Active energy ray-curable resin composition and laminate

Abstract

The present invention, by providing excellent filling performance, addresses the problem of improving productivity of an FRP coated article that has high designability, and protecting the FRP coated article from long-term outdoor exposure. This active energy ray-curable resin composition comprises: component (A) which is an acrylic polyol; component (B) which is a (meth)acrylate having three or more functional groups; component (C) which is a viscosity modifier composed of a cellulose ester resin; component (D1) which is an acylphosphine-based photopolymerization initiator; component (D2) which is a hydrogen abstraction type photopolymerization initiator; component (E) which is an ultraviolet absorber; component (F) which is a dilution solvent; and component (G) which is a polyisocyanate.

Description

Active energy ray-curable resin composition and laminate

[0001] The present invention relates to an active energy ray-curable resin composition and a laminate.

[0002] Fiber-reinforced plastics (hereinafter referred to as "FRP") are lightweight yet have rigidity equal to or greater than that of metals such as iron and aluminum, and because they exhibit various properties depending on the type, shape, and weave of the fibers, they are effective materials for reducing the weight of automobiles and other vehicles.

[0003] In recent years, there has been an increase in painted automobile parts that display fiber patterns as a design and are protected with a transparent paint. However, when a conventional thermosetting transparent resin composition made from an acrylic polyol and a polyisocyanate is applied and baked, pinholes (hereafter referred to as "pinholes") are formed due to tiny air bubbles contained within the fibers, significantly degrading the paint appearance.

[0004] In addition, since the fabric is woven and unevenness occurs at the intersections of the warp and weft threads, a smooth surface could not be obtained even when a conventional resin composition was applied.

[0005] In other words, with conventional methods, polishing, painting, and baking were repeated many times until pinholes and surface irregularities disappeared, resulting in extremely poor production efficiency.

[0006] Furthermore, the matrix resins required for shaping FRP are epoxy resins, acrylic resins, etc., but they do not have the weather resistance to withstand long-term exposure to sunlight, so they need to be protected with a transparent resin composition, which, as mentioned above, consumes a lot of work time, energy, and human resources.

[0007] Although about a century has passed since FRP was invented and began to be widely used, a method for fundamentally resolving issues such as pinholes has yet to be established. Patent Document 1 addresses this issue by combining UV curing and heat curing to suppress the occurrence of pinholes, but this method relies on the use of a mercury lamp that emits a wide range of light from ultraviolet to infrared, and therefore does not adequately suppress pinholes that occur when the substrate is rapidly heated by infrared rays during UV irradiation. Additionally, when applied to transparent resin compositions, there is the issue of insufficient long-term outdoor weather resistance.

[0008] Conventional UV-curable resin compositions for vehicles that have long-term outdoor weather resistance are disclosed in Patent Documents 2 to 4, etc., but because much of the UV light from mercury lamps overlaps with the absorption wavelength of UV absorbers, it has been difficult to ensure UV curability from the deepest recesses to the outermost surface of the coating film in FRP that has scattered surface irregularities, while performing uniform UV curing on a three-dimensional FRP article to suppress pinholes, using a design that only involves UV curing.

[0009] Patent Documents 5 to 7, which are characterized by adding an ultraviolet absorber to a UV-curable resin composition and curing it by light emitted from an LED, are ink compositions for posters and the like that are printed by inkjet printing or the like and are intended for outdoor use, and are not suitable for the long-term outdoor weather resistance required for vehicles that this paint is intended for.

[0010] Patent Document 8 describes a resin composition that is cured by light emitted from an LED for indoor use, such as on a floor, where a certain amount of outdoor light is expected to penetrate. Specifically, malonic acid ester-based ultraviolet absorbers and anilide oxalate-based ultraviolet absorbers are specified, but these are not suitable for the long-term outdoor weather resistance required for the vehicles for which this paint is intended.

[0011] Japanese Patent No. 6940720 Japanese Patent No. 6279800 Japanese Patent Application Laid-Open No. 2023-148022 Japanese Patent No. 6451627 Japanese Patent Application Laid-Open No. 2019-081867 Japanese Patent No. 6988237 Japanese Patent Application Laid-Open No. 2014-083782 Japanese Patent Application Laid-Open No. 2018-131481

[0012] The problem that this invention aims to solve is to improve productivity and protect highly aesthetically pleasing coated FRP articles from long-term outdoor exposure through excellent sealing performance. Sealing performance refers to the ability to seal potential defects in FRP, such as air bubbles, bubble-caused holes, and fiber segregation. Specifically, it refers to the ability to form a smooth coated surface without conforming to crater-like depressions caused by air expansion and bubble bursting that occur when painting FRP, depressions caused by liquid paint being sucked into bubble-caused holes immediately after painting, and uneven surfaces caused by fiber bias and weaving. (At the same time, the use of an LED light source contributes to energy savings and the creation of a mercury-free work environment by eliminating the need for mercury lamps.)

[0013] The active energy ray-curable resin composition according to the present invention comprises: component (A): an acrylic polyol; component (B): a tri- or higher functional (meth)acrylate; component (C): a viscosity modifier consisting of a cellulose ester resin; component (D1): an acylphosphine photopolymerization initiator; component (D2): a hydrogen abstraction photopolymerization initiator; component (E): an ultraviolet absorber; component (F): a diluent solvent; and component (G): a polyisocyanate, wherein the weight average molecular weight of component (A) is 25,000 to 65,000; the hydroxyl value of component (A) is 30 to 100 mgKOH / g; the glass transition temperature (hereinafter referred to as "Tg") of component (A) is -20 to 20°C; component (A) has an acid value; the component (D1) is at least one selected from the group consisting of diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl phenyl(2,4,6-trimethylbenzoyl)phosphinate, bis(2,6-dimethoxybenzoyl)2,4,4-trimethylpentylphosphine oxide, and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide; the content of the component (A) is 35 to 75 parts by mass, relative to a total of 100 parts by mass of the components (A) and (B); the content of the component (C) is 3 to 10 parts by mass, relative to a total of 100 parts by mass of the components (A) and (B); and the content of the component (D1) is 1 to 25 parts by mass, relative to a total of 100 parts by mass of the components (A) and (B). This allows for improved productivity of highly decorative FRP coated articles due to their excellent sealing performance, and also makes it possible to protect them from long-term outdoor exposure.

[0014] In one embodiment of the active energy ray-curable resin composition according to the present invention, the component (B) is at least one selected from the group consisting of tris(2-(meth)acryloyloxyethyl) isocyanurate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate, The component (D2) is selected from the group consisting of benzophenone, 4-methylbenzophenone, 4-phenylbenzophenone, 2-ethylhexyl 2-(1,1'-biphenyl-4-yl)carbonylbenzoate, 4-benzoyl-4'-methyldiphenyl sulfide, methyl 2-benzoylbenzoate, 1-[4-(4-benzoylphenylsulfanyl)phenyl]-2-methyl-2-(4-methylphenylsulfonyl)propan-1-one, polyethylene glycol bis(para-dimethylaminobenzoate), methyl benzoylformate, thioxane at least one selected from the group consisting of coumarin, 2,4-diethylthioxanthen-9-one, 2-isopropylthioxanthone, 3-benzoyl-7-(N,N-diethylamino)coumarin, 7-methoxy-3-(4-tert-butyl-benzoyl)coumarin, 3-(4-tert-butylbenzoyl)benzo[f]coumarin, 7-ethylthio-3-benzoylcoumarin, 3-(4-tert-butylbenzoyl)-5,7-dimethoxycoumarin, and 7-(sec-butylthio)-3-benzoylcoumarin; The component (E) is at least one selected from the group consisting of a benzotriazole-based ultraviolet absorber, a hydroxyphenyltriazine-based ultraviolet absorber, and a benzophenone-based ultraviolet absorber, the content of the component (D2) is 1 to 10 parts by mass per 100 parts by mass of the total of the components (A) and (B), and the content of the component (E) is 1 to 20 parts by mass per 100 parts by mass of the total of the components (A) and (B).

[0015] In one embodiment of the active energy ray-curable resin composition according to the present invention, the component (G) contains at least one selected from the group consisting of a biuret type, an isocyanurate type, and an adduct type, The ratio of the number of moles of isocyanate groups in the component (G) to the number of moles of hydroxyl groups in the component (A) (number of moles of isocyanate groups) / (number of moles of hydroxyl groups) is 0.7 to 3.0.

[0016] In one embodiment of the active energy ray-curable resin composition according to the present invention, the light source device for the active energy rays emitted from the light emitting diode having a peak wavelength of 350 to 420 nm may be a light source device including a plurality of light emitting diodes that emit light of at least one peak wavelength, or a light source device including a plurality of light emitting diodes that emit light of a plurality of peak wavelengths, and the light source device has a peak illuminance of 15 mW / cm. ２ This allows the material to harden.

[0017] The laminate according to the present invention comprises a substrate and a coating film of any one of the above active energy ray-curable resin compositions on at least a portion of the surface of the substrate, the coating film comprising at least one layer.

[0018] In one embodiment of the laminate according to the present invention, the coating film has a thickness of 10 to 120 μm.

[0019] In one embodiment of the laminate according to the present invention, the substrate contains reinforcing fibers, and the reinforcing fibers are at least one selected from the group consisting of carbon fibers, boron fibers, aramid fibers, glass fibers, Kevlar fibers, Dyneema fibers, Zylon fibers, cellulosic fibers, gold threads, and silver threads.

[0020] The active energy ray-curable and thermosetting transparent resin composition of the present invention protects FRP having high designability from long-term outdoor exposure and has excellent sealing properties.

[0021] FIG. 1 is a diagram specifically showing a method for reading Tg from a chart in the method for measuring Tg in the present invention.

[0022] The FRP coated object to which the resin composition of the present invention can be applied is an FRP formed by layering fiber sheets, etc., and is a composite material of a sheet woven with long-chain fibers and a matrix resin.It is lightweight and has specific strength and specific stiffness equivalent to or greater than metal, so it can be used in a variety of applications, from sports and leisure goods to automobiles, aircraft, agricultural machinery, fishing machinery, and space development.

[0023] The resin composition of the present invention is particularly preferably applied directly to the FRP, and may be used on FRP that has been sanded or sandblasted to an extent that does not damage the fibers, or that has had gaps or irregularities generated between intersecting fibers filled with putty.

[0024] Component (A) Component (A) in the above resin composition contains an acrylic polyol, and compared to FRP, which has an extremely high property of returning to its original shape when deformation caused by an external force is removed from the resin (hereinafter referred to as "elasticity"), this component is able to withstand the adhesiveness to the matrix resin and the characteristic behavior of the material over a long period of time.

[0025] Component (A) is an acrylic polyol having a weight-average molecular weight of 25,000 to 65,000, a hydroxyl value of 30 to 100 mgKOH / g, a Tg of −20 to 20° C., and an acid value, and the weight-average molecular weight of component (A) is 25,000 to 65,000, preferably 35,000 to 55,000, and more preferably 40,000 to 50,000. If the weight-average molecular weight is less than 25,000, cracking and peeling are likely to occur in impact tests, etc., and if it is 65,000 or more, atomization during spray coating is poor, resulting in a poor coating appearance.

[0026] The hydroxyl value of the component (A) is 30 to 100 mgKOH / g. If the hydroxyl value is less than 30 mgKOH / g, crosslinking with the component (A) is insufficient, resulting in reduced physical properties such as water resistance. If the hydroxyl value is 100 mgKOH / g or more, impact resistance is reduced.

[0027] The acid value of the component (A) is preferably less than 10 mgKOH / g in view of the balance between adhesion to the substrate and water resistance.

[0028] Component (B) Component (B) in the above resin composition contains a tri- or higher functional (meth)acrylate having at least one partial structure selected from the group consisting of molecular structures containing an isocyanuric acid skeleton, a trimethylolpropane skeleton, and a pentaerythritol skeleton, and is polymerized by radicals generated from the photopolymerization initiators of components (D1) and (D2) upon irradiation with active energy rays, and suppresses pinholes resulting from air bubbles encapsulated in the FRP.

[0029] Component (B) in the resin composition is at least one suitably selected from the group consisting of tris(2-(meth)acryloyloxyethyl) isocyanurate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

[0030] In addition, the component (B) is obtained by reacting an isocyanate of an isocyanurate obtained by trimerization of hexamethylene diisocyanate, isophorone diisocyanate, or the like with a (meth)acrylic monomer having a hydroxyl group, such as 2-hydroxyethyl (meth)acrylate, glycerin di(meth)acrylate, trimethylolpropane di(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, or dipentaerythritol penta(meth)acrylate. Also suitable are urethane (meth)acrylates obtained by reacting a diisocyanate such as urethane (meth)acrylate, hexamethylene diisocyanate, or 4,4'-methylenebis(cyclohexyl isocyanate) with a (meth)acrylic monomer having a hydroxyl group such as trimethylolpropane di(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, or dipentaerythritol penta(meth)acrylate.

[0031] From the viewpoint of coating appearance, tris(2-(meth)acryloyloxyethyl) isocyanurate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate, which have no urethane bond, are more preferably selected.

[0032] When the total mass of the components (A) and (B) is 100 parts by mass, the component (A) is 35 to 75 parts by mass and the component (B) is 25 to 65 parts by mass. If the component (A) is less than 35 parts by mass and the component (B) is 65 parts by mass or more, impact resistance and the like will decrease, and if the component (A) is 75 parts by mass or more and the component (B) is less than 25 parts by mass, pinhole prevention will decrease. Preferably, the component (A) is 40 to 60 parts by mass and the component (B) is 60 to 40 parts by mass.

[0033] Component (C) in the resin composition: Component (C): a viscosity adjuster consisting of at least one cellulose ester resin adjusts the viscosity to suppress suction due to capillary action or the like caused by gaps or depressions between crossing fibers, and improves the heat resistance, impact resistance, etc. of the coating film. The cellulose ester resin is suitably selected from cellulose acetate resin, cellulose propionate resin, and cellulose butyrate resin, and as the cellulose acetate resin, Examples of cellulose propionate resins include CAP-482-20 (manufactured by Eastman Chemical Co.), and examples of cellulose butyrate resins include CAB-551-0.01, CAB-551-0.2, CAB-553-0.4, CAB-381-0.1, CAB-381-0.5, CAB-381-2, CAB-381-2 BP, CAB-381-20, and CAB-381-20 BP (manufactured by Eastman Chemical Co.).

[0034] The amount of the component (C) is 3 to 10 parts by mass, preferably 4 to 6 parts by mass, per 100 parts by mass of the total of the components (A) and (B).

[0035] Component (D1) Component (D1): at least one acylphosphine-based photopolymerization initiator in the resin composition suppresses pinholes originating from air bubbles encapsulated in the FRP in combination with active energy rays emitted from a light-emitting diode having a peak wavelength of 350 to 420 nm, component (D2), and component (B).

[0036] Component (D1) is at least one compound selected from diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl phenyl(2,4,6-trimethylbenzoyl)phosphinate, bis(2,6-dimethoxybenzoyl)2,4,4-trimethylpentylphosphine oxide, and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, and is contained in an amount of 1 to 25 parts by mass per 100 parts by mass of the total of components (A) and (B). If the amount of component (D1) added is less than 1 part by mass, pinhole suppression will be reduced due to insufficient curing of component (B) by active energy rays, while if it is 25 parts by mass or more, polishability, water resistance, solvent resistance, etc. will be reduced.

[0037] Component (D2) Component (D2): at least one hydrogen abstraction photopolymerization initiator in the resin composition suppresses pinholes resulting from air bubbles encapsulated in the FRP in combination with active energy rays emitted from a light-emitting diode having a peak wavelength of 350 to 420 nm, and with components (D1) and (B).

[0038] Examples of the component (D2) include benzophenone, 4-methylbenzophenone, 4-phenylbenzophenone, 2-ethylhexyl 2-(1,1'-biphenyl-4-yl)carbonylbenzoate, 4-benzoyl-4'-methyldiphenyl sulfide, methyl 2-benzoylbenzoate, 1-[4-(4-benzoylphenylsulfanyl)phenyl]-2-methyl-2-(4-methylphenylsulfonyl)propan-1-one, polyethylene glycol bis(para-dimethylaminobenzoate), methyl benzoylformate, thioxanthone, 2,4- Diethylthioxanthen-9-one, 2-isopropylthioxanthone, 3-benzoyl-7-(N,N-diethylamino)coumarin, 7-methoxy-3-(4-tert-butyl-benzoyl)coumarin, 3-(4-tert-butylbenzoyl)benzo[f]coumarin, 7-ethylthio-3-benzoylcoumarin, 3-(4-tert-butylbenzoyl)-5,7-dimethoxycoumarin, 7-(sec-butylthio)-3-benzoylcoumarin, 2,3,5,6-1H,4H-tetrahydroquinolizino[9,9a,1-gh]coumarin The compound is one or more compounds selected from the group consisting of 3-benzoyl-5,7-dimethoxycoumarin, 7-methoxy-3-(4-methylbenzoyl)coumarin, 3-(4-methylbenzoyl)benzo[f]coumarin, TR-PSS-202 (manufactured by TRONLY), and ESACURE 3644 (manufactured by IGM Resins), and is contained in an amount of 0.5 to 5 parts by mass per 100 parts by mass of the total of components (A) and (B). If the amount of component (D2) added is less than 0.5 parts by mass, pinhole suppression will be reduced due to insufficient curing of component (B) by active energy rays, and if it is 5 parts by mass or more, polishing properties will be reduced.

[0039] Component (E) Component (E): at least one ultraviolet absorber in the resin composition protects the cured coating film of the resin composition and the matrix resin of the FRP from ultraviolet rays contained in sunlight over a long period of time.

[0040] As the component (E), a benzotriazole-based ultraviolet absorber, a hydroxyphenyltriazine-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, or a cyanoacrylate-based ultraviolet absorber is preferably used.

[0041] Examples of the benzotriazole-based ultraviolet absorber include 2-(5-tert-butyl-2-hydroxyphenyl)benzotriazole, C7-C9-alkyl-3-[3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl]propionether, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, Tinuvin PS, Tinuvin 384-2, Tinuvin 900, Tinuvin 928, and Tinuvin 1130 (manufactured by BASF).

[0042] Examples of hydroxyphenyltriazine-based ultraviolet absorbers include 2-[4-[(2-hydroxy-3-tridecylpropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 4-[4,6-bis(2,4-xylyl)-1,3,5-triazin-2-yl]benzene-1,3,5-triazine, which has 5-[3-(2-ethylhexyloxy)-2-hydroxypropoxy]-2-[4,6-bis(2,4-xylyl)-1,3,5-triazin-2-yl]phenol as the main component. reaction products of 4,4',4''-(1,3,5-triazine-2,4,6-triyl)tris(benzene-1,3-diol) containing 5,5'-dibutoxy-2,2'-[6-(2,4-dibutoxyphenyl)-1,3,5-triazine-2,4-diyl]diphenol as the main component and butyl bromide; and TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 477, and TINUVIN 479 (manufactured by BASF).

[0043] Examples of the benzophenone-based ultraviolet absorber include octabenzone, dioxybenzone, 2,4-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, KEMISORB11, KEMISORB12, KEMISORB111 (manufactured by Chemipro Chemical Co., Ltd.), Eversorb10, Eversorb11, Eversorb12, Eversorb51, Eversorb52, EversorbCP01, and EversorbCP02 (manufactured by Everlite Chemical Co., Ltd.).

[0044] Examples of cyanoacrylate ultraviolet absorbers include Uvinal 3035, Uvinal 3039, and Uvinal 3030FF.

[0045] Component (E) is contained in an amount of 1 to 20 parts by mass per 100 parts by mass of the total of components (A) and (B). If the amount of component (E) added is less than 1 part by mass, weather resistance decreases, and if it is 20 parts by mass or more, water resistance, abrasion resistance, and economy decrease. If the amount of component (E) added is 1 to 2 parts by mass, the coating film thickness becomes thick, and if it is 15 to 20 parts by mass, no problems arise in weather resistance, etc., even if the film thickness is thin.

[0046] Component (E) may be composed of any of the ultraviolet absorbers alone, but depending on the ultraviolet absorption characteristics, it may be better to use a combination of two or more types, and it is more preferable to combine a benzotriazole-based ultraviolet absorber with a hydroxyphenyltriazine-based ultraviolet absorber.

[0047] Component (E) may be a combination of light stabilizers, and examples of light stabilizers include bis[2,2,6,6-tetramethyl-1-(octyloxy)piperidin-4-yl] decanedioate, bis[1,2,2,6,6-pentamethyl-4-piperidinyl] 2-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]-2-butylpropanedioate, bis[1,2,2,6,6-pentamethyl-4-piperidinyl] 2,4-bis[N-butyl-N-(1-cyclohexyl-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-(2-hydroxyethylamine)-1,3,5-trimethylpropanedioate, and bis[1,2,2,6,6-tetramethyl-1-octyloxy)piperidin-4-yl] methyl]-2-butylpropanedioate. azine, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1-methyl 10-(1,2,2,6,6-pentamethyl-4-piperidinyl) decanedioate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis[2,2,6,6-tetramethyl-1-(octyloxy)piperidin-4-yl] decanedioate, TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 249, TINUVIN 292, TINUVIN 770DF, TINUVIN 5100 (manufactured by BASF Co., Ltd.), and the like.

[0048] Component (F) Component (F): dilution solvent in the resin composition is used to adjust the viscosity when applied to the FRP, and the amount and type can be selected according to the application method, such as air spray method, airless spray method, or bell coating method.

[0049] Component (G) Component (G): at least one polyisocyanate in the above resin composition reacts with the hydroxyl groups of the acrylic polyol of component (A) to form urethane bonds, thereby increasing the crosslink density of the cured coating film and improving the weather resistance, chemical resistance, adhesion, and hardness of the cured coating film.

[0050] The polyisocyanate of component (G) is not particularly limited as long as it is a compound having two or more isocyanate groups, and examples thereof include aromatic compounds such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, and metaxylylene diisocyanate; aliphatic compounds such as hexamethylene diisocyanate; alicyclic compounds such as isophorone diisocyanate; and monomers thereof and polymers such as biuret types, nurate types, and adduct types thereof.

[0051] Commercially available polyisocyanates of component (G) include Duranate 24A-90PX (manufactured by Asahi Kasei Corporation), Sumidur N-3200-90M (manufactured by Sumitomo Bayer Urethanes Co., Ltd.), Takenate D165N-90X (manufactured by Mitsui Chemicals, Inc.), Sumidur N-3300, Sumidur N-3500 (manufactured by Sumitomo Bayer Urethanes Co., Ltd.), Duranate TPA-100 (manufactured by Asahi Kasei Corporation), etc. Blocked isocyanates obtained by blocking these isocyanates can also be used as needed.

[0052] The compounding ratio of component (G) polyisocyanate to component (A) acrylic polyol is preferably such that NCO / OH [number of moles of isocyanate groups in polyisocyanate (B) / total number of moles of hydroxyl groups in acrylic polyol (A)] is 0.7 to 3.0, more preferably 1.0 to 2.5, and even more preferably 1.2 to 2.0. If the ratio is below the lower limit, the crosslink density of the cured coating film will be insufficient, resulting in reduced water resistance, etc. If the ratio is above the upper limit, the abrasion resistance after irradiation with active energy rays will be reduced.

[0053] For the resin composition of the present invention, the irradiation energy and irradiation time of active energy rays may be adjusted depending on the estimated time required to produce one FRP product (hereinafter referred to as "takt time"). When a long irradiation time can be ensured, the amounts of component (D1) and component (D2) may be reduced, and when the irradiation time is to be shortened, the amounts of component (D1) and component (D2) may be increased.

[0054] In addition, assuming that the resin composition of the present invention is applied to an FRP having an uneven surface, the film thickness of the resin composition of the present invention is 10 to 120 μm. In the case of a thin film, the amounts of component (D1) and component (D2) should be small, and in the case of a thick film, the amounts of component (D1) and component (D2) should be large.

[0055] If the film thickness of the resin composition of the present invention is less than 10 μm, it will not be possible to form a film that conceals the surface irregularities of the FRP, and if it is 120 μm or more, it will result in poor appearance such as sagging and an increased amount of paint used, which is economically disadvantageous. The film thickness is preferably 20 to 80 μm, more preferably 30 to 60 μm.

[0056] The resin composition of the present invention is characterized in that it undergoes a polymerization reaction using active energy rays having a wavelength selected from at least one type emitted from an LED having a peak wavelength of 350 to 420 nm.

[0057] If an LED with a peak wavelength less than 350 nm is used, the wavelength overlaps with the absorption wavelength band of the ultraviolet absorber (component (E)), which has strong absorption in the 280-340 nm range, preventing the polymerization reaction from proceeding, resulting in reduced pinhole sealing, water resistance, abrasion resistance, and weather resistance. Additionally, since the present invention is a transparent resin composition, the irradiated active energy rays also irradiate the FRP. The absorption wavelengths calculated from the carbon-hydrogen and carbon-carbon bond energies are 293 nm and 339 nm, respectively. Therefore, if an LED with a peak wavelength less than 350 nm is used, the curing reaction of the coating film and the deterioration reaction of the resin composition and FRP occur in parallel, preventing the long-term outdoor weather resistance targeted by the present invention from being achieved. These phenomena are also observed when using a mercury lamp, xenon lamp, or other lamp with numerous emission lines less than 350 nm. E = hc / λ (Equation 1), where h is Planck's constant (6.626 x 10 －３４ J・s) c: Speed ​​of light (2.998×10 ８ m / s) λ: wavelength of electromagnetic wave (10 －９ m) Carbon-hydrogen bond: 458.0 kJ / mol (293 nm) Carbon-carbon bond: 353.2 kJ / mol (339 nm)

[0058] When an LED with a peak wavelength of 420 nm or more is used, the photopolymerization initiators of components (D1) and (D2) do not have a high absorption band, and therefore the polymerization reaction does not proceed, resulting in a decrease in water resistance, abrasion resistance, weather resistance, and the like.

[0059] When using mercury lamps, xenon lamps, or other lamps that emit numerous emission lines above 420 nm, it is not possible to completely prevent pinholes from occurring when the bubbles contained within the FRP suddenly expand and burst due to the heat from the lamp bulb and the infrared rays emitted during emission.

[0060] The resin composition of the present invention uses active energy rays emitted from an LED having a peak wavelength of 350 to 420 nm, so the above-mentioned phenomenon does not occur and FRP coated articles having long-term outdoor weather resistance can be obtained.

[0061] The LED for curing the present resin composition with active energy rays has a peak wavelength of 350 to 420 nm, preferably 380 to 415 nm, and more preferably 390 to 410 nm.

[0062] The energy required for curing the resin composition of the present invention is measured using an actinometer specifically designed for LEDs, and the cumulative light amount is 250 mJ / cm. ２ Peak irradiance 15mW / cm ２ As described above, there is no limitation on the irradiation time, but from the viewpoint of productivity, it is preferable to adjust the irradiation time to a longer time in accordance with the takt time.

[0063] The resin composition may contain other known additives or auxiliaries such as resins, dispersants, anti-settling agents, thickeners, rust inhibitors, surface conditioners, antifoaming agents, substrate wetting agents, electrostatic aids, light stabilizers, fluorescent brighteners, amine synergists, urethane curing catalysts, and anti-blocking agents, and may also contain known colorants such as color pigments, extender pigments, rust inhibitors, and dyes in a concentration range in which the material pattern of the FRP can be visually confirmed.

[0064] The transparent resin composition of the present invention may contain an amine synergist, which has the effect of reducing irradiation energy or shortening irradiation time. Examples of the amine synergist include 2-ethylhexyl-4-(dimethylamino)benzoate, ethyl-4-(dimethylamino)benzoate, poly(ethylene glycol)bis(para-dimethylaminobenzoate), N-methyldiethanolamine, N,N-dimethylaminoethanol, N,N-dibutylaminoethanol, Omnirad EHA, Omnirad EDB, Omnirad ASA, Esacure A198 (manufactured by IGM Resins), Amino Alcohol MDA, Amino Alcohol 2Mabs, and Amino Alcohol 2B (manufactured by Nippon Nyukazai Co., Ltd.).

[0065] The urethane curing catalyst may be selected from acids, bases, transition metals, or tin-based catalysts, titanium-based catalysts, zirconia-based catalysts, bismuth-based catalysts, and organic amine-based catalysts, and examples thereof include acetic acid, trifluoroacetic acid, ammonia, triethylamine, diethylamine, Ti, Ni, Sn, di-n-butyltin(IV) dilaurate, titanium diisopropoxybis(ethylacetoacetate), titanium tetra-n-butoxide, titanium tetra-2-ethylhexoxide, titanium tetraacetylacetonate, zirconium tetraacetylacetonate, zirconium tetra-n-butoxide, zirconium dibutoxybis(ethylacetoacetate), bismuth tris(2-ethylhexanoate), 1,8-diazabicyclo[5.4.0]undecene-7, 1,5-diazabicyclo[4.3.0]nonene-5, and the like.

[0066] A fluorescent brightening agent may be added to the transparent resin composition of the present invention, and has the effect of converting unused active energy rays into usable wavelengths, thereby reducing the irradiation energy or shortening the irradiation time.

[0067] Examples of the fluorescent whitening agent are selected from 2,5-bis(5-tert-butyl-2-benzoxazolyl)thiophene, 7-diethylamino-4-methylcoumarin, 7-(2H-naphtho[1,2-d]triazol-2-yl)-3-phenyl-2H-1-benzopyran-2-one, Tinopal OB CO (manufactured by BASF Co., Ltd.), and the like.

[0068] The resin composition of the present invention can be suitably used as a putty or primer for coated automotive FRP parts that exhibit a fiber pattern as a design and are protected with a transparent paint. The use as a putty will be described in detail below.

[0069] Examples of reinforcing fibers having irregularities resulting from the weave of the fibers include, but are not limited to, FRPs that use fibers woven from carbon, boron, aramid, glass, Kevlar, Dyneema, Zylon, cellulose, gold, silver, or other fibers, either alone or in combination.

[0070] The matrix resin that encases the woven fiber fabric is not particularly limited, but may be made of materials such as epoxy, acrylic, nylon, ABS, ASA, PET, PBT-PET, PMMA, polycarbonate, polydicyclopentadiene, etc. These materials are used in vehicle components such as roofs, hoods, fenders, door panels, wings, bumpers, rocker moldings, pillars, luggage doors, spoilers, grilles, and windshields, and therefore the resin composition of the present invention can be suitably used as a vehicle paint.

[0071] The FRP to be coated with the photocurable resin composition of the present invention may be sandblasted or polished with sandpaper before coating.

[0072] The method for applying the photocurable resin composition of the present invention is not particularly limited, and for example, after cleaning an FRP molded article with a wiping solvent or an aqueous cleaner, the resin composition can be applied to the surface of the molded article and then irradiated with active energy rays to form a coating film. Furthermore, after application, in order to remove the solvent remaining in the coating, air drying or a desolvation step to shorten the process may be performed before irradiating with active energy rays.

[0073] The method for applying the resin composition is not particularly limited, and can be carried out by known methods such as air spray coating, electrostatic coating, and dip coating.

[0074] The coating is preferably carried out so that the dry film thickness is 10 to 120 μm, and the solvent is evaporated by air drying or preheating at room temperature to 100° C. for 1 to 25 minutes, preferably 3 to 20 minutes, prior to the ultraviolet irradiation. If the preheating temperature exceeds 100° C., the performance is not affected, but the smoothness of the coating film is reduced.

[0075] After the air drying or preheating, the resin composition is irradiated with active energy rays using an LED light source device with a peak wavelength of 350 to 420 nm at a peak irradiance of 15 mW / cm. ２ Irradiation is continued under the above conditions until the reaction rate of the coating film reaches 75% or more. If the irradiation time exceeds 1 hour, the performance is not affected, but it is disadvantageous in terms of production efficiency.

[0076] After the resin composition of the present invention is cured with active energy rays, it is preferable to apply a topcoat paint such as a clear paint, and before applying the topcoat paint, repairs such as polishing may be carried out as necessary, and active energy rays may be irradiated using an LED light source device.

[0077] The method for applying the topcoat resin composition is not particularly limited, and for example, air spray coating, airless spray coating, bell coating, etc. can be used.

[0078] The baking temperature of the topcoat resin composition is preferably, for example, 70 to 130°C, in order to balance rapid curing with prevention of deformation of the FRP molded product. It is more preferably 80 to 120°C. The baking time is usually 10 to 60 minutes, preferably 15 to 50 minutes, and even more preferably 20 to 40 minutes. Baking times of less than 10 minutes result in insufficient curing of the coating film, and the cured coating film's properties, such as water resistance and solvent resistance, are reduced. On the other hand, baking times of more than 60 minutes result in reduced adhesion during recoating, longer overall coating process times, and higher energy costs. Note that this baking time refers to the time during which the substrate surface actually maintains the target baking temperature. More specifically, it refers to the time during which the target temperature is maintained after it is reached, regardless of the time it takes to reach the target baking temperature.

[0079] Examples of heating devices used to simultaneously bake the uncured coating film include drying ovens that use heat sources such as hot air, electricity, gas, and infrared rays. It is also preferable to use a drying oven that uses two or more of these heat sources in combination, as this shortens the drying time.

[0080] The present invention will be described below with reference to examples. In the examples, "%" and "parts" used in the formulations mean "% by mass" and "parts by mass" unless otherwise specified. The present invention is not limited to the examples described below.

[0081] Production Example 1: Synthesis of Component (A): Acrylic Polyol A-1 100 parts of n-butyl acetate were charged into a four-neck flask equipped with a heater, stirrer, thermometer, reflux condenser, nitrogen inlet tube, and dropping device, and the temperature was raised to 120°C while stirring and introducing nitrogen. Next, a mixed solution of 20.0 parts of methyl methacrylate, 16.2 parts of n-butyl acrylate, 57.2 parts of n-butyl methacrylate, 6.2 parts of 2-hydroxyethyl acrylate, 0.4 parts of acrylic acid, and 0.2 parts of Kayaester-O (a polymerization initiator) was added dropwise from the dropping device over a period of 3 hours. Stirring was then continued for 120 minutes to complete the reaction, yielding the desired acrylic polyol A-1 (resin solids content: 50%). The blending amounts and physical properties of acrylic polyol A-1 are shown in Table 1.

[0082] Production Examples 2 to 11 Production of Acrylic Polyols A-2 to A-11 Using the same equipment as used in the synthesis of Acrylic Polyol A-1, the same synthesis procedures and operations as those for Acrylic Polyol A-1 were carried out, except that the solvent, monomers, and polymerization initiator were changed so as to obtain the amounts shown in Table 1. Acrylic polyols A-2 to A-11 shown in Table 1 were obtained. The properties are also shown in Table 1.

[0083] (Hydroxyl Value (OHV)) The hydroxyl value was determined by the neutralization titration method described in JIS K 0070 using an aqueous potassium hydroxide solution.

[0084] (Acid Value (AV)) The acid value was determined by the neutralization titration method described in JIS K 0070 using an aqueous potassium hydroxide solution.

[0085] (Weight Average Molecular Weight (Mw)) The weight average molecular weight is a value measured by GPC (gel permeation chromatography) and is a weight average molecular weight converted into polystyrene.

[0086] (Glass Transition Temperature (Tg)) The glass transition temperature was measured using a DSC (Differential Scanning Calorimeter) manufactured by Seiko Instruments Inc.

[0087] MMA: methyl methacrylate nBA: n-butyl acrylate nBMA: n-butyl methacrylate HEA: 2-hydroxyethyl acrylate AA: acrylic acid Polymerization initiator: Kayaester-O (hydrogen peroxide-based polymerization initiator manufactured by Kayaku Akzo Co., Ltd.)

[0088] Component (B) B-1: SR368NS (tris(2-acryloyloxyethyl) isocyanurate manufactured by Arkema) B-2: Aronix M-408 (ditrimethylolpropane tetraacrylate manufactured by Toagosei Co., Ltd.) B-3: SR399NS (mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate manufactured by Arkema) B-4: Aronix M-211B (ethoxylated bisphenol A diacrylate manufactured by Toagosei Co., Ltd.) B-5: Aronix M-215 (bis(2-acryloyloxyethyl) isocyanurate manufactured by Toagosei Co., Ltd.) B-6: NK Ester A-DCP (tricyclodecane dimethanol diacrylate manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0089] Component (C) C-1: CAB-381-20 (cellulose ester resin manufactured by Eastman Chemical Company)

[0090] Component (D1) Component (D1-1): Omnirad TPO (an acylphosphine-based photopolymerization initiator manufactured by IGM Resins) Component (D1-2): Omnirad TPO-L (an acylphosphine-based photopolymerization initiator manufactured by IGM Resins) Component (D1-3): Omnirad 819 (an acylphosphine-based photopolymerization initiator manufactured by IGM Resins) Component (D1-4): Omnirad 184 (an alkylphenone-based photopolymerization initiator manufactured by IGM Resins) Component (D1-5): Omnirad 379 (an alkylphenone-based photopolymerization initiator manufactured by IGM Resins)

[0091] Component (D2) Component (D2-1): Omnirad 4PBZ (a hydrogen abstraction photopolymerization initiator manufactured by IGM Resins) Component (D2-2): Omnirad 3644 (a hydrogen abstraction photopolymerization initiator manufactured by IGM Resins) Component (D2-3): Omnirad BP Flakes (a hydrogen abstraction photopolymerization initiator manufactured by IGM Resins)

[0092] Component (E) Component (E-1): TINUVIN PS (benzotriazole-based UV absorber manufactured by BASF) Component (E-2): TINUVIN 400 (hydroxyphenyltriazine-based UV absorber manufactured by BASF) Component (E-3): UVINAL 3039 (cyanoacrylate-based UV absorber manufactured by BASF) Component (E-4): HOSTAVIN PR-25 (malonic acid ester-based UV absorber manufactured by Clariant Chemicals) Component (E-5): HOSTAVIN VSU (oxalic acid anilide-based UV absorber manufactured by Clariant Chemicals)

[0093] Component (F): T-6500 thinner (thinner manufactured by Nippon Paint Automotive Coatings Co., Ltd.)

[0094] Component (G) Component (G): Polyisocyanate was Duranate TPA-100: hexamethylene isocyanurate manufactured by Asahi Kasei Corporation, NCO (%) = 23.0%, and the compounding ratio with component (A) acrylic polyol was NCO / OH [number of moles of isocyanate groups in polyisocyanate (B) / total number of moles of hydroxyl groups in acrylic polyol (A)] was 1.2.

[0095] LED light source device Light source-1 LED-355nm Light source-2 LED-365nm Light source-3 LED-385nm Light source-4 LED-395nm Light source-5 LED-405nm Light source-6 LED-415nm Light source-7 LED-280nm Light source-8 LED-313nm Light source-9 LED-436nm Light source-10 High-pressure mercury lamp Light source-11 Metal halide lamp (high-pressure mercury lamp doped with iron) Light source-12 Gallium lamp (high-pressure mercury lamp doped with gallium, etc.)

[0096] Examples of additives and adjuvants that are commonly used in the resin composition of the present invention include: light stabilizer: Tinuvin 292 (manufactured by BASF); surface conditioner: BYK-320 (manufactured by BYK-Chemie); amine synergist: Omnipol ASA (manufactured by IGM Resins); fluorescent brightener: Tinopal OB CO (manufactured by BASF); and urethane curing catalyst: DBTDL (dibutyltin dilaurate).

[0097] An example of a clear top coating to be applied after curing the resin composition of the present invention is clear coating R-2830 Clear (manufactured by Nippon Paint Automotive Coatings Co., Ltd.).

[0098] Calculation of active energy ray reaction rate In FT-IR, peak wavelength A: 1730 cm －１ Carbon-oxygen double bond derived from ester bond Peak wavelength B: 810 cm －１ The carbon-carbon double bond peak B derived from the acrylate is reduced by radical polymerization due to irradiation with active energy rays, and the reaction rate can be calculated from the area ratio of peak A to peak B before and after irradiation with active energy rays. The irradiation with active energy rays was carried out under conditions that resulted in the reaction rate of 75% or more.

[0099] The paint viscosity was adjusted to 12 to 13 seconds at a liquid temperature of 20°C in a No. 4 Ford cup by diluting with T-6500 thinner (component (F)).

[0100] Example 1 The components shown in Table 2-1 were placed in a container equipped with a stirrer, and while stirring, component (F) was added in an amount such that the solid content of the coating was 40%, and the mixture was stirred for 30 minutes to obtain an active energy ray-curable resin composition. The obtained resin composition was spray-coated to a dry film thickness of 10 μm, and the mixture was left to stand at room temperature for 10 minutes to remove the solvent. Next, using a light source device using an LED with an emission wavelength of 355 nm, the active energy ray-curable resin composition was spray-coated to a dry film thickness of 10 μm, and the mixture was left to stand at room temperature for 10 minutes to remove the solvent. Next, the active energy ray-curable resin composition was spray-coated to a peak irradiance of 200 mW / cm. ２ The coating film was irradiated for 10 minutes at 1000 kJ / s. The reaction rate of the coating film was measured and confirmed to be 75% or higher. The peak irradiance of the active energy ray irradiation was measured using an Eye UV Meter UVPF-A2 (light receiving element: PD-3040A2) manufactured by Eye Graphics.

[0101] Examples 2 to 37 and Comparative Examples 1 to 23 The coating films of Examples 2 to 37 and Comparative Examples 1 to 23 were formed in the same manner as in Example 1, except that the formulations were changed to those shown in Tables 2-1, 3-1, 4-1 and 5-1, to obtain final coated panels.

[0102] FRP Coating Substrate The FRP to be coated was a carbon composite ZC-60 manufactured by TIP Composites, which uses plain woven carbon fiber. It was polished with #800 sandpaper and degreased with isopropyl alcohol before use.

[0103] Formation of Laminated Film After coating and curing the transparent resin compositions of the above Examples and Comparative Examples, a laminated film was formed by the following method. The transparent resin compositions of the above Examples and Comparative Examples were coated and cured with active energy rays to obtain test pieces. Subsequently, a clear resin composition (R-2830 Clear, manufactured by Nippon Paint Automotive Coatings Co., Ltd.) was coated so that the dry film thickness was 50 μm. After coating was completed, the coating was left to stand for 10 minutes and then heat-cured at 80°C for 30 minutes to obtain test pieces with multi-layer coating films.

[0104] In the examples and comparative examples, the following properties were evaluated: sealing ability, smoothness, adhesion, adhesion after a hot water resistance test, impact resistance, and accelerated weather resistance. The results are shown in Tables 2-2, 3-2, 4-2, and 5-2.

[0105] [Effect of sealing]: Effect of preventing paint from flowing into recesses on the FRP material and preventing pinholes caused by foaming The state of recesses and pinholes on the coating film of the painted FRP was evaluated according to the following criteria: ◎: When the recesses and pinholes are hidden and there are no defects when visually inspected ○: When slight recesses or pinholes are found △: When either the recesses or pinholes are not hidden ×: When the recesses and pinholes are not hidden

[0106] [Coating Film Appearance Evaluation (Smoothness)] The smoothness of the cured coating film was evaluated by measuring the arithmetic mean roughness (Ra) of the roughness curve. The Ra value of the obtained cured coating film was measured in accordance with JIS-B0601 using an evaluation type surface roughness measuring instrument (Mitutoyo Corporation, SURFTEST SJ-201P). Seven measurements were made using a sample with a 2.5 mm wide cutoff (5 sections), and the Ra value was obtained by averaging the top and bottom erase results. The obtained Ra values ​​were evaluated according to the following criteria: ◎: Ra value less than 0.2 μm ○: Ra value 0.2 μm or more but less than 0.4 μm △: Ra value 0.4 μm or more but less than 1.0 μm ×: Ra value 1.0 μm or more

[0107] [Adhesion] 100 grids were made at 2 mm intervals on a painted FRP evaluation board with a single-edged razor, and cellophane adhesive tape (JIS Z 1522) was firmly pressed onto them and quickly peeled off in a 90° direction, and the peeling state of the coating film was evaluated by the number of grids remaining. ◯: 100 grids remained △: 60 to 99 grids remained ×: Fewer than 60 grids

[0108] [Adhesion after hot water resistance test] Test pieces prepared in the same manner as above were immersed in hot water at 40°C for 240 hours, removed from the water, and dried at room temperature for 24 hours, after which the adhesion to the substrate was examined in the same manner as in the initial adhesion evaluation. ○: When 100 pieces remain. △: When 60 to 99 pieces remain. ×: When less than 60 pieces remain.

[0109] [Impact resistance test] Test pieces prepared in the same manner as above were dropped from a height of 30 cm at a room temperature of 25°C with a 300 g weight at a 1 / 2 inch impact point in a DuPont impact tester, and the cracking and adhesion of the coating film near the impact point were examined (JIS K5600-5-3). ○: No cracks in the coating film and adhered. △: Cracks in the coating film but adhered. ×: Cracks in the coating film and peeling.

[0110] [Accelerated Weathering Test] Test pieces prepared in the same manner as above were subjected to accelerated weathering using an Iwasaki Electric Eye Super UV Tester SUV-W161, and the coating surface was inspected for defects such as cracks and adhesion. (JIS A1501 Method A) Light intensity (300-400 nm) for one year of sunlight exposure = 300 MJ / m ２ ◎: 1500 MJ / m ２ After exposure, when there are no cracks or the like and the film is adhered, ○: 1200 MJ / m ２ After exposure, when there are no cracks or the like and the film is adhered, △: 1200 MJ / m ２ After exposure, defects such as cracks occur, but adhesion remains. ×: 1200 MJ / m ２ When peeling occurs after exposure

[0111]

[0112]

[0113]

[0114]

[0115]

[0116]

[0117]

[0118]

[0119] From the results of the above-mentioned examples, it is clear that the photocurable resin composition of the present invention can provide good coating properties and good coating film properties.

[0120] The photocurable resin composition of the present invention can be suitably used as a resin composition to be directly coated on a resin member having an uneven surface.

Claims

1. An active energy ray-curable resin composition, wherein the active energy ray-curable resin composition comprises: Component (A): an acrylic polyol; Component (B): a trifunctional or higher (meth)acrylate; Component (C): a viscosity modifier comprising a cellulose ester resin; Component (D1): an acylphosphine-based photoinitiator; Component (D2): a hydrogen abstraction-type photoinitiator; Component (E): an ultraviolet absorber; Component (F): a diluent solvent; Component (G): a polyisocyanate. The weight average molecular weight of the component (A) is 25,000 to 65,000; The hydroxyl value of the component (A) is 30 to 100 mgKOH / g; The glass transition temperature of the component (A) is -20 to 20°C; The component (A) has an acid value; The component (D1) is at least one selected from the group consisting of diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl phenyl(2,4,6-trimethylbenzoyl)phosphinate, and bis(2,6-dimethoxybenzoyl)2,4,4-trimethylpentylphosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide; The content of the component (A) is 35 to 75 parts by mass based on 100 parts by mass in total of the component (A) and the component (B); The content of the component (C) is 3 to 10 parts by mass based on 100 parts by mass in total of the component (A) and the component (B); The content of the component (D1) is 1 to 25 parts by mass based on 100 parts by mass in total of the component (A) and the component (B). An active energy ray-curable resin composition.

2. The component (B) is at least one selected from the group consisting of tris(2-(meth)acryloyloxyethyl) isocyanurate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; the component (D2) is at least one selected from the group consisting of benzophenone, 4-methylbenzophenone, 4-phenylbenzophenone, 2-(1,1'-biphenyl-4-yl)carbonylbenzoic acid 2-ethylhexyl, 4-benzoyl-4'-methyldiphenyl sulfide, methyl 2-benzoylbenzoate, 1-[4-(4-benzoylphenylsulfanyl)phenyl]-2-methyl-2-(4-methylphenylsulfonyl)propan-1-one, polyethylene glycol bis(paradimethylaminobenzoate), methyl benzoylformate, thioxanthone, 2,4-diethylthioxanthen-9-one, 2-isopropylthioxanthone, 3-benzoyl-7-(N,N-diethylamino)coumarin, 7-methoxy-3-(4-tert-butyl-benzoyl)coumarin, 3-(4-tert-butylbenzoyl)benzo[f]coumarin, 7-ethylthio-3-benzoylcoumarin, 3-(4-tert-butylbenzoyl)-5,7-dimethoxycoumarin, and 7-(sec-butylthio)-3-benzoylcoumarin; the component (E) is at least one selected from the group consisting of benzotriazole-based ultraviolet absorbers, hydroxyphenyltriazine-based ultraviolet absorbers, and benzophenone-based ultraviolet absorbers; the content of the component (D2) is 1 to 10 parts by mass with respect to 100 parts by mass in total of the components (A) and (B); and the content of the component (E) is 1 to 20 parts by mass with respect to 100 parts by mass in total of the components (A) and (B). The active energy ray-curable resin composition according to claim 1.

3. The component (G) contains at least one selected from the group consisting of the following biuret type, isocyanurate type, and adduct type, The active energy ray-curable resin composition according to claim 1, wherein the ratio of the number of moles of isocyanate groups in the component (G) to the number of moles of hydroxyl groups in the component (A) ([number of moles of isocyanate groups] / [number of moles of hydroxyl groups]) is 0.7 to 3.

0.

4. The light source device for the active energy ray emitted from the light emitting diode having the peak wavelength of 350 to 420 nm may be a light source device composed of a plurality of light emitting diodes that emit light of at least one peak wavelength, or a light source device composed of a plurality of light emitting diodes that emit light of a plurality of peak wavelengths, and the peak illuminance is 15 mW / cm ２ The active energy ray curable resin composition according to claim 1, which can be cured with the above.

5. A laminate having a substrate and a coating film of the active energy ray-curable resin composition according to any one of claims 1 to 4 on at least a part of the surface of the substrate, the coating film having at least one layer.

6. The laminate according to claim 5, wherein the coating film has a film thickness of 10 to 120 μm.

7. The laminate according to claim 5, wherein the substrate contains reinforcing fibers, and the reinforcing fibers are at least one selected from the group consisting of carbon fibers, boron fibers, aramid fibers, glass fibers, Kevlar fibers, Dyneema fibers, Zylon fibers, cellulose-based fibers, gold threads, and silver threads.

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