Black ultraviolet curable resin composition, black resin cured product, material for manufacturing electronic component, and electronic component

Abstract

A black UV-curable resin composition, a black cured resin, and a material for manufacturing an electronic component and an electronic component provided with the black UV-curable resin composition and the black cured resin, the black UV-curable resin composition containing a black pigment, a photopolymerizable compound, and a photopolymerization initiator, the pigment composition is characterized in that when epsilon '(lambda) at a wavelength lambda nm is represented by epsilon' (lambda) = OD (lambda) / (c * l) according to the optical density OD (lambda) at the wavelength lambda nm, the pigment concentration c, and the optical path length l, the ratio epsilon '(550) / epsilon' (365) of epsilon '(550) at a wavelength of 550 nm to epsilon' (365) at a wavelength of 365 nm is within the range of 1.00-2.00.

Description

Technical Field

[0001] The present invention relates to a black ultraviolet curable resin composition, a black resin cured product, a material for producing an electronic component, and an electronic component.

[0002] This application claims priority based on patent application No. 2023-056995 filed in Japan on March 31, 2023, and the contents are incorporated herein by reference. Background Art

[0003] For example, a black ultraviolet-curable resin composition including a black pigment is used as a black matrix for a display device (display) composed of a liquid crystal or an organic EL, a light-shielding material for a contact image sensor, a light-shielding material for an optical component, a light-shielding filter, an IR (infrared) cut filter, a cover film, a light-shielding film for an electronic component, a black film, a UV-curable adhesive, etc.

[0004] For example, Patent Document 1 proposes a composition comprising zirconium nitride as a black pigment, a curable compound, and a photopolymerization initiator as a sealant composition for liquid crystal display elements having high light-shielding properties against visible light and high photocurability against ultraviolet rays.

[0005] Patent Document 1: Japanese Patent Publication No. 2020-076794 (A)

[0006] However, as described in the Examples, the sealant composition for liquid crystal display elements disclosed in Patent Document 1 cannot achieve sufficient curability by photocuring alone, and therefore requires simultaneous curing by thermal curing. In other words, the ultraviolet light curing property of Patent Document 1 is insufficient. Summary of the Invention

[0007] The present invention has been made in view of the above-mentioned circumstances, and its object is to provide a black ultraviolet-curable resin composition and a black resin cured product having excellent light-shielding properties for visible light and excellent photocurability for ultraviolet light, as well as materials for electronic component manufacturing and electronic components comprising the above-mentioned black ultraviolet-curable resin composition and black resin cured product.

[0008] The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have obtained the following findings.

[0009] By defining a new constant ε′(λ) as ε′(λ) = OD(λ) / (c×l) based on the optical density OD(λ) at a wavelength of λnm, the pigment concentration c (g / L), and the optical path length l (cm), it can be treated as a universal constant that depends on the concentration and the optical path length. Furthermore, by setting the ratio of ε′(550) at a wavelength of 550nm, which affects light-shielding properties, to ε′(365) at a wavelength of 365nm, which affects ultraviolet curing, within an appropriate range, it is possible to achieve both visible light-shielding properties and ultraviolet light-curing properties in a well-balanced manner.

[0010] The black ultraviolet curable resin composition of aspect 1 of the present invention is completed based on the above-mentioned findings. It is a black ultraviolet curable resin composition containing a black pigment, a photopolymerizable compound and a photopolymerization initiator, characterized in that, based on the optical density OD(λ) under light of wavelength λnm, the pigment concentration c(g / L), and the optical path length l(cm), when ε′(λ) under light of wavelength λnm is set to ε′(λ)=OD(λ) / (c×l), the ratio ε′(550) / ε′(365) of ε′(550) under light of wavelength 550nm to ε′(365) under light of wavelength 365nm is in the range of greater than 1.00 and less than 2.00.

[0011] According to aspect 1 of the present invention, the black ultraviolet curable resin composition has excellent light-shielding properties against visible light and excellent ultraviolet light curing properties because when ε'(λ) under light of wavelength λnm is set to ε'(λ)=OD(λ) / (c×l) based on the optical density OD(λ) under light of wavelength λnm, the pigment concentration c(g / L), and the optical path length l(cm), the ratio ε'(550) / ε'(365) of ε'(550) under light of wavelength 550nm to ε'(365) under light of wavelength 365nm is within the range of 1.00 or more and 2.00 or less.

[0012] The black ultraviolet curable resin composition according to the second aspect of the present invention is characterized in that, in the black ultraviolet curable resin composition according to the first aspect of the present invention, the photopolymerizable compound has a carboxyl group in a repeating unit in the molecule or at a molecular terminal.

[0013] According to the black ultraviolet curable resin composition of the second aspect of the present invention, since the photopolymerizable compound has a carboxyl group in a repeating unit in the molecule or at a molecular terminal, particle dispersibility is improved, and optical properties can be improved.

[0014] The black ultraviolet curable resin composition according to aspect 3 of the present invention is characterized in that, in the black ultraviolet curable resin composition according to aspect 1 or 2 of the present invention, the mass ratio X / Y of the content X of the black pigment to the content Y of the photopolymerization initiator is within a range of 0.3 or more and 10 or less.

[0015] According to the black ultraviolet curable resin composition of aspect 3 of the present invention, since the mass ratio X / Y of the content X of the black pigment to the content Y of the photopolymerization initiator is in the range of greater than 0.3 and less than 10, the above-mentioned ε′(550) / ε′(365) can be stably adjusted in the range of greater than 1.00 and less than 2.00.

[0016] The black resin cured product according to claim 4 of the present invention is characterized in that the black resin cured product is a cured product of the black ultraviolet curable resin composition according to any one of claims 1 to 3 of the present invention.

[0017] The black resin cured product according to aspect 4 of the present invention is a cured product of the black ultraviolet curable resin composition according to any one of aspects 1 to 3 of the present invention, and therefore has sufficiently excellent light-shielding properties and sufficient hardness, and is particularly suitable as a light-shielding component.

[0018] The material for manufacturing electronic components according to aspect 5 of the present invention is characterized in that it includes at least one or both of the black ultraviolet curable resin composition described in any one of aspects 1 to 3 of the present invention and a black resin cured product obtained by curing the black ultraviolet curable resin composition described in any one of aspects 1 to 3 of the present invention.

[0019] According to the electronic component manufacturing material of claim 5 of the present invention, since the black ultraviolet curable resin composition having excellent visible light shielding properties and ultraviolet light curing properties and the black resin cured product thereof are provided, electronic components having various excellent properties can be manufactured.

[0020] The electronic component of aspect 6 of the present invention is characterized in that it includes at least one or two of the black ultraviolet curable resin composition described in any one of aspects 1 to 3 of the present invention and a black resin cured product formed by curing the black ultraviolet curable resin composition described in any one of aspects 1 to 3 of the present invention.

[0021] According to the sixth aspect of the present invention, the electronic component has excellent various properties because it comprises a black ultraviolet curable resin composition having excellent light-shielding properties for visible light and photocurability for ultraviolet light, and a black resin cured product thereof.

[0022] The present invention provides a black ultraviolet curable resin composition having excellent visible light shielding properties and excellent ultraviolet light curing properties, a black resin cured product, and a material for producing an electronic component and an electronic component comprising the black ultraviolet curable resin composition and the black resin cured product. DETAILED DESCRIPTION

[0023] The embodiments of the present invention will be described below. The embodiments shown below are specifically described for better understanding of the gist of the invention and do not limit the present invention unless otherwise specified.

[0024] The black ultraviolet curable resin composition according to the present embodiment contains a black pigment, a photopolymerizable compound, and a photopolymerization initiator.

[0025] Moreover, based on the optical density OD(λ) under light of wavelength λnm, the pigment concentration c(g / L), and the optical path length l(cm), when ε′(λ) under light of wavelength λnm is set to ε′(λ)=OD(λ) / (c×l), the ratio ε′(550) / ε′(365) of ε′(550) under light of wavelength 550nm to ε′(365) under light of wavelength 365nm is in the range of greater than 1.00 and within the range of 2.00.

[0026] The optical density OD is expressed by the following formula (1) using the transmittance T. As can be seen from the formula (1), the higher the value of the optical density OD, the higher the light-shielding property.

[0027] (1) Formula: OD(λ) = log 10 [1 / T(λ)]

[0028] Next, the absorbance A is expressed by the following formula (2): In formula (2), ε is the molar absorption coefficient (L / cm / g), c is the particle concentration (g / L), and l is the optical path length (cm).

[0029] (2) Formula: A = log 10 [1 / T] = ε × c × l

[0030] According to equations (1) and (2), since the definition of optical density (OD) is essentially equivalent to that of absorbance (A), OD can be considered proportional to ε × c × l. Therefore, a new constant ε′ is defined as shown in equation (3) below. This constant ε′ can be treated as a universal constant that is independent of particle concentration and optical path length.

[0031] (3) Formula: ε′(λ)=OD / (c×l)

[0032] Furthermore, in the black ultraviolet curable resin composition of this embodiment, the ratio ε′(365) / ε′(365) of ε′(365) at a wavelength of 365 nm that affects ultraviolet curing to ε′(550) at a wavelength of 550 nm that affects light-shielding properties is set in the range of greater than 1.00 and less than 2.00.

[0033] When ε′(550) / ε′(365) is less than 1.00, ultraviolet rays are not sufficiently transmitted, and ultraviolet curing becomes insufficient, thereby potentially causing insufficient light shielding properties. On the other hand, when ε′(550) / ε′(365) is greater than 2.00, the sensitivity of the photopolymerization initiator to ultraviolet rays decreases, and ultraviolet curing becomes insufficient, thereby potentially causing insufficient light shielding properties.

[0034] Furthermore, ε′(550) / ε′(365) is preferably 1.20 or greater, more preferably 1.40 or greater. Furthermore, ε′(550) / ε′(365) is preferably 1.80 or less, more preferably 1.70 or less.

[0035] Although the above-mentioned ε'(λ) is determined by the concentration c (g / L) of the black pigment, since the photopolymerization initiator also contributes to the light-shielding property, sufficient light-shielding property can be ensured even if ε'(550) / ε'(365) is 1.00 or less.

[0036] Here, the value of ε'(550) / ε'(365) can be controlled by adjusting the concentration ratio of the black pigment and the photopolymerization initiator.

[0037] In this embodiment, the mass ratio X / Y of the content X of the black pigment to the content Y of the photopolymerization initiator is set in the range of 0.2 to 20. Although not particularly limited, the mass ratio X / Y of the content X of the black pigment to the content Y of the photopolymerization initiator can be 0.3 to 10.

[0038] Next, the photopolymerizable compound, the photopolymerization initiator, and the black pigment included in the black ultraviolet curable resin composition according to the present embodiment will be described.

[0039] As the photopolymerizable compound included in the black ultraviolet curable resin composition involved in this embodiment, a free radical polymerizable compound, a cationic polymerizable compound, or an anionic polymerizable compound can be used. For example, as the free radical polymerizable compound, a monomer and oligomer having an ethylenically unsaturated bond or a polyfunctional monomer having three or more ethylenically unsaturated bonds can be used.

[0040] The monomer having an ethylenically unsaturated bond may be an acrylic monomer having one or more (meth)acryloyl groups. Examples of acrylic monomers include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, octadecyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylate. Monofunctional monomers such as propyl ester, isoamyl acrylate, N,N-dimethylacrylamide, 4-acryloylmorpholine, tetrahydrofuran (meth)acrylate, isobornyl (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, (2-ethyl-2-methyl-1,3-dioxolane-4-yl) (meth)acrylate methyl ester; and bifunctional monomers such as 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, ethylene oxide-modified bisphenol A di(meth)acrylate, and neopentyl triethylene glycol di(meth)acrylate.

[0041] The oligomer having an ethylenically unsaturated bond may be an acrylic oligomer having two or more (meth)acryloyl groups. Acrylic oligomers are low molecular weight polymers formed by polymerization of acrylic monofunctional monomers. Examples of acrylic oligomers include acrylic (meth)acrylates, urethane (meth)acrylates, epoxy (meth)acrylates, polyester (meth)acrylates, and the like. The molecular weight of the acrylic oligomer may be, for example, in the range of 300 to 10,000, as measured by number average molecular weight.

[0042] The (meth)acrylate monomers and oligomers described above can be used alone or in combination of two or more. In addition, the acrylic oligomer is not limited to the oligomers described above, and a wide range of general oligomers can be used. The multifunctional monomer having an ethylenically unsaturated bond can be an acrylic multifunctional monomer having three or more (meth)acryloyl groups. Examples of acrylic multifunctional monomers include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and trimethylolpropane tri(meth)acrylate.

[0043] Examples of the cationic polymerizable compound include epoxy compounds and oxetane compounds. The epoxy compound is not particularly limited as long as it is a compound having a reactive epoxy group, and examples thereof include epoxy monomers, bisphenol A epoxy, bisphenol F epoxy, biphenyl epoxy, biphenyl mixed epoxy, naphthalene epoxy, cresol epoxy epoxy, dicyclopentadiene epoxy, trisphenol ethane epoxy, tetraphenol ethane epoxy, aliphatic epoxy, and alicyclic epoxy.

[0044] Specific examples of epoxy monomers include n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, lauryl glycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, allyl glycidyl ether, ethylene glycol diglycidyl ether, resorcinol diglycidyl ether, polypropylene glycol glycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, 1,2;5,6-diepoxyhexahydroindene, 3',3'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and 1,2-epoxy-4-vinylcyclohexane.

[0045] Examples of the oxetane compound include 2-ethylhexyloxetane, 3-ethyl-3-(hydroxymethyl)oxetane, 3-ethyl-3-(4-hydroxybutoxymethyl)oxetane, 3-ethyl-3-[(phenoxy)methyl]oxetane, 3-ethyl-3-(hexyloxymethyl)oxetane, 3,3'-(oxybismethylene)bis(3-ethyloxetane), 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, (3-ethyl-3-oxetane) cyclobutyl) methyl methacrylate, 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl, bis[(3-ethyl-3-oxetanyl)methyl]isophthalate, 3-ethyl-3([3-ethyloxetanyl-3-yl]methoxy)methyloxetane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl], and oligomers obtained by partially polymerizing these.

[0046] The content of the photopolymerizable compound is preferably within a range of, for example, 5 parts by mass or more and 99 parts by mass or less relative to 100 parts by mass of the black ultraviolet curable resin composition.

[0047] Here, in the present embodiment, the photopolymerizable compound preferably has a structure having a carboxyl group in a repeating unit in the molecule or at a molecular terminal.

[0048] By using a photopolymerizable compound having a carboxyl group in the molecule, the dispersibility of the particles is improved.

[0049] As the photopolymerization initiator contained in the black ultraviolet curable resin composition according to the present embodiment, a compound capable of absorbing ultraviolet rays (specifically, light having a wavelength of 100 to 400 nm) and initiating a polymerization reaction is preferable.

[0050] The content of the photopolymerization initiator is preferably within a range of, for example, 0.5 parts by mass or more and 15 parts by mass or less relative to 100 parts by mass of the black ultraviolet curable resin composition.

[0051] The photopolymerization initiator included in the black ultraviolet curable resin composition according to this embodiment may be, for example, a free radical generator or a photoacid generator. Examples of ultraviolet curing agents include acetophenone compounds, benzophenone compounds, benzoin ether compounds, triazine compounds, phosphine oxide compounds, sulfonium compounds, iodonium compounds, and organic peroxides.

[0052] Examples of acetophenone compounds include acetophenone, dimethylacetophenone, 2-hydroxy-2-methylacetophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1. Examples of benzophenone compounds include benzophenone and 2-chlorobenzophenone. Examples of benzoin ether compounds include benzoin and benzoin methyl ether. Examples of phosphine oxide compounds include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide. Examples of sulfonium compounds include triphenylsulfonium tetrafluoroborate, tri-p-tolylsulfonium trifluoromethanesulfonate, diphenyl[4-(phenylthio)phenyl]sulfonium hexafluoroantimonate, and diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate. Examples of iodonium compounds include bis(4-tert-butylphenyl)iodonium hexafluorophosphate and diphenyliodonium hexafluorophosphate. Examples of organic peroxides include benzoyl peroxide and cumene peroxide.

[0053] The black ultraviolet curable resin composition according to the present embodiment may further include an organic solvent as a diluent. Examples of the organic solvent include glycol ethers such as ethyl carbitol, ethyl carbitol acetate, butyl carbitol acetate (BCA), butyl carbitol, methyl cellosolve, ethyl cellosolve, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether, α-terpineol, methyl ethyl ketone (MEK), ethyl acetate, butyl acetate, n-propanol, isopropyl alcohol, methanol, ethanol, and toluene.

[0054] The black ultraviolet curable resin composition involved in this embodiment may further include a plasticizer as a diluent. As the plasticizer, for example, a phosphate plasticizer, a phthalate plasticizer, an aliphatic monobasic acid ester plasticizer, an aliphatic dibasic acid ester plasticizer, a glycol ester plasticizer, and an oxygen-containing acid ester plasticizer can be used. Examples of phosphate plasticizers include tributyl phosphate and 2-ethylhexyl phosphate. Examples of phthalate plasticizers include dimethyl phthalate and dibutyl phthalate. Examples of aliphatic monobasic acid plasticizers include butyl oleate and glycerol monooleate. Examples of aliphatic dibasic acid ester plasticizers include dibutyl adipate and di-2-ethylhexyl sebacate. Examples of glycol ester plasticizers include diethylene glycol dibenzoate and triethylene glycol di-2-ethylbutyrate. Examples of the oxo acid ester plasticizer include methyl acetyl ricinoleate and acetyl tributyl citrate.

[0055] The black pigment included in the black ultraviolet curable resin composition according to the present embodiment includes black particles.

[0056] The optimal content of the black pigment varies depending on the desired thickness of the black resin cured product, but is not limited thereto. For example, the content may be in the range of 0.001 parts by mass to 60 parts by mass, or in the range of 1 part by mass to 40 parts by mass, or in the range of 5 parts by mass to 20 parts by mass, relative to 100 parts by mass of the black ultraviolet-curable resin composition.

[0057] Examples of black particles include zirconium nitride particles, carbon black, titanium black, and iron oxide. The zirconium nitride particles preferably contain 80% or more zirconium nitride by mass, more preferably 90% or more. Furthermore, the zirconium nitride particles may contain oxygen or other metal elements other than zirconium. While not particularly limited, the oxygen content may be 1% or more by mass, and may be 10% or more by mass. Furthermore, while not particularly limited, the content of metal elements other than zirconium may be 0.1% or more by mass, and may be 1.0% or more by mass.

[0058] The type of carbon black is not particularly limited, and commercially available carbon black produced by conventional furnace, acetylene, and tank processes can be used. Carbon black that has been surface-treated to improve affinity with the components of the composition is particularly preferred.

[0059] Titanium black can be made from Mitsubishi Materials Corporation, etc. Specifically, 13M, 13M-C, 13M-T, 12S, UF-8, etc. can be used.

[0060] The particle size measurement of black particles using a transmission electron microscope (TEM) can be performed, for example, as follows. A black dispersion is dropped onto a substrate and dried to obtain a sample for TEM observation. The obtained sample is observed using TEM, and the particle size of the primary particles of 500 black particles is measured. The particle size is the maximum Feret diameter. Using the obtained particle size, a volume-based undersize cumulative distribution is prepared assuming that the particles are spheres. From the obtained undersize cumulative distribution, the particle size (50% cumulative distribution diameter) when the cumulative distribution is 50% and the particle size (90% cumulative distribution diameter) when the cumulative distribution is 90% are read.

[0061] The 50% cumulative distribution diameter (D50) of the black particles measured using the dynamic light scattering method can be in the range of 30 nm or more and 120 nm or less, or in the range of 40 nm or more and 100 nm or less. The 90% cumulative distribution diameter (D90) of the black particles measured using the dynamic light scattering method can be 200 nm or less, more preferably in the range of 60 nm or more and 150 nm or less. The cumulative amount diameter measured using dynamic light scattering can be 60 nm or more and 140 nm or less. In the volume-based undersieve cumulative distribution of the black particles measured using the dynamic light scattering method, the content of black particles above 300 nm can be 1% or less, and the content of black particles above 250 nm can be 5% or less.

[0062] The black ultraviolet curable resin composition according to the present embodiment may contain a plasticizer and other additives (surfactant, leveling agent, etc.) in addition to the photopolymerizable compound, the photopolymerization initiator, and the black pigment.

[0063] Next, the method for producing the black ultraviolet curable resin composition according to the present embodiment will be described.

[0064] First, a black dispersion is prepared by dispersing a black pigment in a solvent. The solvent can be a monomer having a reactive functional group within the molecule, water, or an organic solvent. Examples of monomers having a reactive functional group within the molecule include (meth)acrylic monomers having a (meth)acryloyl group, epoxy monomers having an epoxy ring such as an epoxy group or a glycidyl group, vinyl monomers having a vinyl or vinyl ether group, and oxetane monomers having an oxetane group.

[0065] From the viewpoint of improving the dispersion efficiency of the black pigment, it is preferred to use a low-viscosity solvent having a viscosity of 100 Pa·s or less at 25° C.

[0066] Here, the black dispersion may contain a dispersant. As the dispersant, for example, an organic substance having a group (adsorption functional group) having affinity for the black pigment and a structure having steric hindrance can be used.

[0067] Examples of groups (adsorption functional groups) having an affinity for black pigments include secondary amine groups, tertiary amine groups, carboxylic acid groups, phosphoric acid groups, and phosphate groups. Dispersants that can be used include polymer dispersants with molecular weights ranging from several hundred to several tens of thousands, silane coupling agents such as organotriethoxysilane and organotrimethoxysilane, and titanate coupling agents.

[0068] The structure having steric hindrance is not particularly limited, and alkyl chains, polyethylene glycol chains, polypropylene glycol chains, polyether chains, etc. can be used. The structure of the dispersant can be a structure in which a structure having steric hindrance extends linearly from a single adsorbed functional group, a comb-like structure in which graft chains extend in a comb-like manner from multiple adsorbed functional groups, etc.

[0069] The black dispersion can be produced, for example, by mixing a solvent, a black pigment, and a dispersant and subjecting the resulting mixture to a dispersion treatment. As a dispersion treatment apparatus, a paint shaker, a bead mill, an ultrasonic disperser, or the like can be used.

[0070] The black dispersant, photopolymerizable compound, and photopolymerization initiator obtained as described above are mixed. The mixing method is not particularly limited, and mixing can be performed using, for example, a planetary mixer, a three-roll mill, a kneader, or other mixing device.

[0071] In this manner, the black ultraviolet curable resin composition of the present embodiment is produced.

[0072] The black resin cured product of the present embodiment is a cured product obtained by curing the black ultraviolet curable resin composition of the present embodiment described above.

[0073] The black resin cured product of this embodiment is formed, for example, by applying the black UV-curable resin composition of this embodiment onto a substrate to form a coating film. Subsequently, the coating film is irradiated with ultraviolet light to polymerize the photopolymerizable compound. The ultraviolet light source can be a halogen lamp, a metal halide lamp, a UV-LED, or the like, with no particular limitation as long as the light source has a wavelength that matches the absorption wavelength of the photopolymerization initiator.

[0074] The electronic component manufacturing material and the electronic component of this embodiment include at least one or both of the black ultraviolet curable resin composition of this embodiment and a black resin cured product obtained by curing the black ultraviolet curable resin composition of this embodiment.

[0075] Specific examples of materials and electronic components for manufacturing electronic components include black matrices and black columnar spacers for color filters, CMOS camera modules, sealing materials for liquid crystal display elements, partition materials for micro LEDs, semiconductor packaging materials, underfill materials, black pastes for hiding circuits, light-shielding solder resists, black UV-curable inks, optical adhesives, and the like.

[0076] According to the black ultraviolet curable resin composition of the present embodiment constructed as described above, when ε'(λ) under light of wavelength λnm is set to ε'(λ)=OD(λ) / (c×l) based on the optical density OD(λ) under light of wavelength λnm, the pigment concentration c(g / L), and the optical path length l(cm), the ratio ε'(550) / ε'(365) of ε'(550) under light of wavelength 550nm and ε'(365) under light of wavelength 365nm is within the range of 1.00 or more and 2.00 or less, so the black ultraviolet curable resin composition has excellent light-shielding property against visible light and excellent ultraviolet light curing property.

[0077] Here, in the black ultraviolet curable resin composition of this embodiment, when the photopolymerizable compound has a carboxyl group in a repeating unit in the molecule or at a molecular terminal, particle dispersibility is improved, and optical properties can be further improved.

[0078] In the black ultraviolet curable resin composition of the present embodiment, when the mass ratio X / Y of the content X of the black pigment to the content Y of the photopolymerization initiator is in the range of greater than 0.3 and less than 20, and more preferably in the range of greater than 0.3 and less than 10, the above-mentioned '(550) / ε'(365) can be stably adjusted in the range of greater than 1.00 and less than 2.00.

[0079] The black resin cured product of the present embodiment is made of the black ultraviolet curable resin composition of the present embodiment and therefore has sufficiently excellent light-shielding properties and sufficient hardness, and is therefore particularly suitable as a light-shielding member.

[0080] According to the materials and electronic components for manufacturing electronic components of this embodiment, since they contain at least one or both of the black ultraviolet curable resin composition of this embodiment and the black resin cured product obtained by curing the black ultraviolet curable resin composition of this embodiment, electronic components with various excellent properties can be provided.

[0081] As mentioned above, although one embodiment of the present invention has been described, the present invention is not limited thereto, and appropriate changes can be made without departing from the technical concept of the present invention.

[0082] Example

[0083] A confirmation experiment conducted to confirm the effectiveness of the present invention will be described.

[0084] (Example 1 of the present invention)

[0085] 20 parts by mass of a black pigment composed primarily of zirconium nitride, prepared according to Example 1 of Japanese Patent Publication No. 2019-160829, 2 parts by mass (10% by mass relative to the black pigment content) of a phosphoric acid-based comb polymer as a dispersant, and benzyl acrylate as photopolymerizable compound 1 were weighed to a total of 100 parts by mass. The weighed components were dispersed and mixed in a bead mill using 0.3 mm diameter zirconium oxide beads for a residence time of 15 minutes to produce a black dispersion. The resulting black dispersion contained 20% by mass of zirconium nitride particles.

[0086] 10 parts by mass of the obtained black dispersion, 89 parts by mass of a polyester acrylate having a carboxyl group in its structure as the photopolymerizable compound 2 (EBERCRYL 450, manufactured by Daicel Allnex Co., Ltd.), and 1 part by mass of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide as a photopolymerization initiator were weighed, and mixed and degassed at 1000 rpm for more than 3 minutes using a planetary mixer (Degassing Rentaro, manufactured by Thinky Co., Ltd.) to produce an ultraviolet-curable black resin composition of Example 1 of the present invention.

[0087] In the obtained black ultraviolet curable resin composition, the content of the black pigment was 2% by mass, the content of the photopolymerization initiator was 1% by mass, and the content of the photopolymerizable compound was 89% by mass.

[0088] (Example 2 of the present invention)

[0089] 20 parts by mass of a black pigment composed primarily of zirconium nitride, prepared according to Example 1 of Japanese Patent Publication No. 2019-160829, 2 parts by mass (10% by mass relative to the black pigment content) of a phosphoric acid-based comb polymer as a dispersant, and isobornyl acrylate as photopolymerizable compound 1 were weighed to a total of 100 parts by mass. The weighed components were dispersed and mixed in a bead mill using 0.3 mm diameter zirconium oxide beads for a residence time of 15 minutes to produce a black dispersion A. The resulting black dispersion contained 20% by mass of zirconium nitride particles.

[0090] Furthermore, 20 parts by mass of carbon black, 10 parts by mass of a polyimide-based comb polymer as a dispersant, and isobornyl acrylate as photopolymerizable compound 1 were weighed to a total amount of 100 parts by mass. The weighed components were mixed and dispersed using an ultrasonic homogenizer for 1 hour to produce a black dispersion B.

[0091] The black dispersion liquid A and the black dispersion liquid B were mixed at a mass ratio of 9:1 to obtain a black dispersion liquid.

[0092] Regarding the production of the black ultraviolet curable resin composition, the same procedure as in Example 1 of the present invention was carried out except that the photopolymerizable compound 2, the photopolymerization initiator, and their blending amounts were as shown in Table 1, to obtain respective black ultraviolet curable resin compositions.

[0093] (Examples 3 and 4 of the present invention)

[0094] Each black ultraviolet curable resin composition was obtained in the same manner as in Example 1 except that the black dispersion liquid, photopolymerizable compound 1, photopolymerizable compound 2, photopolymerization initiator, and their blending amounts were as shown in Table 1.

[0095] (Example 5 of the present invention)

[0096] 30 parts by mass of a black pigment primarily composed of zirconium nitride prepared according to Example 1 of Japanese Patent Publication No. 2019-160829, 3 parts by mass (10% by mass relative to the black pigment) of a polyimide comb polymer as a dispersant, 4.5 parts by mass of trimethylolpropane triacrylate as the photopolymerizable compound 1, and 150 parts by mass of polypropylene glycol monomethyl ether acetate (PGMEA) as a diluent were weighed. These components were dispersed and mixed in a bead mill using zirconia beads with a diameter of 0.3 mm for a residence time of 15 minutes to produce a black dispersion.

[0097] A black ultraviolet curable resin composition was obtained in the same manner as in Example 1 of the present invention except that the black dispersion, photopolymerizable compound 1, photopolymerizable compound 2, photopolymerization initiator, and their blending amounts were as shown in Table 1.

[0098] (Example 6 of the present invention)

[0099] 20 parts by mass of a black pigment composed primarily of zirconium nitride, prepared according to Example 1 of Japanese Patent Publication No. 2019-160829, 2 parts by mass (10% by mass relative to the black pigment content) of a phosphoric acid-based comb polymer as a dispersant, and isobornyl acrylate as photopolymerizable compound 1 were weighed to a total of 100 parts by mass. The weighed components were dispersed and mixed in a bead mill using 0.3 mm diameter zirconium oxide beads for a residence time of 15 minutes to produce a black dispersion A. The resulting black dispersion contained 20% by mass of zirconium nitride particles.

[0100] Furthermore, 20 parts by mass of Titanium Black 13M-C (Mitsubishi Materials Electronic Chemicals Co., Ltd.), 10 parts by mass of a polyimide-based comb polymer as a dispersant, and isobornyl acrylate as the photopolymerizable compound 1 were weighed to a total amount of 100 parts by mass. The weighed components were mixed and dispersed and mixed in a bead mill using zirconia beads with a diameter of 0.3 mm for a residence time of 15 minutes to produce a black dispersion B.

[0101] The black dispersion liquid A and the black dispersion liquid B were mixed at a mass ratio of 9:1 to obtain a black dispersion liquid.

[0102] Regarding the production of the black ultraviolet curable resin composition, the same procedure as in Example 1 of the present invention was carried out except that the photopolymerizable compound 2, the photopolymerization initiator, and their blending amounts were as shown in Table 1, to obtain respective black ultraviolet curable resin compositions.

[0103] (Example 7 of the present invention)

[0104] A black ultraviolet-curable resin composition was obtained in the same manner as in Example 6 of the present invention, except that the mixing ratio of black dispersion liquid A to black dispersion liquid B was changed to 8:2 by mass, and the photopolymerizable compound 1, photopolymerizable compound 2, photopolymerization initiator, and their mixing amounts were set as shown in Table 1.

[0105] (Example 8 of the present invention)

[0106] A black ultraviolet curable resin composition was obtained in the same manner as in Example 1 of the present invention except that the black dispersion, photopolymerizable compound 1, photopolymerizable compound 2, photopolymerization initiator, and their blending amounts were as shown in Table 1.

[0107] (Comparative Example 1)

[0108] A black ultraviolet curable resin composition was obtained in the same manner as in Example 1 of the present invention except that the black dispersion, photopolymerizable compound 1, photopolymerizable compound 2, photopolymerization initiator, and their blending amounts were as shown in Table 2.

[0109] (Comparative Example 2)

[0110] A black ultraviolet curable resin composition was obtained in the same manner as in Example 2 of the present invention, except that the mixing ratio of the black dispersion liquid A and the black dispersion liquid B was changed to 7:3 in terms of mass ratio.

[0111] (Comparative Example 3)

[0112] A black ultraviolet curable resin composition was obtained in the same manner as in Example 1 of the present invention except that the black dispersion, photopolymerizable compound 1, photopolymerizable compound 2, photopolymerization initiator, and their blending amounts were as shown in Table 2.

[0113] The obtained black ultraviolet curable resin composition was diluted with BCA (butyl carbitol acetate) until the transmittance at a wavelength of 365 nm and a wavelength of 550 nm was 10% or more and 90% or less. The concentration of the black pigment in the dilution was 25 mg / kg (ppm by mass). The dilution was filled into a cuvette with an optical path length of 1 cm, and a spectrophotometer (UH4150, manufactured by Hitachi High-Tech Corporation) was used to continuously measure the transmittance at a wavelength of 300 nm to 1000 nm with a scale width of 1 nm. At this time, the cuvette filled with BCA was measured in advance, and the transmittance of the black ultraviolet curable resin composition at each wavelength was measured while the cuvette was subtracted as a background (baseline). The transmittances at 365 nm and 550 nm were read from the obtained transmission spectrum, and the OD at each wavelength and ε′(365) and ε′(550) were calculated according to formula (1). The evaluation results are shown in Table 3.

[0114] The obtained ultraviolet curable black composition was poured into a mold having a diameter of 5 mm and a depth of 2 mm, and then irradiated with an illuminance of about 250 mW / cm using a spot-type UV-LED irradiator (8332C, manufactured by CCS Corporation). 2 , UV light with a wavelength of 365nm for 15 seconds (cumulative illuminance 3750mJ / cm 2 ) was subjected to ultraviolet curing. The obtained cured product was removed from the mold and the uncured liquid portion was wiped off, thereby obtaining a black resin cured product.

[0115] The OD of the obtained black resin cured product was measured using a transmission densitometer (T5plus, manufactured by Ihara Electronics Industry Co., Ltd.) VIS The OD obtained using the transmission densitometerVIS The evaluation results are shown in Table 3.

[0116]

[0117]

[0118] [Table 3]

[0119]

[0120] In Examples 1 to 8 of the present invention, in which the ratio ε′(550) / ε′(365) of ε′(550) under light of a wavelength of 550 nm to ε′(365) under light of a wavelength of 365 nm was within the range of 1.00 or more and 2.00 or less, UV curing of the resin composition was sufficiently performed, and OD VIS It is 3.1 or higher, showing a high value.

[0121] On the other hand, in Comparative Example 1 where ε'(550) / ε'(365) exceeds 2.00 and X / Y also exceeds 10, the photopolymerization initiator has insufficient responsiveness to ultraviolet rays and UV curing is not performed at a sufficient thickness, so OD VIS These values ​​are smaller than those of Examples 1 to 8 of the present invention.

[0122] Regarding Comparative Examples 2 and 3 where ε′(550) / ε′(365) is less than 1.00, the transmittance of ultraviolet rays is insufficient and UV curing is not performed at a sufficient thickness, so OD VIS These values ​​are smaller than those of Examples 1 to 8 of the present invention.

[0123] As described above, according to the present invention, it has been confirmed that a black ultraviolet curable resin composition and a black resin cured product having excellent light-shielding properties against visible light and excellent ultraviolet light curing properties can be provided.

[0124] The black ultraviolet curable resin composition of the present invention can be suitably used as a material for forming a black pattern such as a black resist or a black ink for inkjet.

[0125] The black resin cured product of the present invention, which is a cured product of the black ultraviolet curable resin composition of the present invention, can be used as a black matrix of an image forming element used in a display device such as a liquid crystal display (display) or an organic EL display device, or as a light-shielding material in an image sensor such as a CMOS sensor.

[0126] Furthermore, the black resin cured product of the present invention can also be used as a sealing material for liquid crystal display elements, a black columnar spacer, a partition material for micro LEDs, a semiconductor packaging material, an underfill material, a black paste for concealing circuits, a light-shielding solder resist, a black UV-curable ink, and a material for an optical adhesive.

Claims

1. A black ultraviolet curable resin composition comprising a black pigment, a photopolymerizable compound and a photopolymerization initiator, characterized in that: Based on the optical density OD(λ) at wavelength λnm, the pigment concentration c, and the optical path length l, ε′(λ) at wavelength λnm is set to ε′(λ)=OD(λ) / (c×l). The ratio ε′(500) / ε′(365) of ε′(550) under light of a wavelength of 550 nm to ε′(365) under light of a wavelength of 365 nm is in the range of 1.00 or more and 2.00 or less.

2. The black ultraviolet curable resin composition according to claim 1, wherein The photopolymerizable compound has a structure having a carboxyl group in a repeating unit in the molecule or at a molecular terminal.

3. The black ultraviolet curable resin composition according to claim 1, wherein The mass ratio X / Y of the content X of the black pigment to the content Y of the photopolymerization initiator is within a range of 0.3 or more and 10 or less.

4. A black resin cured product, characterized in that: The black resin cured product is a cured product of the black ultraviolet curable resin composition according to any one of claims 1 to 3.

5. A material for manufacturing electronic components, characterized in that: The invention comprises at least one or both of the black ultraviolet curable resin composition according to any one of claims 1 to 3 and a black resin cured product obtained by curing the black ultraviolet curable resin composition according to any one of claims 1 to 3.

6. An electronic component, characterized in that The invention comprises at least one or both of the black ultraviolet curable resin composition according to any one of claims 1 to 3 and a black resin cured product obtained by curing the black ultraviolet curable resin composition according to any one of claims 1 to 3.

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