Curable resin compositions, cured products, and electronic components

Abstract

To provide a cured product capable of forming a protective layer with antistatic properties that does not deteriorate over time by UV curing alone without the use of ionic liquids, and a curable resin composition that provides such a cured product. [Solution] The photocurable resin composition of the present invention is a curable resin composition containing (A) an ethylenically unsaturated group-containing compound, (B) a photopolymerization initiator, and (C) an antistatic agent, characterized in that the (C) antistatic agent is not an ionic liquid, the curable resin composition does not contain an ionic liquid, and the content of the organic solvent is less than 8% by mass of the entire curable resin composition.

Description

[Technical Field]

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

[0002] Displays are used in a wide range of fields, including personal computers, monitors, smartphones, automobiles, and gaming devices, for the purpose of displaying information and images. Displays generally utilize many electrically insulating materials, such as insulating inks and polarizing plates used for substrate protection. Therefore, insulating materials like glass substrates and polarizing plates tend to generate static electricity. This static electricity can cause problems such as disruption of liquid crystal molecule orientation in liquid crystal displays and display abnormalities in organic EL displays. One method to prevent abnormalities in image display caused by static electricity is to form an antistatic layer using coatings, interlayer materials, or substrate protective materials. Patent Document 1 describes an adhesive sheet that serves as an interlayer material containing an antistatic agent. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] International Publication No. 2022 / 004238 [Overview of the project] [Problems that the invention aims to solve]

[0004] The adhesive sheet described in Patent Document 1 could not dissipate the static electricity that accumulated on the substrate during manufacturing, raising concerns that components such as chips and LEDs might be damaged. Furthermore, while the adhesive sheet described in Patent Document 1 uses an ionic liquid as a conductive material, it is generally known that ionic liquids are highly dependent on humidity and their antistatic function deteriorates significantly over time. In addition, ionic liquids have the characteristic of exhibiting antistatic function through a bleed-out phenomenon, but in substrates without a heat treatment process, the bleed-out phenomenon is unlikely to occur, and there is a risk that the antistatic function may not be exhibited. In consideration of the above problems, the present invention aims to provide a cured product capable of forming a protective layer with antistatic properties that does not deteriorate over time by UV curing alone without the use of ionic liquids, and a curable resin composition that provides such a cured product. [Means for solving the problem]

[0005] To achieve the above objective, the present inventors have discovered that a cured product obtained by curing a curable resin composition containing (A) an ethylenically unsaturated group-containing compound, (B) a photopolymerization initiator, and (C) an antistatic agent, without containing an ionic liquid, and with an organic solvent content of less than 8% by mass relative to the entire curable resin composition, provides a cured product with excellent antistatic performance and its stability over time, thus completing the present invention. That is, the present invention is as follows.

[0006] [1] A curable resin composition comprising (A) an ethylenically unsaturated group-containing compound, (B) a photopolymerization initiator, and (C) an antistatic agent, The aforementioned (C) antistatic agent is not an ionic liquid, The curable resin composition does not contain an ionic liquid. A curable resin composition characterized in that the content of organic solvent is less than 8% by mass of the entire curable resin composition. [2] The curable resin composition according to [1], wherein the (C) antistatic agent is at least one selected from the group consisting of liquid surfactants and conductive fillers. [3] The curable resin composition according to [2], wherein the conductive filler is at least one selected from the group consisting of conductive carbon, elemental metal powder, conductive metal oxide, and nonmetallic conductive powder. [4] The content of the (A) ethylenically unsaturated group-containing compound is 30.0% by mass or more and 90.0% by mass or less in terms of solid content with respect to the whole curable resin composition, the curable resin composition according to any one of [1] to [3]. [5] The content of the (C) antistatic agent is 0.02% by mass or more and 60.0% by mass or less in terms of solid content with respect to the whole curable resin composition, the curable resin composition according to any one of [1] to [4]. [6] The curable resin composition according to any one of [1] to [5], further comprising a (D) thiol-based additive. [7] The curable resin composition according to any one of [1] to [6], further comprising a phosphoric acid compound. [8] A cured product obtained by photocuring the curable resin composition according to any one of [1] to [7]. [9] The surface resistance value is 1.0×10 7 Ω / sq or more and 1.0×10 10 Ω / sq or less, the cured product according to [8].

[10] An electronic component comprising a substrate and the cured product according to [8].

[11] An electronic component comprising a substrate and the cured product according to [9]. [Advantages of the Invention]

[0007] According to the present invention, it is possible to provide a cured product having a long-term stable antistatic effect only by UV curing and a curable resin composition that gives the cured product. The cured product of the present invention can be expected to have a long-term stable antistatic effect immediately after curing and is useful for protecting the substrate and preventing charging. [Embodiments for Carrying Out the Invention]

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

[0009] The curable resin composition according to one aspect of the present invention has a film thickness of 15 μm and an integrated light quantity of 3000 mJ / cm 2The surface resistance value measured in accordance with JIS K6911 of the cured product obtained by irradiating active energy rays so as to be preferably 1.0×10 7 Ω / sq or more and 1.0×10 10 Ω / sq or less, more preferably 1.0×10 8 Ω / sq or more and 1.0×10 9 Ω / sq or less, and the surface resistance value over time after one month is preferably 1.0×10 7 Ω / sq or more and 1.0×10 10 Ω / sq or less, and the difference in surface resistance value between immediately after curing and after one month is within 1.0×10 n Ω / sq (n: the order of the surface resistance value immediately after curing). Also, the storage conditions for the above one month will be described later in the examples.

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

[0011] [1. Curable resin composition] The curable resin composition according to one embodiment of the present invention contains (A) an ethylenically unsaturated group-containing compound, (B) a photopolymerization initiator, and (C) an antistatic agent, and does not contain an ionic liquid. Hereinafter, each component will be described in detail.

[0012] [1-1. (A) Ethylenically unsaturated group-containing compound] In the present invention, the ethylenically unsaturated group-containing compound is a photopolymerizable compound having one or more ethylenically unsaturated double bonds in one molecule. As the compound, any of a monomer, an oligomer, and a polymer can be used. By including the compound, the crosslinking density during photopolymerization of the curable resin composition can be increased, and the heat resistance of the curable resin composition and the chemical resistance of the cured product can be improved. 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 may 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 acrylate obtained via diisocyanate, 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] <Acrylate ester group-containing monomers and their polymers> Commercially available monomers and polymers containing acrylic acid ester groups 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 Corporation, and "SP-4010," "SP-1507," and "SP-1509" from Resona Corporation.

[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, based on the solid content of 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 initiator] (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 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 cy-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, Michlar's ketone, methylbenzophenone, 4,4'-dichlorobenzophenone, and 4,4'-bisdiethylaminobenzophenone;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)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyloxime)] Examples include oxime esters such as s(η5-2,4-cyclopentadiene-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, and other titanosenes; phenyl disulfide 2-nitrofluorene, butyroin, anisoin ethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide, etc.

[0020] <Acylphosphine oxide-based photopolymerization initiator> 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 an oxime-based polymerization initiator, it is preferable to use an oxime-based photopolymerizing agent having the structure represented by the following formula (1).

[0023] [ka]

[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).

[0025] A commercially available oxime-based photopolymerization initiator having the structure represented by formula (1) is, 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 Arclus 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 curable resin composition. When the photopolymerization initiator content is 0.1% by mass or more, the photocurability of the curable 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 on 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 curable resin compositions. By absorbing light of specific wavelengths as needed, the photoreactivity of the surface can be increased, changing the line shape and apertures 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) Any antistatic agent is acceptable as long as it is a compound having conductive properties and is not an ionic liquid, and one type can be used alone or in combination of two or more types. Examples include conductive fillers and liquid surfactants.

[0031] <Conductive filler> Examples of conductive fillers include conductive carbon, elemental metal powders, conductive metal oxides, and non-metallic conductive powders. Among these, conductive carbon and non-metallic conductive powders are preferred, and conductive carbon is more preferred, from the viewpoint of exhibiting excellent conductivity even in small amounts.

[0032] (Conductive carbon) Examples of conductive carbon include amorphous carbon, graphite carbon, and carbon nanotubes. Commercially available conductive carbon products include "Ketjenblack EC300J," "Ketjenblack ECP," "Ketjenblack EC600JD," and "Ketjenblack ECP600JD" from Lion Specialty Chemicals Co., Ltd., and "Matrix 204" and "Matrix 301" from OCSiAl Co., Ltd.

[0033] (Individual metal powders) Examples of elemental metal powders include elemental metal powders such as gold, silver, copper, nickel, chromium, palladium, rhodium, ruthenium, indium, aluminum, tungsten, molybdenum, and platinum, as well as alloy powders such as copper-nickel alloys, silver-palladium alloys, copper-tin alloys, silver-copper alloys, and copper-manganese alloys, metal particles, or metal-coated particles in which the surface of alloy powder is coated with silver or the like. Examples of commercially available single-component metal powders include "AA-4703" and "K-0082" (silver powder) from Metalo Technologies, and "FMC-SB," "FMC-10," "FMC-30," and "FMC-40" (metallic copper powder, granular powder); and "FMC-11H," "FMC-31H," and "FMC-41H" (metallic copper powder, flat powder) from Furukawa Chemicals Corporation.

[0034] (Conductive metal oxides) Examples of conductive metal oxides include silver oxide, indium oxide, tin oxide, zinc oxide, and ruthenium oxide. Element-doped conductive metal oxides such as Sb-doped SnO2, as well as mixtures of indium-tin oxides and tin-antimony oxides, can also be used. The particle shape can be spherical, needle-shaped, or any other. Furthermore, particles with a layer of conductive metal oxide surrounding a core particle may also be used. Commercially available conductive metal oxides include "T-1" (tin-antimony oxide) and "SP-2" from Mitsubishi Materials Corporation, "SN-100P" (Sb-doped SnO2, spherical) and "FS-10P" (Sb-doped SnO2, needle-shaped) from Ishihara Sangyo Co., Ltd., and "6010" (SnO2) and "4410" (conductive layer: Sb-doped SnO2, core particles: BaSO4) from Mitsui Mining & Smelting Co., Ltd.

[0035] (Nonmetal conductive powder) In this application, the non-metallic conductive powder refers to a non-metallic conductive powder other than the conductive carbon mentioned above. For example, non-metallic conductive powders include conductive coated powders, and among these, conductive silica can be preferably used. One example of a commercially available non-metallic conductive powder is "VP NIT-52" manufactured by Nippon Aerosil Co., Ltd.

[0036] <Liquid surfactant> Examples of liquid surfactants include nonionic, anionic, and cationic surfactants. Commercially available liquid surfactants include Kao Corporation's "HS-12N" (nonionic surfactant), "ME-2" (anionic surfactant), and "KS-555" (cationic surfactant).

[0037] <Ionic Liquid> The antistatic agent (C) used in the present invention does not contain an ionic liquid. In the prior art, ionic liquids have been used as antistatic agents, but it is generally known that ionic liquids are highly dependent on humidity and their antistatic function deteriorates significantly over time. In addition, ionic liquids have the characteristic of exhibiting their antistatic function through a bleed-out phenomenon, but in substrates without a heat treatment process, the bleed-out phenomenon is unlikely to occur, and there is a risk that the antistatic function will not be exhibited. Ionic liquids are compounds composed of cations and anions. Examples of cations include imidazolium, pyridinium, pyrrolidinium, piperidinium, ammonium, and phosphonium cations, among which quaternary ammonium cations, pyridinium cations, and quaternary phosphonium cations are 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" (hydroxyl-functional ammonium salt), "Efka IO6782" (short-chain alkyl-modified quaternary ammonium salt), "Efka IO6785", "Efka IO 6786" (non-functional imidazolium salt), and "Efka IO6779" from BASF.

[0038] (C) The content of the antistatic agent is preferably 0.02% by mass or more and 60.0% by mass or less, and more preferably 0.2% by mass or more and 50.0% by mass or less, based on the solid content of the entire curable 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] The photocurable resin composition of the present invention may contain a (D) thiol-based additive to further improve adhesion to a glass substrate. The (D) thiol-based additive may be any compound having a thiol group, and known and commonly used compounds can be used. The (D) thiol-based additive can be a compound having primary, secondary, or tertiary thiol groups. Among these, from the viewpoint of having good reactivity, it is preferable that the (D) thiol-based additive contains a secondary thiol compound.

[0040] Examples of compounds containing 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) If thiol additives are included, the content is preferably 4.0% by mass or more and 15.0% by mass or less on a solid content basis, based on the entire curable resin composition, and more preferably 5.0% by mass or more and 12.0% by mass or less.

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

[0043] [1-5. Optional components of curable resin compositions] The curable resin composition according to this embodiment may further contain, if necessary, phosphoric acid compounds, non-conductive fillers, and other additive components.

[0044] <Phosphate compounds> Any phosphate compound containing a phosphate ester group in its molecule can be used, and known and commonly used compounds are permitted. Specifically, these include 2-hydroxyethyl methacrylate acid phosphate, methyl acid phosphate, ethyl acid phosphate, and butyl acid phosphate. 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 phosphorus compounds include acrylic polymers with polar groups 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", and "EBECRYL 168" and "KRM 8762" from Daicel Ornex Co., Ltd. Among these, preferred options include "KRM 8762" manufactured by Daicel Ornex Corporation and "Light Ester P1-M" manufactured by Kyoeisha Chemical Co., Ltd.

[0046] If a phosphate compound is present, its content is preferably 5% by mass or less relative to the total solid content of the curable resin composition. When the content of the phosphate compound 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) The photocurable resin composition of the present invention may, in addition to a conductive filler used as an antistatic agent (C), 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 be improved.

[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, and 3-mercaptopropyltrimethoxysilane, which can be used alone or in combination. It is preferable that these silane-based coupling agents are pre-adsorbed or immobilized on the surface of the filler by reaction. Here, the amount of coupling agent processed per 100 parts by mass of filler is preferably 0.5 to 10 parts by mass.

[0050] (Coloring agent) The curable resin composition of the present invention may contain a coloring agent. The coloring agent is not particularly limited, and known coloring agents such as red, blue, green, and yellow can be used. It may be a pigment, dye, or colorant, but from the viewpoint of reducing environmental impact and minimizing effects on the human body, a halogen-free coloring agent is 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 (CI; issued by The Society of Dyers 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, 216, 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 and anthraquinone compounds, while pigments include compounds classified as pigments, such as Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, and 60. Dyes 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, benzimidazolon, 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. Benzimidazolon 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, 183, etc. 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, 198, etc.

[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, CIPigment 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 curable 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 curable resin composition.

[0057] [Organic solvents] The curable resin composition of the present invention may contain a predetermined amount of organic solvent for purposes such as preparing the composition or adjusting its viscosity when applied 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 less than 8% by mass, preferably less than 2% by mass, and more preferably less than 0.5% by mass, relative to the entire curable resin composition.

[0059] [Other additives] The curable resin composition of the present invention may optionally further contain 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 defoamers, flame retardants such as imidazole-based, thiazole-based, and triazole-based silane coupling agents, and phosphorus compounds such as phosphinates, phosphate ester derivatives, and phosphazene compounds. These components may be those known in the field of electronic materials.

[0060] [Method for producing a curable resin composition] The curable resin composition of the present invention can be prepared by weighing and blending each component, followed by pre-mixing with a stirrer. Subsequently, the components are dispersed in a kneader and kneaded.

[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 curable resin composition of the present invention described above. 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] [Application] The curable 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. Furthermore, the curable resin composition of the present invention can be used for applications that form a patterned layer, and can also be used not only for applications that form a patterned layer, but also for applications that do not form a patterned layer, 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 the electronic component as long as the cured product is a component of it. Examples include sensors, actuators, capacitors, inductors, transistors, converters, thermistors, connectors, transformers, capacitors, diodes, regulators, motors, antennas, switches, etc., and it may also have multiple applications from among these.

[0065] [Base material] Examples of substrates include glass substrates, printed circuit boards and flexible printed circuit boards with circuits pre-formed using copper, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / nonwoven epoxy, glass cloth / paper epoxy, synthetic fiber epoxy, copper-clad laminates using materials such as fluororesin / polyethylene / polyphenylene ether, polyphenylene oxide / cyanate, and others such as metal substrates, polyimide films, polyethylene terephthalate films, polyethylene naphthalate (PEN) films, ceramic substrates, and wafers. Furthermore, in the form in which the curable resin composition of the present invention contains a thiol-based additive, a glass substrate is also preferred because it exhibits excellent glass adhesion.

[0066] [Manufacturing methods for electronic components] As a non-limiting example of a method for manufacturing electronic components of the present invention, a method for manufacturing a backlight substrate is provided. In the method for manufacturing a backlight substrate, for example, the curable resin composition of the present invention is applied to a substrate by a method such as a bar coater or screen printing, and then irradiated with active energy rays to form a tack-free resin layer. There are no particular limitations 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 100-2000 mJ / cm² 2 It can be within the range of [Examples]

[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 unless otherwise specified.

[0069] [1. Preparation of curable resin composition] The curable resin compositions of Examples 1-7 and Comparative Examples 1-5 were prepared by blending ethylenically unsaturated group-containing compounds, photopolymerization initiators, antistatic agents, thiol-based additives, and other additives in the amounts (parts by mass) shown in Table 1, pre-mixing with a stirrer, and then kneading with a three-roll mill. Note that unless otherwise specified, the ingredient amounts in Table 1 represent parts by mass.

[0070] [Table 1]

[0071] The details of each component listed in Table 1 are as follows. Note that the amounts of each component are based on the solid content, excluding the solvent. <Compounds containing ethylenically unsaturated groups> *1: EBECRYL 8465 (manufactured by Daicel Ornex Co., Ltd., trifunctional urethane acrylate) *2: AOMA (manufactured by Nippon Shokubai Co., Ltd., a vinyl group-containing monomer) <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)) <Antistatic agent> *4: VP NIT52 (manufactured by Nippon Aerosil Co., Ltd., non-metallic conductive powder; conductive nanosilica) *5:4410 (Manufactured by Mitsui Mining & Smelting Co., Ltd., conductive metal oxide; barium sulfate core ATO) *6: Ketjenblack ECP600JD (manufactured by Lion Specialty Chemicals, Inc., conductive carbon; carbon black) *7: ME-2 (manufactured by Kao Corporation, anionic liquid surfactant) *8: K-0082 (Manufactured by Metalo Co., Ltd., silver powder) <Ionic Liquid> *9: ILP14-2 (manufactured by Koei Chemical Co., Ltd., bis(fluorosulfonyl)imidolithium salt) <Non-conductive filler> *10: Aerosil #R974 (manufactured by Aerosil Japan Co., Ltd., nanosilica filler) <Thiol-based additives> *11: KarenzMT PE-1 (manufactured by Resonaq Corporation, a tetrafunctional secondary thiol compound) <Phosphate compounds> *12: KRM 8762 (manufactured by Daicel Ornex Co., Ltd., phosphate-modified (meth)acrylate) *13: PMA (Propylene glycol monomethyl ether acetate)

[0072] [2. Preparation of cured samples for evaluation and characterization of the cured samples for evaluation] <Preparation of hardened samples for evaluation> Curable resin compositions prepared with the proportions shown in Table 1 were printed onto a 1.8 mm thick glass epoxy substrate using a 400-mesh screen, and exposed to UV light at 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 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 acceptable. [Judgment criteria] ◎: 1.0 × 10 8 Ω / sq or more 1.0×10 9 Less than Ω / sq ○: 1.0 × 10 7 Ω / sq or more 1.0×10 8 Less than Ω / sq, or 1.0 × 10⁻⁶ 9 Ω / sq or more 1.0×10 10 Less than Ω / sq ×: Other range

[0074] <Adhesion> A cross-cut test was performed on the coating portion of the cured product used for evaluation, in accordance with ASTM D3359-23. The measurement results are shown in Table 2. ◎ and ○ were considered pass / fail. [Judgment criteria] ◎: 5B 〇:4B △: 1B~3B ×: Peeling off

[0075] <Surface resistance stability over time> For the coating portion of the cured material used for evaluation, the surface resistance value was measured one month after curing under the storage conditions described below, using the same method as for the <Surface Resistance Value> above. The time-dependent surface resistance stability was evaluated according to the following criteria. The results are shown in Table 2. A circle (○) indicates a pass. [Storage conditions] Temperature: 25℃ Humidity: 50~55% dark place [Judgment criteria] ○: After 1 month, the surface resistance value is 1.0 × 10 7 Ω / sq or more 1.0×10 10 Within the range of Ω / sq or less, and the difference in surface resistance between immediately after curing and one month later is 1.0 × 10⁻⁶. n Within Ω / sq (n: order of magnitude of surface resistance immediately after curing) △: Surface resistance value after 1 month is 1.0 × 10 7 Ω / sq or more 1.0×10 10 Within the range of Ω / sq or less, and the difference in surface resistance between immediately after curing and one month later is 1.0 × 10⁻⁶. n Ω / sq super 5.0×10 n Within Ω / sq (n: order of magnitude of surface resistance immediately after curing) ×: Other than the above

[0076] [Table 2]

[0077] The curable resin composition of Example 2 was evaluated for adhesion in the same manner as described above, except that a glass substrate was used instead of a glass epoxy substrate. The evaluation result was excellent (◎).

[0078] The evaluation coating film prepared using the curable resin composition of Comparative Example 1 did not contain either an antistatic agent or an ionic liquid, and therefore its surface resistance value did not fall within the target range, confirming that the antistatic function was not exhibited. These results show that, when comparing the curable resin compositions of Examples 1-7 and Comparative Example 1, the addition of one or more antistatic agents results in the development of antistatic functionality.

[0079] It was found that the surface resistance of the evaluation coatings prepared using the curable resin compositions of Comparative Examples 2 to 4 deteriorated over time. These results show that, when comparing the curable resin compositions of Examples 1-7 and Comparative Examples 2-4, the surface resistance of coatings using ionic liquids as antistatic agents does not stabilize over time, while the surface resistance of coatings without ionic liquids remains stable over time.

[0080] The evaluation coating film prepared using the curable resin composition of Comparative Example 5 had an organic solvent content of 8% by mass or more, resulting in a surface resistance value that did not fall within the target range, poor adhesion, and a deterioration in surface resistance value over time.

[0081] The evaluation coating film prepared using the curable resin composition of Example 2 contained a thiol-based additive, and it was confirmed that it exhibited good adhesion not only to glass epoxy substrates but also to glass substrates.

Claims

1. A curable resin composition comprising (A) an ethylenically unsaturated group-containing compound, (B) a photopolymerization initiator, and (C) an antistatic agent, The aforementioned (C) antistatic agent is not an ionic liquid, The curable resin composition does not contain an ionic liquid. A curable resin composition characterized in that the content of organic solvents is less than 8% by mass of the entire curable resin composition.

2. The curable resin composition according to claim 1, wherein the (C) antistatic agent is at least one selected from the group consisting of liquid surfactants and conductive fillers.

3. The curable resin composition according to claim 2, wherein the conductive filler is at least one selected from the group consisting of conductive carbon, elemental metal powder, conductive metal oxide, and non-metallic conductive powder.

4. The curable 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 curable resin composition.

5. The curable resin composition according to claim 1, wherein the content of the antistatic agent (C) is 0.02% by mass or more and 60.0% by mass or less in terms of solid content relative to the entire curable resin composition.

6. (D) The curable resin composition according to claim 1, further comprising a thiol-based additive.

7. The curable resin composition according to claim 1, further comprising a phosphoric acid compound.

8. A cured product obtained by photocuring the curable resin composition according to any one of claims 1 to 7.

9. Surface resistance value is 1.0 × 10 ７ Ω / sq or more 1.0×10 １０ The cured product according to claim 8, wherein the Ω / sq is less than or equal to Ω.

10. An electronic component comprising a base material and a cured product according to claim 8.

11. An electronic component comprising a base material and a cured product according to claim 9.

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