol ether-di(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, and 0.01 parts by weight of thermal stabilizer N-phenylmaleimide-styrene-methyl methacrylate. The support layer is prepared by a melt extrusion process and has a thickness of 25 μm.

[0111] The materials of the light conversion layer include: 90 parts by weight of the second resin acrylic resin AC-1 (Changxing Chemical), 5 parts of the light conversion agent NaYGd:Er, 4 parts of the curing agent isophorone diisocyanate prepolymer, 5 parts by weight of the curing agent triethylenetetramine, and 1 part by weight of the catalyst stannous octoate. The preparation method of the light conversion layer is: on one side of the support layer, the material composition of the light conversion layer is coated on the support layer by a texture coating process at 150° C., the coating thickness is 7 μm, and the light conversion layer is obtained after drying.

[0112] The materials of the photosensitive layer include: 100 parts of alkali-soluble resin acid-modified epoxy acrylate resin (Nippon Kayaku ZFR-1401H, bisphenol F type, acid value 98 mgKOH / g, molecular weight 25000), 10 parts of photopolymerization monomer poly (propylene glycol) diacrylate, 3 parts of photoinitiator 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, and 15 parts of thermal curing agent cresol novolac type epoxy resin (DICEPICLON N-660, epoxy equivalent 202-212 g / eq). The preparation method of the photosensitive layer is: coating the material composition of the photosensitive layer on the surface of the light conversion layer with a coating thickness of 30 μm, and drying at 85° C. for 10 minutes to obtain the photosensitive layer.

[0113] Example 2-2

[0114] The difference from Example 2-1 is that the light-converting photosensitive laminate provided in this example includes a light-converting layer, a supporting layer, a photosensitive layer and a protective layer which are stacked in sequence.

[0115] During the preparation process, the material composition of the photosensitive layer is coated on the surface of the support layer away from the light conversion layer.

[0116] Example 2-3

[0117] The difference from Example 2-1 is that the ratio of the light conversion agent NaYGd:Er in the light conversion layer of this example is 50 parts.

[0118] Embodiment 2-4

[0119] The difference from Example 2-1 is that the light conversion agent NaYGd:Er in the light conversion layer of this example is 0.1 parts.

[0120] Embodiment 2-5

[0121] The difference from Example 2-1 is that the second resin in the light conversion layer of this embodiment is 90 parts by weight of fluorocarbon resin GK570 (Daikin, Japan).

[0122] Embodiment 2-6

[0123] The difference from Example 2-1 is that the second resin in the light conversion layer of this example is 90 parts by weight of epoxy resin SM716 (Jiangsu Sanmu Chemical Co., Ltd.).

[0124] Embodiment 2-7

[0125] The difference from Example 2-1 is that the second resin in the light conversion layer of this example is 60 parts.

[0126] Example 3-1

[0127] The present embodiment provides a photoconverting sensitive laminate, which includes a supporting layer, a photosensitive layer, and a protective layer stacked in sequence, wherein the photosensitive layer contains a photoconverter, and the protective layer is a PET film with a thickness of 15 μm; the photosensitive layer includes a first photosensitive layer, a second photosensitive layer, and a third photosensitive layer stacked in sequence, and the mass content of the photoconverter in the first photosensitive layer is greater than the mass content of the photoconverter in the second photosensitive layer and the mass content of the photoconverter in the third photosensitive layer.

[0128] The material of the support layer includes: 99 parts by weight of polyethylene terephthalate, 0.9 parts by weight of silicon oxide, 0.05 parts by weight of hydrolysis stabilizer I powder (Rhein Chemie), 0.04 parts by weight of antioxidant triethylene glycol ether-di(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, and 0.01 parts by weight of thermal stabilizer N-phenylmaleimide-styrene-methyl methacrylate. The support layer is prepared by a melt extrusion process.

[0129] The materials of the first photosensitive layer include: 100 parts of alkali-soluble resin acid-modified epoxy acrylate resin (Nippon Kayaku ZFR-1401H, bisphenol F type, acid value 98 mgKOH / g, molecular weight 25000), 10 parts of light conversion agent NaYGd:Er, 10 parts of photopolymerization monomer poly(propylene glycol) diacrylate, 3 parts of photoinitiator 2,4,6-trimethylbenzoyl diphenylphosphine oxide, 15 parts of thermal curing agent cresol novolac type epoxy resin (DIC EPICLON N-660, epoxy equivalent 202-212 g / eq). The preparation method of the first photosensitive layer is: coating the material composition of the photosensitive layer on the surface of the support layer, the coating thickness is 10 μm, and drying at 65° C. for 6 minutes to obtain the first photosensitive layer.

[0130] The materials of the second photosensitive layer include: 100 parts of alkali-soluble resin acid-modified epoxy acrylate resin (Nippon Kayaku ZFR-1401H, bisphenol F type, acid value 98 mgKOH / g, molecular weight 25000), 6 parts of light conversion agent NaYGd:Er, 10 parts of photopolymerizable monomer poly(propylene glycol) diacrylate, 3 parts of photoinitiator 2,4,6-trimethylbenzoyl diphenylphosphine oxide, 15 parts of thermal curing agent cresol novolac type epoxy resin (DIC EPICLON N-660, epoxy equivalent 202-212 g / eq). The preparation method of the second photosensitive layer is: coating the material composition of the second photosensitive layer on the surface of the first photosensitive layer, the coating thickness is 10 μm, and drying at 75° C. for 6 minutes to obtain the second photosensitive layer.

[0131] The materials of the third photosensitive layer are: 100 parts of alkali-soluble resin acid-modified epoxy acrylate resin (Nippon Kayaku ZFR-1401H, bisphenol F type, acid value 98 mgKOH / g, molecular weight 25000), 2 parts of light conversion agent NaYGd:Er, 10 parts of photopolymerizable monomer poly(propylene glycol) diacrylate, 3 parts of photoinitiator 2,4,6-trimethylbenzoyl diphenylphosphine oxide, 15 parts of thermosetting agent cresol novolac type epoxy resin (DIC EPICLON N-660, epoxy equivalent 202-212 g / eq). The preparation method of the third photosensitive layer is: coating the material composition of the third photosensitive layer on the surface of the second photosensitive layer with a coating thickness of 10 μm, drying at 85° C. for 6 minutes to obtain the third photosensitive layer. The first photosensitive layer, the second photosensitive layer and the third photosensitive layer are sequentially stacked to obtain a photosensitive layer.

[0132] Example 3-2

[0133] The difference from Example 3-1 is that this embodiment includes five photosensitive layers, each of which is 6 μm thick; in terms of stacking order, the materials of the second photosensitive layer, the third photosensitive layer and the fourth photosensitive layer are respectively the same as the materials of the first photosensitive layer, the second photosensitive layer and the third photosensitive layer in Example 3-1;

[0134] The materials of the first photosensitive layer include: 100 parts of alkali-soluble resin acid-modified epoxy acrylate resin (Nippon Kayaku ZFR-1401H, bisphenol F type, acid value 98 mgKOH / g, molecular weight 25000), 15 parts of light conversion agent NaYGd:Er, 10 parts of photopolymerizable monomer poly(propylene glycol) diacrylate, 3 parts of photoinitiator 2,4,6-trimethylbenzoyl diphenylphosphine oxide, 15 parts of thermal curing agent cresol novolac type epoxy resin (DIC EPICLON N-660, epoxy equivalent 202-212 g / eq). The preparation method of the first photosensitive layer is: coating the material composition of the photosensitive layer on the surface of the support layer, the coating thickness is 6 μm, and drying at 65° C. for 6 minutes to obtain the first photosensitive layer.

[0135] The materials of the fifth photosensitive layer include: 100 parts of alkali-soluble resin acid-modified epoxy acrylate resin (Nippon Kayaku ZFR-1401H, bisphenol F type, acid value 98 mgKOH / g, molecular weight 25000), 0.01 parts of light conversion agent NaYGd:Er, 10 parts of photopolymerizable monomer poly(propylene glycol) diacrylate, 3 parts of photoinitiator 2,4,6-trimethylbenzoyl diphenylphosphine oxide, 15 parts of heat curing agent cresol novolac type epoxy resin (DIC EPICLON N-660, epoxy equivalent 202-212 g / eq). The preparation method of the fifth photosensitive layer is: coating the material composition of the photosensitive layer on the surface of the fourth photosensitive layer, the coating thickness is 6 μm, and drying at 65° C. for 6 minutes to obtain the fifth photosensitive layer.

[0136] Example 4-1

[0137] The present embodiment provides a light-converting photosensitive laminate, which includes a supporting layer, a first photosensitive layer, a second photosensitive layer and a protective layer stacked in sequence, wherein the first photosensitive layer contains a light-converting agent, and the protective layer is a PET film with a thickness of 15 μm.

[0138] The materials of the support layer include: 99 parts by weight of polyethylene terephthalate, 0.9 parts by weight of silicon oxide, 0.05 parts by weight of hydrolysis stabilizer I powder (Rhein Chemie), 0.04 parts by weight of antioxidant triethylene glycol ether-di(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, and 0.01 parts by weight of thermal stabilizer N-phenylmaleimide-styrene-methyl methacrylate. The support layer is prepared by a melt extrusion process.

[0139] The materials of the first photosensitive layer include: 100 parts of alkali-soluble resin acid-modified epoxy acrylate resin (Nippon Kayaku ZFR-1401H, bisphenol F type, acid value 98 mgKOH / g, molecular weight 25000), 10 parts of light conversion agent NaYGd:Er, 10 parts of photopolymerization monomer poly(propylene glycol) diacrylate, 3 parts of photoinitiator 2,4,6-trimethylbenzoyl diphenylphosphine oxide, 15 parts of thermal curing agent cresol novolac type epoxy resin (DIC EPICLON N-660, epoxy equivalent 202-212 g / eq). The preparation method of the first photosensitive layer is: coating the material composition of the first photosensitive layer on the surface of the support layer, the coating thickness is 15 μm, and drying at 70° C. for 8 minutes to obtain the first photosensitive layer.

[0140] The materials of the second photosensitive layer include: 100 parts of alkali-soluble resin acid-modified epoxy acrylate resin (Nippon Kayaku ZFR-1401H, bisphenol F type, acid value 98 mgKOH / g, molecular weight 25000), 10 parts of photopolymerizable monomer poly(propylene glycol) diacrylate, 3 parts of photoinitiator 2,4,6-trimethylbenzoyl diphenylphosphine oxide, 15 parts of thermal curing agent cresol novolac type epoxy resin (DIC EPICLON N-660, epoxy equivalent 202-212 g / eq). The preparation method of the second photosensitive layer is: coating the material composition of the second photosensitive layer on the surface of the first photosensitive layer, the coating thickness is 15 μm, and drying at 85° C. for 10 minutes to obtain the second photosensitive layer.

[0141] Example 4-2

[0142] The difference from Example 4-1 is that the ratio of the light conversion agent NaYGd:Er in the first photosensitive layer of this example is 30 parts.

[0143] Example 4-3

[0144] The difference from Example 4-1 is that the light conversion agent NaYGd:Er in the first photosensitive layer of this example is 0.01 parts.

[0145] Example 4-4

[0146] The difference from Example 4-1 is that the first photosensitive layer in this example contains 5 parts of poly(propylene glycol) diacrylate and 1 part of the photoinitiator 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

[0147] Embodiment 4-5

[0148] The difference from Example 4-1 is that the first photosensitive layer in this example contains 50 parts of poly(propylene glycol) diacrylate and 10 parts of the photoinitiator 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

[0149] Comparative Example 1

[0150] The difference from Example 1-1 is that the support layer does not contain a light conversion agent.

[0151] Comparative Example 2

[0152] This comparative example provides a light-converting photosensitive laminate, which includes a supporting layer, a photosensitive layer and a protective layer stacked in sequence, wherein the photosensitive layer is a single layer and contains a light-converting agent, and the protective layer is a PET film with a thickness of 15 μm.

[0153] The material of the support layer includes: 99 parts by weight of polyethylene terephthalate, 0.9 parts by weight of silicon oxide, 0.05 parts by weight of hydrolysis stabilizer I powder (Rhein Chemie), 0.04 parts by weight of antioxidant triethylene glycol ether-di(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, and 0.01 parts by weight of thermal stabilizer N-phenylmaleimide-styrene-methyl methacrylate. The support layer is prepared by a melt extrusion process.

[0154] The materials of the photosensitive layer include: 100 parts of alkali-soluble resin acid-modified epoxy acrylate resin (Nippon Kayaku ZFR-1401H, bisphenol F type, acid value 98 mgKOH / g, molecular weight 25000), 10 parts of light conversion agent NaYGd:Er, 10 parts of photopolymerization monomer poly (propylene glycol) diacrylate, 3 parts of photoinitiator 2,4,6-trimethylbenzoyl diphenylphosphine oxide, 15 parts of thermal curing agent cresol novolac type epoxy resin (DIC EPICLON N-660, epoxy equivalent 202-212 g / eq). The preparation method of the photosensitive layer is: coating the material composition of the photosensitive layer on the surface of the support layer, the coating thickness is 30 μm, and drying at 85° C. for 10 minutes to obtain the photosensitive layer.

[0155] [Test method]

[0156] 100-grid method: Use a vacuum laminating machine to remove the protective layer of the laminated body samples obtained in the embodiment and the comparative example and attach them to the commercial copper-clad laminate. 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 flattening section is 6kgf, the flattening time is 50s, and the temperature is 85°C. After the attachment is completed, the standard test mask film is exposed at ST8 / 21 sensitivity energy, thermally cured, and other layers are removed to retain only the photosensitive layer. 100 grids are cut on the surface of the photosensitive layer with a 100-grid knife, and then pulled up with 3M 600 tape at 90° to observe whether it falls off. Repeat 3 times, and replace the new tape each time. Record the total number of squares that fall off in 3 tests. The test results are shown in Table 1.

[0157] Sensitivity: After removing the protective layer from the laminated body samples obtained in the embodiment and the comparative example, the laminated body samples were attached to the commercial copper clad laminate using a vacuum laminating machine. The pressure of the vacuum section was 6kgf, the vacuum time was 20s, the pressing time was 30s, and the temperature was 65°C; the pressure of the flattening section was 6kgf, the flattening time was 50s, and the temperature was 85°C. After the attachment was completed, the exposure was developed at the ST21 step exposure scale, and the lowest energy that was not developed and completely exposed at the ST8 step was 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. The test results are shown in Table 1.

[0158] Edge steepness and resolution: The laminate samples obtained in the embodiment and the comparative example were attached to the commercial copper-clad laminate after removing the protective layer using a vacuum laminating machine. The pressure of the vacuum section was 6kgf, the vacuum time was 20s, the lamination time was 30s, and the temperature was 65°C; the pressure of the leveling section was 6kgf, the leveling time was 50s, and the temperature was 85°C. After the attachment was completed, the standard test mask film was exposed at ST8 / 21 sensitivity energy, developed, and thermally cured to remove other layers and only retain the photosensitive layer. The edge steepness and resolution were observed and recorded under a metallographic microscope through slicing. The edge steepness indicates the width of the actual line sidewall being excessively etched based on the ideal line sidewall 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. The test results are shown in Table 1.

[0159] Table 1

[0160]

[0161]

[0162] From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects:

[0163] The photosensitive laminate provided in the present application contains a photoconverter, which has an "up-conversion function" and can induce an "anti-Stokes" phenomenon, absorbing long wavelength, low energy and releasing short wavelength, high energy. Therefore, when an exposure machine irradiates the photosensitive laminate, the longer wavelength light emitted by the exposure machine is absorbed by the photoconverter and converted into shorter wavelength light that can be 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 of the photosensitive layer.

[0164] 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 light-converting photosensitive laminate, characterized in that: The light-converting photosensitive laminate comprises a supporting layer, a photosensitive layer and an optional protective layer which are sequentially stacked, and the light-converting photosensitive laminate contains a light-converting agent; 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 light conversion photosensitive laminate according to claim 1, characterized in that: The support layer contains the light conversion agent. By weight, the material of the support layer includes 65-99 parts of the first resin, 0.1-15 parts of the light conversion agent, 0.9-30 parts of the first filler, and 0.1-5 parts of the first auxiliary agent; Preferably, the first resin is selected from at least one of polyethylene terephthalate, polyethylene naphthalate, polyethylene, and polypropylene; Preferably, the first filler is selected from at least one of calcium titanate, calcium carbonate, titanium dioxide, zinc oxide, antimony trioxide, silicon oxide, hollow glass microspheres, and barium sulfate; Preferably, the first auxiliary agent is selected from at least one of ultraviolet absorbers, hindered amine light stabilizers, antioxidants, heat stabilizers, catalysts, hydrolysis stabilizers, nucleating and permeability enhancers, and toughening agents.

3. The light conversion photosensitive laminate according to claim 1, characterized in that: The light-converting photosensitive laminate further includes a light-converting layer, which is disposed between the supporting layer and the photosensitive layer or on a side of the supporting layer away from the photosensitive layer, and contains the light-converting agent.

4. The light conversion photosensitive laminate according to claim 3, characterized in that: In parts by mass, the material of the light conversion layer includes 60-90 parts of the second resin, 0.1-50 parts of the light conversion agent, 0-30 parts of the second filler, 0.001-20 parts of the curing agent, and 0.001-1 parts of the second auxiliary agent; Preferably, the second resin is selected from at least one of acrylic resin, fluorocarbon resin, polyester resin, epoxy resin, polyurethane resin and terpene resin; Preferably, the second filler is at least one selected from calcium titanate, calcium carbonate, titanium dioxide, zinc oxide, antimony trioxide, silicon oxide, hollow glass microspheres, and barium sulfate; Preferably, the curing agent is selected from at least one of hexamethylene diisocyanate trimer, hexamethylene diisocyanate prepolymer, isophorone diisocyanate trimer, isophorone diisocyanate prepolymer, hydrogenated xylylene isocyanate trimer, hydrogenated xylylene isocyanate prepolymer, methylated polymethylol melamine resin, butylated polymethylol melamine resin, mixed etherified polymethylol melamine resin, polyamide, polymethylene diamine, diethylene triamine, pentamethyl diethylene triamine, triethylene tetramine, diethylene triamine, triethylene tetramine, and (2, 3-dimethyl) dibutylene triamine; Preferably, the second auxiliary agent is selected from at least one of ultraviolet absorbers, hindered amine light stabilizers, antioxidants, heat stabilizers, catalysts, hydrolysis stabilizers, nucleating and permeability enhancers, and toughening agents.

5. The photosensitive laminate according to claim 1, wherein The photosensitive layer includes a first photosensitive layer and a second photosensitive layer which are stacked in sequence, wherein the first photosensitive layer is arranged between the supporting layer and the second photosensitive layer, and the first photosensitive layer contains the light conversion agent.

6. The photosensitive laminate according to claim 5, wherein: The material of the first photosensitive layer includes, by weight, 100 parts of a first alkali-soluble resin, 5 to 50 parts of a first photopolymerizable monomer, 0.1 to 10 parts of a first photoinitiator, and 0.01 to 30 parts of the light conversion agent; And / or, the material of the second photosensitive layer includes 100 parts of a second alkali-soluble resin, 5 to 50 parts of a second photopolymerizable monomer, and 0.1 to 10 parts of a second photoinitiator.

7. The light conversion photosensitive laminate according to claim 1, characterized in that: The photosensitive layer contains the light conversion agent, the light conversion agent is distributed in a gradient manner in the photosensitive layer, and the content of the light conversion agent gradually decreases along the thickness direction away from the support layer; Preferably, the material of the photosensitive layer includes, by mass, 100 parts of a third alkali-soluble resin, 5 to 50 parts of a third photopolymerizable monomer, 0.1 to 10 parts of a third photoinitiator and 0.01 to 30 parts of the light conversion agent; and the content of the light conversion agent decreases gradually along the thickness direction away from the support layer.

8. A cured film, characterized in that: The cured film is formed by photocuring or photothermal dual curing of the photosensitive layer according to any one of claims 1 to 7.

9. A circuit board, characterized in that: The circuit board comprises the cured film according to claim 8.

10. An electronic device, characterized in that: The electronic device comprises the cured film according to claim 8 or the circuit board according to claim 9.

Images