Photocurable resin composition, cured product, and electronic component

Abstract

[Problem] To provide a cured product that achieves antistatic performance only by UV curing and makes it possible to form a protection layer that favorably adheres to a glass substrate and a photocurable resin composition that makes it possible to obtain the cured product. [Solution] This photocurable resin composition is characterized by including (A) an ethylenically unsaturated group–containing compound, (B) a photopolymerization initiator, (C) an antistatic agent, and (D) a thiol additive, the (D) thiol additive content being 4.0–15.0 mass% of the entire photocurable resin composition in terms of solid content.

Description

Photocurable resin compositions, cured products, and electronic components

[0001] This invention relates to photocurable resin compositions, cured products, and electronic components.

[0002] Displays are used in a wide range of fields, including personal computers, monitors, smartphones, automobiles, and game consoles, for the purpose of displaying information and images. Displays generally use many electrically insulating materials, such as insulating inks and polarizing plates used for substrate protection. As a result, insulating materials such as glass substrates and polarizing plates tend to generate static electricity. Static electricity can cause problems such as disruption of the orientation of liquid crystal molecules in liquid crystal displays and display abnormalities in organic EL displays. Methods to prevent abnormalities in image display due to static electricity include forming an antistatic layer using coatings, interlayer materials, and substrate protection materials. Patent Document 1 describes an adhesive sheet that serves as an interlayer material containing an antistatic agent.

[0003] International Publication No. 2022 / 004238

[0004] The adhesive sheet described in Patent Document 1 could not dissipate static electricity that accumulated on the substrate during display substrate manufacturing, raising concerns that components such as chips and LEDs might be damaged. Currently, glass substrates are used in a wide range of display substrates, including OLED, liquid crystal, miniLED, and microLED. However, glass substrates generally have poor affinity with solder resist and protective materials, resulting in poor adhesion. Furthermore, it has been found that UV-curable resin compositions without a heat treatment process exhibit even worse adhesion to glass substrates. The present invention aims to address the above problems by providing a cured product that has antistatic properties through UV curing alone and can form a protective layer that adheres well to a glass substrate, as well as a photocurable resin composition that provides such a cured product.

[0005] To achieve the above objective, the present inventors have discovered that a cured product obtained by curing a photocurable resin composition containing (A) an ethylenically unsaturated group-containing compound, (B) a photopolymerization initiator, (C) an antistatic agent, and (D) a thiol-based additive provides a cured product with excellent antistatic performance and glass adhesion, and have completed the present invention. That is, the present invention is as follows.

[0006] [1] A photocurable resin composition comprising (A) an ethylenically unsaturated group-containing compound, (B) a photopolymerization initiator, (C) an antistatic agent, and (D) a thiol-based additive, wherein the content of the (D) thiol-based additive is 4.0% by mass or more and 15.0% by mass or less on a solid content basis with respect to the total amount of the photocurable resin composition. [2] The photocurable resin composition according to [1], wherein the (D) thiol-based additive comprises a secondary thiol compound. [3] The photocurable resin composition according to [1] or [2], wherein the (C) antistatic agent comprises at least one selected from the group consisting of conductive fillers, liquid surfactants, and ionic liquids. [4] The photocurable resin composition according to any one of [1] to [3], wherein the content of the (A) ethylenically unsaturated group-containing compound is 30.0% by mass or more and 90.0% by mass or less on a solid content basis with respect to the entire photocurable resin composition. [5] The photocurable resin composition according to any one of [1] to [4], wherein the content of the antistatic agent (C) is 2.0% by mass or more and 50.0% by mass or less in terms of solid content relative to the entire photocurable resin composition. [6] The photocurable resin composition according to any one of [1] to [5], further comprising a phosphoric acid compound. [7] The photocurable resin composition according to any one of [1] to [6], further comprising a coloring agent. [8] The photocurable resin composition according to any one of [1] to [7], for use with a glass substrate. [9] A cured product obtained by photocuring the photocurable resin composition according to any one of [1] to [8].

[10] An electronic component comprising a substrate and the cured product according to [9].

[11] The electronic component according to

[10] , wherein the substrate is a glass substrate.

[0007] According to the present invention, it is possible to provide a cured product that has an antistatic effect and adheres to a glass substrate, and a photocurable resin composition that provides the cured product. The cured product of the present invention has excellent adhesion to glass substrates and is useful for protecting display substrates and for antistatic purposes.

[0008] Preferred embodiments of the present invention will be described in detail below. However, the present invention is not limited to the following embodiments.

[0009] A photocurable resin composition according to one aspect of the present invention has a film thickness of 15 μm and an integrated light intensity of 3000 mJ / cm². ２ The surface resistance value of the cured product obtained by irradiating it with active energy rays in such a manner, as measured in accordance with JIS K6911, is preferably 1.0 × 10⁻⁶. ５ Ω / sq or more 1.0×10 １１ Ω / sq or less, more preferably 1.0 × 10 ６ Ω / sq or more 1.0×10 １１ Ω / sq or less, more preferably 1.0 × 10⁻⁶ ７ Ω / sq or more 1.0×10 １０ It will be less than or equal to Ω / sq.

[0010] A photocurable resin composition according to one aspect of the present invention has a film thickness of 15 μm and an integrated light intensity of 3000 mJ / cm². ２ The glass adhesion of the cured product obtained by irradiating it with active energy rays in such a manner is preferably 4B or higher, and more preferably 5B, as measured in accordance with ASTM D3359-23.

[0011] [1. Photocurable Resin Composition] A photocurable resin composition according to one embodiment of the present invention contains (A) an ethylenically unsaturated group-containing compound, (B) a photopolymerization initiator, (C) an antistatic agent, and (D) a thiol-based additive.

[0012] [1-1. (A) Ethylene-Unsaturated Group-Containing Compounds] In the present invention, an ethylenically unsaturated group-containing compound is a photopolymerizable compound having one or more ethylenically unsaturated double bonds in one molecule. The compound can be a monomer, oligomer, or polymer. By including this compound, the crosslinking density during photopolymerization of the photocurable resin composition is increased, improving the heat resistance of the photocurable resin composition and the chemical resistance of the cured product. The (A) ethylenically unsaturated group-containing compound used in this embodiment may be any compound having an ethylenically unsaturated group, and known and commonly used compounds can be used. The (A) ethylenically unsaturated group-containing compound can be used alone or in combination of two or more. Examples include photopolymerizable monomers such as acrylic acid ester group-containing monomers or vinyl or allyl group-containing monomers, or their oligomers and polymers.

[0013] Examples of the above monomers include conventionally known polyester (meth)acrylates, polyether (meth)acrylates, urethane (meth)acrylates, carbonate (meth)acrylates, epoxy (meth)acrylates, etc. Specifically, alkyl acrylates such as 2-ethylhexyl acrylate and cyclohexyl acrylate; hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; mono- or diacrylates of alkylene oxide derivatives such as ethylene glycol, propylene glycol, diethylene glycol, and dipropylene glycol; acrylamides such as N,N-dimethylacrylamide, N-methylolacrylamide, and N,N-dimethylaminopropylacrylamide; aminoalkyl acrylates such as N,N-dimethylaminoethyl acrylate and N,N-dimethylaminopropyl acrylate; hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, trishydroxyethyl isocyanurate, etc. Polyhydric acrylates such as polyhydric alcohols or their alkylene oxide adducts or ε-caprolactone adducts; polyhydric acrylates derived from phenols such as phenoxyacrylate and bisphenol A diacrylate or their alkylene oxide adducts; acrylates derived from glycidyl ethers such as glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, and triglycidyl isocyanurate; and, not limited to the above, acrylates obtained by directly acrylateting polyols such as polyether polyols, polycarbonate diols, hydroxyl-terminated polybutadienes, and polyester polyols, or by urethane acrylates obtained via diisocyanates, as well as melamine acrylate and at least one of each methacrylate corresponding to the acrylates can be appropriately selected and used. Such photopolymerizable monomers can also be used as reactive diluents.

[0014] <Acrylic acid ester group-containing monomers and their polymers> Examples of commercially available acrylic acid ester group-containing monomers and their polymers include "Viscoat #200", "IBXA", and "MEDOL-10" from Osaka Organic Chemical Industry Co., Ltd., "EBECRYL 270", "EBECRYL 8411", "EBECRYL 8409", "EBECRYL 8804", "EBECRYL 8807", "EBECRYL 8465", "EBECRYL 8701", "EBECRYL 8606", "EBECRYL 8904", and "EBECRYL 8452" from Daicel Ornex Co., Ltd., and "SP-4010", "SP-1507", and "SP-1509" from Resonac Co., Ltd.

[0015] <Vinyl or Allyl Group-Containing Monomers> Examples of commercially available vinyl or allyl group-containing monomers include "AOMA" manufactured by Nippon Shokubai Co., Ltd. and "TAIC" manufactured by Mitsubishi Chemical Corporation.

[0016] (A) The content of the ethylenically unsaturated group-containing compound is preferably 30.0% by mass or more and 90.0% by mass or less, and more preferably 45.0% by mass or more and 80.0% by mass or less, on a solid content basis, relative to the entire photocurable resin composition. (A) When the content of the ethylenically unsaturated group-containing compound is within the above numerical range, the photocurability is good and the properties of the cured product obtained by photocuring are good.

[0017] [1-2. (B) Photopolymerization initiators] (B) Photopolymerization initiators are compounds that generate active species capable of initiating polymerization of polymerizable compounds upon irradiation with active energy rays.

[0018] Any known photopolymerization initiator can be used as the (B) photopolymerization initiator described above. Examples include oxime-based photopolymerization initiators and acylphosphine oxide-based photopolymerization initiators. The (B) photopolymerization initiator can be used individually or in combination of two or more.

[0019] Examples of photopolymerization initiators include, specifically, bis-(2,6-dichlorobenzoyl)phenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis-(2,6-dimethoxybenzoyl)phenylphosphine oxide, and bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl phenylphosphine oxide. Sphingoxides, bisacylphosphine oxides such as bis-(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphine methyl ester, 2-methylbenzoyldiphenylphosphine oxide, pivaloylphenylphosphine Monoacylphosphine oxides such as sopropyl esters and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; ethyl phenyl(2,4,6-trimethylbenzoyl)phosphinate, 1-hydroxycyclohexylphenyl ketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)-benzyl]phenyl}-2-methyl-propan-1-one, 2-hydroxy Hydroxyacetophenones such as C-2-methyl-1-phenylpropan-1-one; benzoins such as benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, and benzoin n-butyl ether; benzoin alkyl ethers; benzophenones such as benzophenone, p-methylbenzophenone, Michla's ketone, methylbenzophenone, 4,4'-dichlorobenzophenone, and 4,4'-bis-diethylaminobenzophenone;Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-(dimethylamino)-2-[(4-methylphenyl)methyl)-1-[4-(4-morpholinyl)phenyl]-1-butanone Acetophenones such as N,N-dimethylaminoacetophenone; thioxanthones such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone; anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2- Anthraquinones such as minoanthraquinone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzoic acid esters such as ethyl-4-dimethylaminobenzoate, 2-(dimethylamino)ethyl benzoate, and p-dimethylbenzoate ethyl ester; 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyloxime)], etanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyloxime) Examples include oxime esters such as s(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium, bis(cyclopentadienyl)-bis[2,6-difluoro-3-(2-(1H-pyrrole-1-yl)ethyl)phenyl]titanium, phenyl disulfide 2-nitrofluorene, butyroin, anisoin ethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide, etc.

[0020] <Acylphosphine oxide-based photopolymerization initiators> Examples of acylphosphine oxide-based photopolymerization initiators include ethyl (2,4,6-trimethylbenzoyl)-phenylphosphenate.

[0021] Examples of commercially available acylphosphine oxide-based photopolymerization initiators include "Omnirad TPO-L" and "Omnirad 819" from IGM Resins.

[0022] <Oxime-based polymerization initiator> As the oxime-based polymerization initiator, it is preferable to use an oxime-based photopolymerizing agent having the structure represented by the following formula (1).

[0023]

[0024] Examples of oxime-based photopolymerization initiators having the structure represented by formula (1) include 1-pentanone, 1-[4-[[4-(2-benzofuranylcarbonyl)phenyl]thio]phenyl]-4-methyl, 1-(o-acetyloxime), 1-propanone, 1-[4-[[4-(2-naphthylcarbonyl)phenyl]thio]phenyl], 1-(o-acetyloxime), and the like.

[0025] Commercially available oxime-based photopolymerization initiators having the structure represented by formula (1) include, for example, "Irgacure OXE-04" manufactured by BASF Japan Ltd. Other commercially available oxime ester-based photopolymerization initiators include Irgacure OXE01 and OXE02 from BASF Japan Ltd., N-1919 from ADEKA Corporation, ADEKA Arcles NCI-831 and NCI-831E, and TR-PBG-304 from Changzhou Strong Electronic New Materials Co., Ltd.

[0026] Other examples include carbazole oxime ester compounds described in Japanese Patent Publication No. 2004-359639, Japanese Patent Publication No. 2005-097141, Japanese Patent Publication No. 2005-220097, Japanese Patent Publication No. 2006-160634, Japanese Patent Publication No. 2008-094770, Japanese Patent Publication No. 2008-509967, Japanese Patent Publication No. 2009-040762, and Japanese Patent Publication No. 2011-80036.

[0027] The content of the photopolymerization initiator is preferably 0.1 to 10% by mass, and more preferably 1 to 7% by mass, based on the solid content of the total amount of the photocurable resin composition. When the content of the photopolymerization initiator is 0.1% by mass or more, the photocurability of the photocurable resin composition is good, and the properties of the cured product, such as chemical resistance, are also good. On the other hand, when the content is 10% by mass or less, light absorption at the surface of the cured product is good, and the deep curing properties do not tend to decrease.

[0028] In combination with the above-mentioned photopolymerization initiator, a photoinitiator, sensitizer, or catalyst may be used. Examples of photoinitiators, sensitizers, or catalysts include benzoin compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, and xanthone compounds. In particular, it is preferable to use thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 4-isopropylthioxanthone. The inclusion of a thioxanthone compound can improve deep curing properties. These compounds can sometimes be used as photopolymerization initiators, but it is preferable to use them in combination with a photopolymerization initiator. Furthermore, one type of photoinitiator, sensitizer, or catalyst may be used alone, or two or more types may be used in combination.

[0029] These photopolymerization initiators, photoinitiation aids, sensitizers, and catalysts absorb specific wavelengths, which can sometimes lead to reduced sensitivity and cause them to function as UV absorbers. However, they are not used solely for the purpose of improving the sensitivity of photocurable resin compositions. By absorbing light of specific wavelengths as needed, the photoreactivity of the surface can be increased, changing the line shape and aperture of the resist pattern to vertical, tapered, or reverse tapered shapes, while also improving the accuracy of line width and aperture diameter.

[0030] [1-3. (C) Antistatic agent] (C) The antistatic agent can be any compound having conductive properties, and one type can be used alone or in combination of two or more types. Examples include conductive fillers, liquid surfactants, and ionic liquids.

[0031] <Conductive filler> Examples of the conductive filler include, for example, conductive carbon, elemental metal powder, conductive metal oxide, and non-metal conductive powder. Among these, from the viewpoint of excellent conductivity even with a small addition amount, conductive carbon and non-metal conductive powder are preferable, and conductive carbon is more preferable.

[0032] (Conductive carbon) Examples of the conductive carbon include amorphous carbon, graphite carbon, carbon nanotubes, etc. Commercially available products of conductive carbon include "Ketjen Black EC300J", "Ketjen Black ECP", "Ketjen Black EC600JD", "Ketjen Black ECP600JD" manufactured by Lion Specialty Chemicals Co., Ltd., "Matrix 204", "Matrix 301", etc. manufactured by OCSiAl Co., Ltd.

[0033] (Elemental metal powder) Examples of the elemental metal powder include elemental metal powders such as gold, silver, copper, nickel, chromium, palladium, rhodium, ruthenium, indium, aluminum, tungsten, molybdenum, platinum, etc., alloy powders such as copper-nickel alloy, silver-palladium alloy, copper-tin alloy, silver-copper alloy, copper-manganese alloy, etc., metal particles, or metal-coated particles in which the surface of the alloy powder is coated with silver or the like. Commercially available products of the elemental metal powder include "AA-4703", "K-0082" (silver powder) manufactured by Metalor Technologies, "FMC-SB", "FMC-10", "FMC-30", "FMC-40" (metallic copper powder, granular powder); "FMC-11H", "FMC-31H", "FMC-41H" (metallic copper powder, flat powder), etc. manufactured by Furukawa Chemicals Co., Ltd.

[0034] (Conductive metal oxide) Examples of the conductive metal oxide include, for example, silver oxide, indium oxide, tin oxide, zinc oxide, ruthenium oxide, etc. Also, Sb-doped SnO ２Element-doped conductive metal oxides such as the above, or mixtures such as indium-tin oxides and tin-antimony oxides can also be used. The particle shape can be any of spherical, needle-like, etc. Particles with a layer of conductive metal oxide formed around the core particles may also be used. As commercially available products of conductive metal oxides, there are "T-1" (tin-antimony oxide), "SP-2" manufactured by Mitsubishi Materials Corporation, "SN-100P" (Sb-doped SnO ２ , spherical) and "FS-10P" (Sb-doped SnO ２ , needle-like) manufactured by Ishihara Sangyo Co., Ltd., "6010" (SnO ２ ) and "4410" (conductive layer: Sb-doped SnO ２ , core particles: BaSO ４ ) manufactured by Mitsui Mining & Smelting Co., Ltd., etc.

[0035] (Non-metallic conductive powder) The non-metallic conductive powder of the present application refers to non-metallic conductive powder other than the above-mentioned conductive carbon. For example, the non-metallic conductive powder includes conductive coating powders, and among them, conductive silica can be preferably used. As a commercially available product of non-metallic conductive powder, there is "VP NIT-52" manufactured by Nippon Aerosil Co., Ltd.

[0036] <Liquid surfactant> As the liquid surfactant, surfactants such as nonionic, anionic, and cationic surfactants can be mentioned. As commercially available products of liquid surfactants, there are "HS-12N" (nonionic surfactant), "ME-2" (anionic surfactant), "KS-555" (cationic surfactant), etc. manufactured by Kao Corporation.

[0037] <Ionic Liquids> Ionic liquids are compounds composed of cations and anions. Examples of cations include imidazolium, pyridinium, pyrrolidinium, piperidinium, ammonium, and phosphonium cations, with quaternary ammonium cations, pyridinium cations, and quaternary phosphonium cations being particularly noteworthy. Examples of anions include halide ions, tetrafluoroborates, hexafluorophosphates, and bis(trifluoromethylsulfonyl)amides. Commercially available ionic liquids include "ILP14-2" (bis(fluorosulfonyl)imide lithium salt) and "ILAP3-15" from Koei Chemical Co., Ltd., and "Efka IO6783" (hydroxy-functional ammonium salt), "Efka IO6782" (short-chain alkyl-modified quaternary ammonium salt), "Efka IO6785", "Efka IO6786" (non-functional imidazolium salt) and "Efka IO6779" from BASF.

[0038] (C) The content of the antistatic agent is preferably 2.0% by mass or more and 50.0% by mass or less, and more preferably 4.0% by mass or more and 40.0% by mass or less, on a solid content basis, based on the entire photocurable resin composition. (C) When the content of the antistatic agent is within the above numerical range, the conductivity of the resin composition is good and it can be suitably used in various electronic components.

[0039] [1-4. (D) Thiol-based additives] By including (D) thiol-based additives in the photocurable resin composition according to an embodiment of the present invention, tack-free properties due to improved surface curability, improved pencil hardness, and excellent glass adhesion can be obtained. For this reason, the photocurable resin composition according to an embodiment of the present invention can be used on glass substrates, which are generally difficult to adhere to. Any compound having a thiol group can be used as the (D) thiol-based additive, and known and commonly used compounds can be used. Compounds having primary, secondary, or tertiary thiol groups can be used as the (D) thiol-based additive. In particular, it is preferable that the (D) thiol-based additive contains a secondary thiol compound because it has good reactivity, excellent storage stability, and can prevent gelation of the resin composition.

[0040] Examples of compounds having a thiol group include ethylene glycol bisthioglycolate, TMMP; trimethylolpropane tris(3-mercaptopropionate), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, PEMP; pentaerythritol tetrakis(3-mercaptopropineauto), tetraethylene glycol bis(3-mercaptopropionate), DPMP; dipentaerythritol hexanes(3-mercaptopropionate), p-xylenethiol, m-xylenethiol, 4,4-thiobisbenzenethiol, 1,6-hexanedithiol, 2,2'-thiobisethanethiol, and 1,3,5-trimercaptobenzene.

[0041] (D) The content of the thiol-based additive is 4.0% by mass or more and 15.0% by mass on a solid content basis, based on the entire photocurable resin composition, preferably 5.0% by mass or more and 12.0% by mass or less. (D) When the content of the thiol-based additive is within the above numerical range, adhesion to the glass substrate is good and the tackiness is also good.

[0042] (D) Examples of commercially available thiol-based additives include "KarenzMT PE-1", "KarenzMT NR-1", "KarenzMT BD-1", and "KarenzMT TPMB" from Resonaq Corporation, and "TMMP", "PEMP", "Multiol Y-3", and "Multiol Y-4" from Sakai Chemical Industry Co., Ltd.

[0043] [1-5. Optional components of the photocurable resin composition] The photocurable resin composition according to this embodiment may further contain phosphoric acid compounds, non-conductive fillers, and other additive components as needed.

[0044] <Phosphate Compounds> Any phosphate compound having a phosphate ester group in its molecule may be used, and known and commonly used compounds are permitted. Specifically, 2-hydroxyethyl methacrylate acid phosphate, methyl acid phosphate, ethyl acid phosphate, and butyl acid phosphate are used. Examples of phosphate ester compounds include butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, isotridecyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, ethylene glycol acid phosphate, dibutyl phosphate, bis(2-ethylhexyl) phosphate, diphenyl phosphate, dibenzyl phosphate, dibutyl phosphate, monobutyl phosphate, didecyl phosphate, (o-phosphorylethanolamine, phenyl phosphate, creatinol phosphate), 2-oxypanone homopolymer 2-[2-methyl-1-oxo-2-propenyl]oxy]ethyl ester phosphate, (2-ethylhexyl)phosphonic acid 2-ethylhexyl, isodecyl acid phosphate, and monoisodecyl phosphate. Among phosphate compounds, phosphate ester compounds are preferred because they have effects such as improved adhesion and improved pigment dispersibility. In this invention, phosphate acrylate compounds are more preferred among them.

[0045] Commercially available phosphoric acid compounds include polar group-containing acrylic polymers such as "Light Ester" P-1M and P-2M from Kyoeisha Chemical Co., Ltd., "PM-2" and "PM-21" from the KAYAMER series from Nippon Kayaku Co., Ltd., and "JP-502," "JP-504," "JP-506H," "JP-508," "JP-512," "JP-513," "JP-518-O," "JP-524R," "EGAP," "JPA-514," "DBP," and "LB-5" from Johoku Chemical Industry Co., Ltd. Examples include "8", "JPCN-300", "NACURE4000" from Kusumoto Chemical Co., Ltd., "PC-88A", "AP-1", "AP-4", "DP-4", "MP-4", "AP-8", "AP-10", "MP-10" from Daihachi Chemical Industry Co., Ltd., the phosphanol series from Toho Chemical Industry Co., Ltd., "RD-510Y", "RD-720N", "RL-210", "RL-310", "RS-410", "RS-610", "RS-710", "EBECRYL 168", "KRM 8762" from Daicel Ornex Co., Ltd. Among these, "KRM 8762" from Daicel Ornex Co., Ltd. and "Light Ester P1-M" from Kyoeisha Chemical Co., Ltd. are preferred.

[0046] If a phosphoric acid compound is present, its content is preferably 5% by mass or less relative to the total solid content of the photocurable resin composition. When the phosphoric acid compound content is within the above numerical range, the curing properties of the cured product of the present invention tend to improve more easily.

[0047] (Non-conductive filler) In addition to the conductive filler used as an antistatic agent, the photocurable resin composition of the present invention may optionally contain a non-conductive filler to increase the physical strength of the cured product. Known inorganic or organic fillers can be used as the non-conductive filler, but barium sulfate, spherical silica, hydrotalcite, and talc are particularly preferred. Furthermore, metal oxides such as metal oxides and aluminum hydroxide can be used as extender pigment fillers to obtain flame retardancy.

[0048] The content of non-conductive fillers, if present, is preferably 20% by mass or less relative to the total solid content of the photocurable resin composition. When the content of non-conductive fillers is within the above numerical range, the curing properties of the cured product of the present invention tend to improve more easily.

[0049] Furthermore, the fillers described above may be surface-treated to improve their dispersibility in the photocurable resin composition. Using surface-treated fillers can suppress aggregation. The surface treatment method is not particularly limited, and any known and conventional method may be used, but it is preferable to treat the surface of the inorganic filler with a surface treatment agent having a curable reactive group, for example, a coupling agent having a curable reactive group as an organic group. As coupling agents, silane-based, titanate-based, aluminate-based, and zircoaluminate-based coupling agents can be used. Among these, silane-based coupling agents are preferred. Examples of such silane-based coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, N-(2-aminomethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-anilinopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, and the like, which can be used alone or in combination. These silane-based coupling agents are preferably immobilized on the surface of the filler by adsorption or reaction beforehand. Here, the amount of coupling agent to be treated per 100 parts by mass of filler is preferably 0.5 to 10 parts by mass.

[0050] (Colorants) The photocurable resin composition of the present invention may contain colorants. The colorants are not particularly limited, and known colorants such as red, blue, green, and yellow can be used. They may be pigments, dyes, or colorants, but from the viewpoint of reducing environmental impact and minimizing effects on the human body, halogen-free colorants are preferred.

[0051] Red colorants include monoazo, disazo, azolake, benzimidazolon, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone, and specifically those that are assigned a color index (C.I.; issued by The Society of Dyersan and Colorists) number, as follows:

[0052] Examples of monoazo-based red colorants include Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151, 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, and 269. Examples of disazo-based red colorants include Pigment Red 37, 38, and 41. Examples of monoazolake-based red colorants include Pigment Red 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 52:2, 53:1, 53:2, 57:1, 58:4, 63:1, 63:2, 64:1, and 68. Examples of benzimidazolone-based red colorants include Pigment Red 171, 175, 176, 185, and 208. Examples of perylene-based red colorants include Solvent Red 135, 179, Pigment Red 123, 149, 166, 178, 179, 190, 194, and 224. Examples of diketopyrrolopyrrole-based red colorants include Pigment Red 254, 255, 264, 270, and 272. Examples of condensed azo-based red colorants include Pigment Red 220, 144, 166, 214, 220, 221, and 242. Examples of anthraquinone-based red colorants include Pigment Red 168, 177, and 216, and Solvent Red 52, 149, 150, and 207. Examples of quinacridone-based red colorants include Pigment Red 122, 202, 206, 207, and 209.

[0053] Blue colorants include phthalocyanine-based and anthraquinone-based compounds, while pigment-based compounds include those classified as pigments, such as Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, and 60. Dye-based compounds such as Solvent Blue 35, 63, 67, 68, 70, 83, 87, 94, 97, 122, and 136 can be used. In addition to the above, metal-substituted or unsubstituted phthalocyanine compounds can also be used.

[0054] Examples of yellow colorants include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, and anthraquinone. For example, anthraquinone yellow colorants include Solvent Yellow 163, Pigment Yellow 24, 108, 193, 147, 199, and 202. Isoindolinone yellow colorants include Pigment Yellow 110, 109, 139, 179, and 185. Condensed azo yellow colorants include Pigment Yellow 93, 94, 95, 128, 155, 166, and 180. Examples of benzimidazolone-based yellow colorants include Pigment Yellow 120, 151, 154, 156, 175, and 181. Examples of monoazo-based yellow colorants include Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62:1, 65, 73, 74, 75, 97, 100, 104, 105, 111, 116, 167, 168, 169, 182, and 183. Furthermore, examples of disazo-based yellow colorants include Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, and 198.

[0055] Other colorants such as purple, orange, brown, black, and white may be added. Specifically, examples include Pigment Black 1, 6, 7, 8, 9, 10, 11, 12, 13, 18, 20, 25, 26, 28, 29, 30, 31, 32, Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, C.I. Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73, Pigment Brown 23, 25, carbon black, titanium dioxide, etc.

[0056] The amount of colorant in the photocurable resin composition is not particularly limited, but it can be 0.5% by mass or more and 10% by mass or less in terms of solid content relative to the entire photocurable resin composition.

[0057] [Organic Solvents] Organic solvents may be added to the photocurable resin composition of the present invention for purposes such as preparing the composition or adjusting the viscosity when applying it to a substrate or film. As organic solvents, known and commonly used organic solvents can be used, such as ketones like methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons like toluene, xylene, and tetramethylbenzene; glycol ethers like cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, and tripropylene glycol monomethyl ether; esters like ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, and propylene carbonate; aliphatic hydrocarbons like octane and decane; and petroleum-based solvents such as petroleum ether, petroleum naphtha, and solvent naphtha. These organic solvents can be used individually or in combination of two or more.

[0058] The content of the organic solvent is not particularly limited and can be appropriately set according to the desired viscosity to facilitate the preparation of the photocurable resin composition, but is preferably less than 8%, more preferably less than 2%, and even more preferably less than 0.5% of the total curable resin composition.

[0059] [Other Additives] The photocurable resin composition of the present invention may further contain, as needed, components such as surface tension modifiers, dispersants, cyanate compounds, mercapto compounds, urethane catalysts, thixonating agents, adhesion promoters, block copolymers, chain transfer agents, polymerization inhibitors, copper damage inhibitors, antioxidants, rust inhibitors, thickeners such as organic bentonite and montmorillonite, defoaming agents and leveling agents such as silicone-based, fluorine-based, and polymer-based agents, silane coupling agents such as imidazole-based, thiazole-based, and triazole-based agents, and flame retardants such as phosphinates, phosphate ester derivatives, and phosphazene compounds. These may include those known in the field of electronic materials.

[0060] [Method for Producing the Photocurable Resin Composition] The photocurable resin composition of the present invention can be prepared by weighing and blending each component, followed by pre-stirring with a stirrer. Subsequently, the components are dispersed in a kneader and kneaded to prepare the composition.

[0061] Examples of the mixing machines mentioned above include bead mills, ball mills, sand mills, three-roll mills, and two-roll mills. Among these, a three-roll mill is preferable to improve dispersibility, especially for relatively high-viscosity inks. A bead mill can also be used for dispersing low-viscosity inks.

[0062] [Cured Product] The cured product of the present invention is obtained by curing the above-described photocurable resin composition of the present invention. Manufacturing conditions such as curing conditions will be described later in [Method for Manufacturing Electronic Components]. Due to its high conductivity, the cured product of the present invention can be suitably used in electronic components. In particular, it is preferably used in display substrates.

[0063] [Applications] The photocurable resin composition of the present invention can be used in electronic components, and due to the high conductivity of the cured product of the present invention, it can be suitably used as a protective material with electrostatic discharge suppression properties for display substrates. In particular, since the photocurable resin composition of the present invention has excellent adhesion to glass, it is preferable to use it for glass substrates. Furthermore, the photocurable resin composition of the present invention can also be used for applications that form pattern layers, and can be used not only for applications that form pattern layers, but also for applications that do not form pattern layers, such as molding applications (sealing applications).

[0064] [Electronic Components] The electronic component of the present invention comprises a substrate and a cured product of the present invention. There are no particular restrictions on the structure, formation method, or application of any electronic component that uses the above cured product as a component, but examples include sensors, actuators, capacitors, inductors, transistors, converters, thermistors, connectors, transformers, capacitors, diodes, regulators, motors, antennas, switches, etc., and may have multiple applications from among these.

[0065] [Substrate] Examples of substrates include glass substrates, printed circuit boards and flexible printed circuit boards with circuits pre-formed using copper or the like, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / nonwoven fabric epoxy, glass cloth / paper epoxy, synthetic fiber epoxy, copper-clad laminates using materials such as fluororesin / polyethylene / polyphenylene ether, polyphenylene oxide / cyanate, metal substrates, polyimide films, polyethylene terephthalate films, polyethylene naphthalate (PEN) films, ceramic substrates, wafers, etc. Since the photocurable resin composition of the present invention has excellent glass adhesion, glass substrates are preferred as the substrate.

[0066] [Method for Manufacturing Electronic Components] As a non-limiting example of the method for manufacturing electronic components of the present invention, a method for manufacturing a backlight substrate is provided. As a method for manufacturing a backlight substrate, for example, the photocurable resin composition of the present invention is applied to a substrate by a bar coater method, a screen printing method, or the like, and then irradiated with active energy rays to form a tack-free resin layer. There are no particular restrictions on the coating film thickness, but generally, the film thickness after curing is appropriately selected in the range of 1 to 150 μm, preferably 5 to 60 μm.

[0067] The exposure machine used for the above-mentioned active energy ray irradiation can be any device equipped with a high-pressure mercury lamp, ultra-high-pressure mercury lamp, metal halide lamp, mercury short-arc lamp, etc., that irradiates ultraviolet light in the range of 350 to 450 nm. Furthermore, a direct writing device (for example, a laser direct imaging device that directly draws images with a laser using CAD data from a computer) can also be used. The lamp light source or laser light source of the direct writing device can have a maximum wavelength in the range of 350 to 450 nm. The exposure amount for image formation varies depending on the film thickness, etc., but is generally 10 to 3000 mJ / cm². ２ Preferably 100 to 2000 mJ / cm² ２ It can be within the range of

[0068] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In the following, "parts" and "%" all refer to mass on a solid content basis unless otherwise specified.

[0069] [1. Preparation of Photocurable Resin Compositions] Ethylene-unsaturated group-containing compounds, photopolymerization initiators, antistatic agents, thiol-based additives, and phosphoric acid compounds and other additives were blended in the amounts (unit: parts by mass) shown in Table 1. After pre-stirring with a stirrer, the mixture was kneaded in a three-roll mill to prepare the photocurable resin compositions of Examples 1 to 5 and Comparative Examples 1 to 4. Unless otherwise specified, the blending amounts in Table 1 are in parts by mass.

[0070]

[0071] The details of each component listed in Table 1 are as follows. Note that the amount of each component is the solid content value. <(A) Compounds containing ethylenically unsaturated groups> *1: EBECRYL 8701 (manufactured by Daicel Ornex Co., Ltd., trifunctional urethane acrylate) *2: Viscoat #200 (manufactured by Osaka Organic Chemical Industry Co., Ltd., monofunctional acrylate) <(B) Photopolymerization initiator> *3: Irgacure OXE-04 (manufactured by BASF Japan Ltd., 1-pentanone, 1-[4-[[4-(2-benzofuranylcarbonyl)phenyl]thio]phenyl]-4-methyl, 1-(o-acetyloxime), 1-propanone, 1-[4-[[4-(2-naphthylcarbonyl)phenyl]thio]phenyl], 1-(o-acetyloxime)) <(C) Antistatic agent> *4: VP NIT52 (manufactured by Nippon Aerosil Co., Ltd., nonmetallic conductive powder; conductive nanosilica) *5: ILP14-2 (manufactured by Koei Chemical Co., Ltd., ionic liquid; bis(fluorosulfonyl)imide lithium salt) <Non-conductive filler> *6: Aerosil #R974 (manufactured by Nippon Aerosil Co., Ltd., nanosilica filler) <(D) Thiol-based additive> *7: KarenzMT PE-1 (manufactured by Resonac Co., Ltd., tetrafunctional secondary thiol compound) *8: TMMP (manufactured by Sakai Chemical Industry Co., Ltd., tetrafunctional primary thiol compound) <Phosphate compound> *9: KRM 8762 (manufactured by Daicel Ornex Co., Ltd., phosphate-modified (meth)acrylate)

[0072] [2. Preparation of cured samples for evaluation and characterization of cured samples for evaluation] <Preparation of cured samples for evaluation> A photocurable resin composition prepared with the proportions shown in Table 1 was printed onto a 1.8 mm thick glass substrate using a 400 mesh screen, and exposed to UV light at an exposure of 3000 mJ / cm² using a UV conveyor. ２ A cured product was fabricated by performing full-surface exposure.

[0073] <Surface Resistance Value> The surface resistance value of the coating portion of the cured material used for evaluation was measured at a temperature of 25°C in accordance with JIS K6911, using a surface resistance measuring device Hiresta-UX MCP-HT800 manufactured by Nitto Seiko Co., Ltd. The measurement results are shown in Table 2. ◎ and ○ were considered to be passing grades. [Judgment Criteria] ◎: 1.0 × 10 ７Ω / sq or more 1.0×10 １０ Less than Ω / sq ○: 1.0 × 10 ５ Ω / sq or more 1.0×10 ７ Less than Ω / sq, or 1.0 × 10⁻⁶ １０ Ω / sq or more 1.0×10 １１ Less than Ω / sq ×: Other range

[0074] <Glass Adhesion> A cross-cut test was performed on the coating portion of the cured material used for evaluation, in accordance with ASTM D3359-23. The measurement results are shown in Table 2. ◎ and ○ were considered pass. [Judgment Criteria] ◎: 5B ○: 4B △: 1B to 3B ×: Peeling

[0075] <Sensitivity and Curability> The coating portion of the cured material used for evaluation above was rubbed with a clean cloth, and the sensitivity and curability were checked according to the following criteria. The results are shown in Table 2. ○ indicates a pass. [Criteria] ○: No cured material adheres to the clean cloth, and the cured material does not peel off from the substrate. △: The cured material has hardened and a coating has formed, and the cured material adheres to the clean cloth or peels off from the substrate. ×: The resin composition does not harden and can be completely wiped off from the substrate.

[0076] <Tackiness> The tackiness of the coated portion of the cured material used for evaluation was checked by touch according to the following criteria. The results are shown in Table 2. ◎ and ○ were considered passing grades. [Criteria] ◎: Tack-free ○: No tackiness, but the surface does not slip when touched △: Sticky enough to leave fingerprints ×: The coated surface is sticky, and ink clearly adheres to the finger

[0077] <Storage Stability> 25 g of the photocurable resin composition ink prepared with the proportions shown in Table 1 was placed in a 30 mL container, the container was sealed, and the container was stored at 25°C under the following storage conditions. Storage stability was confirmed according to the following criteria. The results are shown in Table 2. ◎ and ○ were considered acceptable. [Storage Conditions] Temperature: 25°C, Dark place [Criteria] ◎: No gelation in 1 month ○: No gelation in 2 weeks, gelled in less than 1 month ×: Germinated in less than 1 week

[0078]

[0079] Table 2 shows that the photocurable resin compositions of each example exhibited excellent properties. The evaluation coatings prepared using the photocurable resin compositions of Comparative Examples 1, 2, and 4 showed reduced adhesion and poor tackiness. Comparing the amounts of thiol-based additives in the photocurable resin compositions of Examples 1, 3, and 4, and Comparative Examples 1, 2, and 4, it can be seen that an amount of thiol-based additive of 4.0% to 15.0% by mass is preferable, and 5.0% to 12.0% by mass is more preferable. Furthermore, it was confirmed that the photocurable resin compositions of Examples 1 to 4 exhibited better storage stability than the photocurable resin composition of Example 5. Comparing the thiol-based additives in the resin compositions of Examples 1 and 5, it can be seen that Example 1, which contains a secondary thiol compound, has superior storage stability.

[0080] The evaluation coatings prepared using the photocurable resin compositions of Comparative Examples 3 and 4 had a surface resistance of 10 １１ The surface resistance value exceeded Ω / sq. This result indicates that the addition of an antistatic agent contributes to the reduction in surface resistance when comparing the photocurable resin compositions of Examples 1 and 2, and Comparative Examples 3 and 4. Furthermore, it can be seen that any type of antistatic agent is acceptable.

Claims

1. A photocurable resin composition comprising (A) an ethylenically unsaturated group-containing compound, (B) a photopolymerization initiator, (C) an antistatic agent, and (D) a thiol-based additive, wherein the content of (D) the thiol-based additive is 4.0% by mass or more and 15.0% by mass or less on a solid content basis, relative to the total amount of the photocurable resin composition.

2. The photocurable resin composition according to claim 1, wherein the (D) thiol-based additive comprises a secondary thiol compound.

3. The photocurable resin composition according to claim 1, wherein the (C) antistatic agent comprises at least one selected from the group consisting of conductive fillers, liquid surfactants, and ionic liquids.

4. The photocurable resin composition according to claim 1, wherein the content of the ethylenically unsaturated group-containing compound (A) is 30.0% by mass or more and 90.0% by mass or less on a solid content basis with respect to the entire photocurable resin composition.

5. The photocurable resin composition according to claim 1, wherein the content of the antistatic agent (C) is 2.0% by mass or more and 50.0% by mass or less on a solid content basis with respect to the entire photocurable resin composition.

6. The photocurable resin composition according to claim 1, further comprising a phosphoric acid compound.

7. The photocurable resin composition according to claim 1, further comprising a coloring agent.

8. The photocurable resin composition according to claim 1, for use with glass substrates.

9. A cured product obtained by photocuring a photocurable resin composition according to any one of claims 1 to 8.

10. An electronic component comprising a substrate and a cured product according to claim 9.

11. The electronic component according to claim 10, wherein the substrate is a glass substrate.

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