Photocurable resin composition

Abstract

In a conventional curable resin composition, when a resin is colored in order to conceal a component wiring or the like, curing acceleration by irradiation with an active energy ray is suppressed, and curability may be affected. To this end, the present invention relates to a photocurable resin composition having excellent surface curability even when colored, and capable of obtaining a cured product having excellent tensile strength. The above-mentioned problem is solved by a photocurable resin composition containing components (A) to (D): (A) an organic polymer having two or more alkoxysilyl groups per molecule; component (B): a compound having an isocyanuric acid ring and an alkoxysilyl group per molecule; component (C): a pigment; component (D): a photoacid generator.

Description

Technical Field

[0001] The present invention relates to a photocurable resin composition having excellent curing properties even on a colored surface and capable of obtaining a cured product having excellent tensile strength. Background Art

[0002] Conventionally, curable resin compositions that can be cured by moisture in the air without heating the components have been known and are widely used as adhesives, sealants, coating agents, etc. However, like the above curable resin compositions, curing based on moisture in the air causes unexpected reactions during storage and operation, leading to problems in production efficiency when used as adhesives, sealants, coating agents, etc. Japanese Patent Application Laid-Open No. 2008-274119 discloses a curable composition containing a vinyl polymer having at least one crosslinkable silyl group on average at the terminal and a compound that generates an acid or a base by irradiation with light. The curable composition is disclosed with the aim of curing by irradiation with active energy rays such as ultraviolet rays, and thus has excellent storage stability and can ensure an operation time. Summary of the Invention

[0003] However, when the resin is colored for concealing component wiring or the like, the curing promotion by irradiation with active energy rays is inhibited, causing problems affecting the curability. In response to this, it is known that curing can be achieved by heating by adding a thermal acid generator, but there is a problem that it cannot be used for components that cannot be heated.

[0004] The inventors of the present invention conducted intensive studies to achieve the above object, and as a result, found a method related to a photocurable resin composition that can be cured only by light even when colored, has excellent surface curability, and can obtain a cured product having excellent tensile strength, thereby completing the present invention.

[0005] The gist of the present invention will be described below.

[0006] [1] A photocurable resin composition containing the following components (A) to (D).

[0007] Component (A): An organic polymer having two or more alkoxysilyl groups in each molecule

[0008] Component (B): A compound having an isocyanuric acid ring and an alkoxysilyl group in each molecule

[0009] Component (C): A pigment

[0010] Component (D): A photoacid generator.

[0011] [2]Regarding the photocurable resin composition described in [1], the above component (A) contains an organic polymer having a polyether skeleton and two or more alkoxysilyl groups per molecule.

[0012] [3]Regarding the photocurable resin composition described in [1] or [2], the above component (A) contains an organic polymer having a polyether skeleton and two or more alkoxysilyl groups per molecule, and an organic polymer having a vinyl polymer skeleton and two or more alkoxysilyl groups per molecule.

[0013] [4]Regarding the photocurable resin composition according to any one of [1] to [3], the above component (C) is carbon black.

[0014] [5]Regarding the photocurable resin composition according to any one of [1] to [4], the above component (D) is an onium salt compound.

[0015] [6]Regarding the photocurable resin composition according to any one of [1] to [5], the above component (D) is a sulfonium salt compound.

[0016] [7]Regarding the photocurable resin composition according to any one of [1] to [6], the above component (B) is tris(3-trimethoxysilylpropyl) isocyanurate.

[0017] [8]A cured product obtained by curing the photocurable resin composition according to any one of [1] to [7] above.

[0018] [9]Regarding the cured product described in [8], the total light transmittance is 0.1% or less, and the tensile strength is 0.4 MPa or more.

[0019] Advantages of the Invention

[0020] The present invention provides a photocurable resin composition that has excellent surface curability even when colored and can obtain a cured product with excellent tensile strength. Detailed Description of the Invention

[0021] The present invention will be described in detail below. It should be noted that in this specification, "X to Y" is used to mean including the values (X and Y) described before and after as the lower limit value and the upper limit value, and means "X or more and Y or less". In addition, in this specification, the term (meth)acrylic acid means both acrylic acid and methacrylic acid.

[0022] The component (A) used in the present invention is an organic polymer having two or more alkoxysilyl groups in each molecule. The alkoxysilyl group may be bonded to the terminal or side chain of the organic polymer, but from the viewpoint of excellent curability of the so-called photocurable resin composition, a substance bonded to the terminal is preferably cited. From the viewpoint of operation, the component (A) is preferably liquid at 25°C. The viscosity (25°C) of the component (A) is not particularly limited, but is preferably 0.1 to 1000 Pa·s, more preferably 0.3 to 500 Pa·s, and particularly preferably 0.5 to 200 Pa·s. When the viscosity of the component (A) is 0.1 Pa·s or more, the deep curability is excellent, and when the viscosity of the component (A) is 1000 Pa·s or less, it is a low-viscosity composition, so the workability is excellent.

[0023] The above-mentioned alkoxysilyl group is a group in which 1 to 3 alkoxy groups are bonded to a silicon atom. Examples of the alkoxy group include methoxy, ethoxy, propoxy, isopropoxy, butoxy and the like. From the viewpoint of excellent surface curability, a group in which 3 alkoxy groups are bonded to a silicon atom is preferably used, and the alkoxy group is preferably methoxy. That is, trimethoxysilyl is most preferred.

[0024] The main chain structure of the above-mentioned component (A) is not particularly limited, and examples thereof include a polyether skeleton, a polyester skeleton, a polycarbonate skeleton, a polyalkylene skeleton, a polyurethane skeleton, a polyamide skeleton, a polyurea skeleton, a polyimide skeleton, and a vinyl-based polymer skeleton. Among them, from the viewpoints of excellent curability and tensile strength, a polyether skeleton or a vinyl-based polymer skeleton is preferred. They can be used alone or two or more of them can be used in combination, but it is more preferable to use in combination an organic polymer having a polyether skeleton and an organic polymer having a vinyl-based polymer skeleton, and most preferably to use in combination an organic polymer having a polyether skeleton and an organic polymer having an acrylic-based polymer skeleton.

[0025] As commercially available products of organic polymers having two or more alkoxysilyl groups in each molecule, examples of the polyether skeleton include Sairil (registered trademark) series SAT200, SAT350, SAT400, SAX720, SAX750, SAX510, SAX530, SAX575 (manufactured by KANEKA CORPORATION), etc. Examples of the vinyl polymer skeleton include EPION (registered trademark) series EP100S, EP103S, EP303S, EP505S (manufactured by KANEKA CORPORATION), etc., XMAP series SA100S, SA110S, SA120S, OR100S, OR110S (manufactured by KANEKA CORPORATION), etc. Examples of the mixture of the polyether skeleton and the vinyl polymer skeleton include MA410, MA451, MA480 (manufactured by KANEKA CORPORATION), etc. They can be used alone or two or more of them can be used in combination.

[0026] The component (B) used in the present invention is a compound having an isocyanuric acid ring and an alkoxysilyl group in each molecule. The reason is not clear yet, but a photocurable resin composition excellent in surface curability and tensile strength can be obtained by adding the component (B). The component (B) is not particularly limited, but examples thereof include tris(3-trimethoxysilylmethyl)isocyanurate, tris(3-trimethoxysilylpropyl)isocyanurate, tris(3-triethoxysilylmethyl)isocyanurate, tris(3-triethoxysilylpropyl)isocyanurate, 1-(3-(trimethoxysilyl)propyl)-3,5-di-2-propenyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, etc. They can be used alone or two or more of them can be used in combination. From the viewpoint of excellent surface curability and tensile strength, tris(3-trimethoxysilylpropyl)isocyanurate and 1-(3-(trimethoxysilyl)propyl)-3,5-di-2-propenyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione are most preferred, and tris(3-trimethoxysilylpropyl)isocyanurate is most preferred.

[0027] Examples of commercially available products of the component (B) include KBM-9659, X-12-1290 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc., but are not limited thereto.

[0028] The content of the above-mentioned component (B) is not particularly limited, but it is preferably 1 to 50 parts by mass, more preferably 3 to 30 parts by mass, still more preferably 5 to 20 parts by mass, and most preferably 7 to 15 parts by mass with respect to 100 parts by mass of the component (A). When it is 1 part by mass or more, a photocurable resin composition excellent in surface curability and tensile strength can be obtained, and when it is 50 parts by mass or less, a photocurable resin composition excellent in storage stability can be obtained.

[0029] The (C) component used in the present invention is a pigment. From the viewpoint of excellent hiding power, a black pigment is preferably used. As the black pigment, for example, carbon black, titanium black oxide, copper chromium black, phthalocyanine black, aniline black, etc. can be mentioned. Among them, from the viewpoints of so-called hiding power and dispersibility with respect to the (A) component of the present invention, carbon black is preferred. They can be used alone or two or more of them can be used in combination. In addition, from the viewpoint of dispersibility, the above (C) component is preferably pre-dispersed in a reactive resin or a plasticizer before use.

[0030] As the reactive resin capable of dispersing the (C) component, the above (A) component and an organic polymer having one alkoxysilyl group per molecule (including the silane coupling agent described later) can be mentioned.

[0031] The plasticizer capable of dispersing the (C) component is not particularly limited, but from the viewpoint of so-called not affecting the storage stability of the photocurable resin composition, alkyl phenyl sulfonate and polyoxyalkylene alkyl ether are preferred.

[0032] The content of the above (C) component is not particularly limited, but it is preferably 0.1 to 50 parts by mass, more preferably 0.3 to 30 parts by mass, and most preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the (A) component. When it is 0.1 part by mass or more, hiding power can be imparted to the resin, and when it is 50 parts by mass or less, it does not affect the curability.

[0033] The (D) component used in the present invention is a photoacid generator. A photoacid generator is a compound capable of releasing an acidic substance and crosslinking the (A) component by irradiating active energy rays. As the photoacid generator, for example, onium salt compounds and sulfonate compounds can be mentioned. However, from the viewpoint of excellent curability, onium salt compounds are preferred, and sulfonium salts are particularly preferred. They can be used alone or two or more of them can be used in combination. In addition, from the viewpoint of compatibility, the above (D) component can be pre-dissolved in a solvent such as an organic solvent.

[0034] The onium salt compound that can be used in the present invention is not particularly limited, but for example, iodonium salts or sulfonium salts having anions such as hexafluoroantimonate, tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, hexachloroantimonate, trifluoromethanesulfonate ion, and fluorosulfonate ion can be mentioned. Specifically, diphenyl(4-phenylthio)phenylsulfonium hexafluorophosphate, diphenyl[4-(phenylthio)phenyl]sulfonium·hexafluoroantimonate(V), diphenyl[4-(phenylthio)phenyl]sulfonium = trifluoro tris(pentafluoroethyl)-λ 5- Phosphanuide salts, [4-(1-methylethyl)phenyl](4-methylphenyl)iodonium = tris(trifluoro(1,1,2,2,2-pentafluoroethyl))phosphate, etc. From the viewpoint of reactivity, diphenyl[4-(phenylthio)phenyl]sulfonium = tris(trifluoro(pentafluoroethyl))-λ 5 - Phosphanuide salts.

[0035] Examples of commercially available onium salt compounds include CPI-100P, CPI-101P, CPI-200K, CPI-210S, IK-1 (manufactured by San-Apro Co., Ltd.), WPI-113, WPI-116, WPI-169, WPI-170, WPAG-336, WPAG-367, WPAG-370, WPAG-469, WPAG-638 (manufactured by Fujifilm Wako Pure Chemical Corporation), ADEKA Optomers SP-150, SP-151, SP-170, SP-171, SP-172 (manufactured by ADEKA Corporation), Irgacure (registered trademark) 250 (manufactured by BASF), CD-1010, CD-1011, CD-1012 (manufactured by Sartomer), San-Aid (registered trademark) SI-60, SI-80, SI-100, SI-60L, SI-80L, SI-100L, SIL145, SI-L150, SI-L160, SI-L110, SI-L147 (manufactured by Sanshin Chemical Industry Co., Ltd.), etc.

[0036] The sulfonate compounds that can be used in the present invention are not particularly limited. For example, 1,8-naphthalenedicarboximide trifluoromethanesulfonate, 1,8-naphthalenedicarboximide nonafluorobutanesulfonate, 1,8-naphthalenedicarboximide perfluorooctanesulfonate, 1,8-naphthalenedicarboximide pentafluorobenzenesulfonate, 1,3,6-trioxo-3,6-dihydro-1H-11-thia-azapentalene-2-yl nonafluorobutanesulfonate, 8-isopropyl-1,3,6-trioxo-3,6-dihydro-1H-11-thia-2-azapentalene-2-yl nonafluorobutanesulfonate, 1,2-naphthoquinone-2-diazido-5-sulfonyl chloride, 1,2-naphthoquinone-2-diazido-4-sulfonyl chloride, 1,2-benzoquinone-2-diazido-4-sulfonyl chloride, 1,2-naphthoquinone-2-diazido-5-sodium sulfonate, 1,2-naphthoquinone-2-diazido-4-sodium sulfonate, 1,2-benzoquinone-2-diazido-4-sodium sulfonate, 1,2-naphthoquinone-2-diazido-5-potassium sulfonate, 1,2-naphthoquinone-2-diazido-4-potassium sulfonate, 1,2-benzoquinone-2-diazido-4-potassium sulfonate, 1,2-naphthoquinone-2-diazido-5-methyl sulfonate, 1,2-benzoquinone-2-diazido-4-methyl sulfonate, etc.

[0037] Examples of commercially available sulfonate compounds include SIN-11 (manufactured by Sambo Chemical Laboratories, Inc.) and NT-1TF (manufactured by San-Apro Ltd.).

[0038] The content of the above component (D) is not particularly limited, but is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, and most preferably 0.8 to 5 parts by mass relative to 100 parts by mass of the component (A). By being 0.1 part by mass or more, the curability of the resin can be maintained, and by being 20 parts by mass or less, the storage stability is not affected.

[0039] Furthermore, in the photocurable resin composition of the present invention, various additives can be added within the range that does not impair the characteristics of the present invention. Examples of the additives include filler materials, photo radical polymerization initiators, sensitizers, solvents, plasticizers, curing catalysts, thermal acid generators, silane coupling agents (excluding component (B)), storage stabilizers, antioxidants, ultraviolet absorbers, surfactants, dispersants, defoaming agents, tackifiers, flame retardants, lubricants, foaming agents, and the like.

[0040] Examples of the above filler include fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, calcium carbonate, talc, clay, glass beads. Among them, fumed silica is preferred because of its excellent reinforcing property. In addition, silica whose surface has been hydrophobically treated in advance with a silicone compound such as a silane or a silazane can be used. They can be used alone or in combination of two or more. The compounding amount when adding the filler is 0.1 to 300 parts by mass, more preferably 0.3 to 100 parts by mass, and particularly preferably 0.5 to 50 parts by mass relative to 100 parts by mass of the component (A) of the present invention.

[0041] As commercially available products of the above fumed silica, there is no particular limitation. As untreated fumed silica, for example, AEROSIL (registered trademark) 90, AEROSIL 130, AEROSIL 150, AEROSIL 200, AEROSIL 300, AEROSIL 380, AEROSIL OX50, AEROSIL EG50, AEROSIL TT600 (manufactured by Nippon AEROSIL Co., Ltd.) etc. can be cited. As hydrophobically treated fumed silica, for example, AEROSIL R972, AEROSIL R974, AEROSIL R976, AEROSIL R104, AEROSIL R106, AEROSIL R202, AEROSIL R805, AEROSIL R812, AEROSIL R812S, AEROSIL R816, AEROSIL R7200, AEROSIL R8200, AEROSIL R9200, AEROSIL RY50, AEROSIL NY50, AEROSIL RY300, AEROSIL RY200, AEROSIL RY200S (Nippon AEROSIL Co., Ltd.) etc. can be cited.

[0042] It is preferable to use silica having an average particle diameter of 1 nm or more and 30 μm or less as the above fumed silica. Regarding fumed silica, when using fumed silica having an average primary particle diameter of 1 nm or more and 50 nm or less, the reinforcing effect is particularly high, and thus it is more preferable.

[0043] As the above-mentioned photo radical polymerization initiator, for example, the curability can be improved by using it in combination with the component (D) of the present invention. Specific examples include acetophenones such as diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, 2-hydroxy-2-methyl-1-[4-(1-methylethenyl)phenyl]acetone oligomer; benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenones such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N,N-dimethyl-N-[2-(1-oxo-2-propenyloxy)ethyl]benzyltrimethylammonium bromide (benzenemethanaminium bromide: benzyltrimethylammonium bromide), (4-benzoylbenzyl)trimethylammonium chloride; thioxanthones such as 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-(3-dimethylamino-2-hydroxy)-3,4-dimethyl-9H-thioxanthen-9-one mesochloride (mesochloride: mesochloride); acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyl diphenylphosphine oxide. Among them, acetophenones and acylphosphine oxide compounds are preferred. They can be used alone or in combination of two or more. The compounding amount when adding the radical polymerization initiator is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the component (A) of the present invention.

[0044] As the above-mentioned sensitizer, for example, anthracene compounds, pyrene compounds, anthraquinone compounds, thioxanthone compounds, fluorenone compounds, pigments, etc. can be cited. They can be used alone or in combination of two or more. The compounding amount when adding the sensitizer is 0.1 to 50 parts by mass, preferably 0.3 to 20 parts by mass, and more preferably 0.5 to 10 parts by mass relative to 100 parts by mass of the component (A) of the present invention.

[0045] Examples of the above solvents include aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, alicyclic hydrocarbon solvents, alcohol solvents, aldehyde solvents, ketone solvents, ester solvents, ether solvents, carbonate solvents, petroleum solvents, etc. They may be used alone or in combination of two or more. When adding a solvent, the blending amount is 25 to 200 parts by mass, preferably 50 to 150 parts by mass, and more preferably 75 to 125 parts by mass with respect to 100 parts by mass of the component (D) of the present invention.

[0046] Examples of the above plasticizers include processing oils, liquid hydrocarbon compounds such as poly-α-olefins, phosphate compounds, sulfonate compounds, phthalate compounds, polyether compounds, etc. They may be used alone or in combination of two or more. In addition, the above component (C) may be previously dispersed therein.

[0047] The above curing catalyst is not particularly limited as long as it is a catalyst for crosslinking the component (A). Specifically, examples include tin compounds such as dibutyltin dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin distearate, dibutyltin laurate oxide, dibutyltin diacetylacetonate, dibutyltin dioleylmalate, dibutyltin octoate, dioctyltin oxide, dioctyltin dilaurate; as metal complexes, titanate compounds such as tetra-n-butoxytitanate, tetra-isopropoxytitanate; metal carboxylate salts such as lead octoate, lead naphthenate, nickel naphthenate, cobalt naphthenate, zinc-based compounds, iron-based compounds, bismuth; metal acetylacetone complexes such as aluminum acetylacetone complex, vanadium acetylacetone complex. In addition, amine salts such as dibutylamine-2-ethylhexanoate, organic phosphoric acid compounds such as monomethylphosphoric acid, di-n-butylphosphoric acid, other acidic catalysts and basic catalysts, etc. may also be used. They may be used alone or in combination of two or more, but it is preferred not to contain a catalyst for fear of gradual reaction during storage and increase in viscosity.

[0048] The above thermal acid generator promotes curing by heating, but in the case of being used for members that cannot be heated, it will not promote curing and becomes an impurity, so it is preferably free of a thermal acid generator.

[0049] The above storage stabilizer is not particularly limited as long as it can absorb the moisture of the photocurable resin composition or react with moisture (excluding the component (B)). For example, 4-functional alkoxysilanes such as tetramethoxysilane, tetraethoxysilane and their hydrolyzates, methyltrimethoxysilane, methyltriethoxysilane and their hydrolyzates, silicate compound classes represented by methyl silicate, ethyl silicate, propyl silicate, butyl silicate and their oligomers, etc. They may be used alone or in combination of two or more.

[0050] As the above silane coupling agent, for example, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and other silane coupling agents containing glycidyl groups, vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane and other silane coupling agents containing vinyl groups, γ-methacryloxypropyltrimethoxysilane and other silane coupling agents containing (meth)acryloyl groups, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane and other silane coupling agents containing amino groups, and other γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, styryl silane, ureido silane, thio silane, isocyanate silane, etc. (excluding component (B)). They can be used alone or in combination of two or more. It should be noted that the compounding amount when adding the silane coupling agent is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of component (A) of the present invention.

[0051] The active energy for curing the photocurable resin composition of the present invention, for example, can be ultraviolet rays, visible light, laser, and the cumulative light amount is in the range of 1 to 100 kJ / m 2 and preferably in the range of 5 to 70 kJ / m 2 and most preferably in the range of 10 to 50 kJ / m 2 In addition, as the irradiation source of the active energy ray, for example, high-pressure mercury lamp, LED, electrodeless lamp, xenon lamp, metal halide lamp, sunlight, etc. can be cited.

[0052] The present invention preferably cures at room temperature for 30 minutes to 14 days after irradiating the active energy ray. Since the irradiated composition is subsequently cured by moisture, a tough cured product can be obtained by curing for 30 minutes or more. As the curing time, it is further preferably 1 day to 10 days, and most preferably 5 to 8 days.

[0053] The resin cured product obtained by curing the photocurable resin composition of the present invention has excellent resin strength and can be used for various purposes such as bonding, sealing, casting, coating, coating agent, and forming of optical components. As specific uses, in the fields of automobiles and transportation equipment, it can be used for bonding, sealing, casting, forming, coating agent, etc. of automotive switch parts, headlamps, engine internal parts, electrical equipment parts, drive engines, brake fluid tanks, etc. In addition, in the field of flat panel displays, it can be used for bonding, sealing, casting, forming, coating agent, etc. of liquid crystal displays, organic electroluminescent devices, light emitting diode display devices, and field emission displays. In the recording field, it can be used for bonding, sealing, casting, forming, coating agent, etc. of optical discs, CDs, DVDs, MDs, pickup lenses, peripheries of hard disks (components for spindle motors, components for head actuators, etc.), Blu-ray discs, etc. In the field of electronic materials, examples include sealing materials for electronic components, circuits, electrical contacts or semiconductor elements, chip adhesives, conductive adhesives, anisotropic conductive adhesives, interlayer adhesives for multilayer substrates containing laminated substrates, solder resists, etc. In the battery field, it can be used for bonding, sealing, casting, forming, coating agent, etc. of lithium batteries, manganese batteries, alkaline batteries, nickel-based batteries, fuel cells, silicon-based solar cells, dye-sensitized solar cells, organic solar cells, etc. In the field of optical components, it can be used for bonding, sealing, casting, forming, coating agent, etc. of optical fiber materials, optical passive components, optical circuit components, peripheries of optoelectronic integrated circuits, etc. around optical switches and optical connectors in optical communication systems. In the field of optical devices, it can be used for bonding, sealing, casting, forming, coating, etc. of lens materials for still cameras, viewfinder prisms, target prisms, viewfinder covers, light receiving sensor parts, photographing lenses, projection lenses for projection TVs, etc. In addition, in image display devices such as liquid crystals and touch panels, there is a gap between a protective part such as glass and an image display part, and the photocurable resin composition of the present invention can be used to fill this gap. In addition, the resin cured product obtained by curing the photocurable resin composition of the present invention has excellent concealment of the colorant, so it can also be used for potting of electronic components and wiring.

[0054] Examples

[0055] Next, examples are given to explain the present invention in more detail, but the present invention is not limited to these examples. In addition, unless otherwise specified, the tests are carried out in an environment of 25°C and 55% RH.

[0056] [Examples 1 to 3 and Comparative Examples 1 to 4]

[0057] To prepare the photocurable resin composition, the following components were prepared. Hereinafter, the photocurable resin composition is also simply referred to as the composition.

[0058] (A) Component: An organic polymer having two or more alkoxysilyl groups per molecule

[0059] · SAX530 (an organic polymer having a polyether backbone and trimethoxysilyl groups at both ends, viscosity: 7 Pa·s, manufactured by Kaneka Corporation)

[0060] · MA451 (a mixture of an organic polymer having a polyether backbone and containing trimethoxysilyl groups and an organic polymer having an acrylic polymer backbone and containing trimethoxysilyl groups, viscosity: 90 Pa·s, manufactured by Kaneka Corporation)

[0061] (B) Component: A compound having an isocyanuric acid ring and an alkoxysilyl group per molecule

[0062] · KBM-9659 (tris(3-trimethoxysilylpropyl) isocyanurate, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0063] (B)' Component: A compound other than (B)

[0064] · ARONIX M313 (ethylene oxide-modified triacrylate isocyanurate acid, manufactured by Toagosei Co., Ltd.)

[0065] · KBM-9007 (3-isocyanatopropyltriethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0066] (C) Component: Pigment

[0067] · MV Black T-01 (pigment: carbon black (25% by mass), plasticizer: phenyl alkyl sulfonate (75% by mass), manufactured by Mikuni Pigment Co., Ltd.)

[0068] · ZA Black 3026 (pigment: carbon black (25% by mass), plasticizer: polyoxyalkylene alkyl ether (75% by mass), manufactured by Mikuni Pigment Co., Ltd.)

[0069] (C)' Component: Other colorants

[0070] · elixaBlack 850 (aromatic black dye, ORIENT Chemical Industries Co., Ltd.)

[0071] (D) Component: Photoacid generator

[0072] · CPI-200K (photoacid generator: diphenyl[4-(phenylthio)phenyl]sulfonium = trifluorotris(pentafluoroethyl)-λ 5 -phosphonium hydride salt (50% by mass), solvent: propylene carbonate (50% by mass), manufactured by San-Apro Ltd.).

[0073] The manufacturing methods of the compositions involved in Examples 1 to 3 and Comparative Examples 1 to 4 are as described below. Under shading, the components (A), (B) (or component (B)'), (C) (or component (C)'), and (D) were weighed at room temperature, and stirred for 30 minutes using a planetary mixer. Using the planetary mixer, stirring was further carried out while degassing under vacuum for 30 minutes to obtain a photocurable resin composition. The obtained photocurable resin compositions were all in a liquid state at 25°C. The detailed preparation amounts are as shown in Table 1, and all values are shown in parts by mass.

[0074] <Surface Curing Test>

[0075] The composition was uniformly coated on a SUS304 plate with a thickness of 1.6 mm × width of 25 mm × length of 100 mm to a thickness of 1 mm, and irradiated with a cumulative light amount of 30 kJ / m 2 using a conveyor belt type UV-LED irradiation device. Subsequently, it was cured and aged for 1 week in an environment of 23°C and 50% RH. After aging, the surface of the cured product was touched with a fingertip after cleaning with alcohol to confirm the presence or absence of stickiness, and evaluated according to the following evaluation criteria. Considering the pollution to the surroundings during machining, in the present invention, it is preferably as non-sticky as possible. Therefore, it is preferably △ or ○, and most preferably ○. In addition, "-" in the test results means that the composition was separated and a uniform test piece could not be made.

[0076] [Evaluation Criteria]

[0077] ○: No fingerprints adhered to the surface of the cured product.

[0078] △: Fingerprints adhered to the surface of the cured product.

[0079] ×: Resin adhered to the finger.

[0080] <Total Light Transmittance Measurement>

[0081] The composition was uniformly coated on a non-alkali glass plate with a thickness of 0.7 mm × width of 50 mm × length of 50 mm to a thickness of 30 μm, and irradiated with a cumulative light amount of 30 kJ / m 2 using a conveyor belt type UV-LED irradiation device. Subsequently, it was cured and aged for 1 week in an environment of 23°C and 50% RH. After aging, a total light transmittance measurement was carried out using a spectro haze meter SH7000 manufactured by Nippon Denshoku Industries Co., Ltd. The light transmittance was measured in the wavelength range from 780 nm to 380 nm, the number of tests was n = 3, and the average value was calculated and evaluated based on the following evaluation criteria. The detailed content conforms to JIS K 7361-1:1997. From the viewpoint of concealment, the evaluation is preferably ○. In addition, "-" in the test results means that the composition was not cured and a test piece could not be made.

[0082] [Evaluation Criteria]

[0083] ○: Total light transmittance is 0.1% or less

[0084] ×: Total light transmittance exceeds 0.1%

[0085] <Tensile Strength Test>

[0086] Flow the composition into the set fixture in such a way that the composition forms a sheet with a thickness of 0.5 mm, a width of 200 mm, and a length of 200 mm, and irradiate it with a cumulative light amount of 30 kJ / m using a conveyor - type UV - LED irradiation device 2 Then, cure and solidify it for 1 week in an environment of 23°C and 50% RH. Cut the obtained cured product into strips with a thickness of 0.5 mm, a width of 10 mm, and a length of 60 mm to produce test pieces. Fix both ends of the test piece to the chuck in such a way that the long axis of the produced test piece and the center of the chuck are in a straight line. Use a universal tensile testing machine to stretch the test piece at a stretching speed of 50 mm / min, and measure the maximum load. Take the strength at this maximum load as the "tensile strength (MPa)". The results are shown in Table 1. The detailed content follows JIS K 6251 (2010). It should be noted that in the present invention, from the viewpoint of having an excellent effect on preventing resin cracking caused by vibration, impact, etc., the tensile strength of the cured product is preferably 0.4 MPa or more, more preferably 0.6 MPa or more. There is no particular limitation on the upper limit value of this test, but it is preferably 3.0 MPa or less, and further preferably 1.0 MPa or less. In addition, "-" in the test results means that the composition was not cured and test pieces could not be produced, or the measurement was not carried out due to deteriorated concealment performance

[0087] [Table 1]

[0088]

[0089] Examples 1 - 3 are compositions containing components (A) - (D), and excellent surface curability and tensile strength were confirmed. On the other hand, Comparative Example 1 is a composition using a compound containing an isocyanuric acid ring but no alkoxysilyl group to replace component (B). The surface curability deteriorated, and stickiness was confirmed in the cured product. In addition, even in terms of tensile strength, it was deteriorated compared with Example 1, and a cured product prone to cracking, etc. was confirmed. Comparative Example 2 is a composition in which component (B) is changed to a compound containing an isocyanate group and an alkoxysilyl group. The curability deteriorated, and a cured product could not be produced. Comparative Example 3 is a composition without component (B). The surface curability deteriorated, and stickiness was confirmed in the cured product. In addition, even in terms of tensile strength, it was deteriorated, and a cured product prone to cracking, etc. was confirmed. Comparative Example 4 is a composition using a dye to replace component (C). The total light transmittance is high, and sufficient concealment performance was not obtained

[0090] This application is based on Japanese Patent Application No. 2022-199425 filed on December 14, 2022, the entire disclosure of which is incorporated herein by reference.

[0091] Industrial applicability

[0092] In recent years, plastics have been widely used as components in electrical and electronic parts. Since the heat resistance of plastics is inferior to that of metals, it is desirable to minimize heating. The present invention is a photocurable resin composition that is not heated during curing, and furthermore, even when colored, it has excellent surface curability and strength. Based on these characteristics, the present invention can be used for the assembly and potting of various electrical and electronic parts, etc., and a variety of uses can be developed.

Claims

1. A photocurable resin composition, wherein, Containing the following components (A) to (D); (A) component: an organic polymer having two or more alkoxysilyl groups in each molecule; (B) component: a compound having an isocyanuric acid ring and an alkoxysilyl group in each molecule; (C) component: a pigment; (D) component: a photoacid generator.

2. The photocurable resin composition according to claim 1, wherein the (A) component contains an organic polymer having a polyether backbone and two or more alkoxysilyl groups in each molecule.

3. The photocurable resin composition according to claim 1, wherein the (A) component contains an organic polymer having a polyether backbone and two or more alkoxysilyl groups in each molecule, and an organic polymer having a vinyl-based polymer backbone and two or more alkoxysilyl groups in each molecule.

4. The photocurable resin composition according to claim 1, wherein the (C) component is carbon black.

5. The photocurable resin composition according to claim 1, wherein the (D) component is an onium salt compound.

6. The photocurable resin composition according to claim 1, wherein the (D) component is a sulfonium salt compound.

7. The photocurable resin composition according to claim 1, wherein the (B) component is tris(3-trimethoxysilylpropyl) isocyanurate.

8. A cured product, wherein it is obtained by curing the photocurable resin composition according to claim 1.

9. The cured product according to claim 8, wherein the total light transmittance is 0.1% or less and the tensile strength is 0.4 MPa or more.

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