Active energy ray-curable resin composition and laminate

Abstract

To improve productivity of an FRP coated article having high designability by excellent filling performance, and protect the FRP coated article from long-term outdoor exposure.SOLUTION: An active energy ray-curable resin composition contains component (A): acryl polyol, component (B): tri- or higher functional (meth)acrylate, component (C): a viscosity modifier composed of a cellulose ester resin, component (D1): an acylphosphine-based photopolymerization initiator, component (D2): a hydrogen abstraction type photopolymerization initiator, component (E): an ultraviolet absorber, component (F): a dilution solvent, and component (G): polyisocyanate.SELECTED DRAWING: Figure 1

Description

Technical Field

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

Background Art

[0002] Fiber reinforced plastic (hereinafter referred to as "FRP") is lightweight and has rigidity equivalent to or higher than that of metals such as iron and aluminum. Depending on the type, shape, and weave of the fibers, various properties are exhibited, making it an effective material for weight reduction in automobiles and the like.

[0003] In recent years, there has been an increase in automotive painted parts that show a fiber pattern as a design and are protected with a transparent paint. However, when a thermosetting transparent resin composition composed of a conventional acrylic polyol and polyisocyanate is painted and baked, rupture marks (hereinafter referred to as "pinholes") due to minute air bubbles encapsulated in the fibers occur, significantly deteriorating the painted appearance.

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

[0005] That is, in the conventional method, polishing, painting, and baking were repeated many times until pinholes and surface unevenness no longer occurred, resulting in extremely poor production efficiency.

[0006] Also, although epoxy resins, acrylic resins, etc. are used as the matrix resins necessary for shaping FRP, they do not have weather resistance that can withstand long-term exposure to sunlight, and it is necessary to protect them with a transparent resin composition. However, as described above, a lot of working time, energy, and human resources have been consumed.

[0007] Although about a century has passed since FRP was born and widely used, a method for fundamentally solving these problems such as pinholes has not yet been established. In response to this problem, in Patent Document 1, by using UV curing and heat curing in combination, various problems were solved by suppressing the generation of pinholes. However, it was premised on the use of a mercury lamp that emits light widely from ultraviolet to infrared, and the suppression of pinholes generated by the rapid heating of the coated object by infrared rays during UV irradiation was insufficient. In addition, when applied to a transparent resin composition, there was a problem of insufficient long-term outdoor weather resistance.

[0008] As conventional UV-curable resin compositions for vehicles having long-term outdoor weather resistance, Patent Documents 2 to 4 etc. can be cited. However, since most of the ultraviolet rays from the mercury lamp overlap with the absorption wavelength of the ultraviolet absorber, in FRP with surface irregularities, it is difficult to uniformly perform UV curing to suppress pinholes on the three-dimensional FRP article while ensuring the UV curability from the deepest part of the dent to the outermost surface of the coating film with only a UV curing design.

[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 emission from an LED, are ink compositions for posters etc. assuming outdoor use printed by inkjet printing etc., and are not suitable for the long-term outdoor weather resistance required for vehicles assumed by this paint.

[0010] Patent Document 8 is a resin composition that cures by light emission from an LED for indoor use assuming an environment where outdoor light such as sunlight enters to some extent on the floor etc. Specifically, a malonic ester-based ultraviolet absorber and an oxalic acid anilide-based ultraviolet absorber are defined, but it is not suitable for the long-term outdoor weather resistance required for vehicles assumed by this paint.

Prior Art Documents

Patent Documents

[0011]

Patent Document 1

Patent Document 2

Patent Document 3

[0012] Therefore, the problem to be solved by the present invention is to improve the productivity of FRP coated articles having high design quality with excellent blocking performance and protect them from long-term outdoor exposure. The blocking performance is the performance of sealing defect points such as encapsulated air bubbles, holes derived from the air bubbles, and fiber segregation potentially present in the FRP. Specifically, it is to form a smooth coating surface on the surface without following the crater-like indentations caused by the air expansion and bubble rupture in the air bubbles generated when coating the FRP, the indentations generated when the liquid paint immediately after coating is sucked into the holes derived from the air bubbles, and the uneven surfaces caused by fiber deviation, weaving, etc. (At the same time, by using the LED light source device, it contributes to energy saving and the construction of a mercury-free working environment without using a mercury lamp.) [Means for Solving the Problems

[0013] The active energy ray curable resin composition according to the present invention is Component (A): Acrylic polyol, Component (B): A (meth) acrylate having three or more functional groups, Component (C): A viscosity modifier composed of a cellulose ester resin, Component (D1): An acylphosphine-based photoinitiator, Component (D2): A hydrogen abstraction type photoinitiator, Component (E): Ultraviolet absorber, Component (F): Diluting solvent, Component (G): Polyisocyanate, containing The weight average molecular weight of the said component (A) is 25,000 to 65,000, The hydroxyl value of the said component (A) is 30 to 100 mgKOH / g, The glass transition temperature (hereinafter referred to as "Tg") of the said component (A) is -20 to 20°C, The said component (A) has an acid value, The said 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 said component (A) is 35 to 75 parts by mass with respect to a total of 100 parts by mass of the said component (A) and component (B), The content of the said component (C) is 3 to 10 parts by mass with respect to a total of 100 parts by mass of the said component (A) and component (B), The content of the said component (D1) is 1 to 25 parts by mass with respect to a total of 100 parts by mass of the said component (A) and component (B). It is an active energy ray-curable resin composition. Thereby, an FRP coated article having high designability can be produced with excellent blocking performance, and can be protected 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 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), 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).

[0015] In one embodiment of the active energy ray-curable resin composition according to the present invention, the component (G) is comprising at least one selected from the group consisting of the following biuret type, isocyanurate type and adduct type,

Chemical formula

[0016] In one embodiment of the active energy ray-curable resin composition according to the present invention, the light source device of the active energy ray emitted from a light-emitting diode having a peak wavelength of 350 to 420 nm is a light source device comprising a plurality of light-emitting diodes that emit light of at least one peak wavelength, or a light source device comprising a plurality of light-emitting diodes that emit light of a plurality of peak wavelengths, and is curable with a peak illuminance of 15 mW / cm 2 or more.

[0017] The laminate according to the present invention has an object to be coated and a coating film of any one of the above active energy ray-curable resin compositions on at least a part of the surface of the object to be coated, The coating film is a laminate having at least one layer.

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

[0019] In one embodiment of the laminate according to the present invention, the object to be coated contains reinforcing fibers, 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.

Advantages of the Invention

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

Brief Description of Drawings

[0021]

Figure 1

Embodiments for Carrying Out the Invention

[0022] The FRP coated article to which the resin composition of the present invention is applied is FRP formed by laminating fiber sheets or the like, and is a composite material of a sheet in which long fibers are woven and a matrix resin. Since it is lightweight and has a specific strength and specific modulus equal to or higher than that of metal, it is used in various applications such as sports and leisure goods, automobiles, aircrafts, agricultural machinery, fishing machinery, and space development.

[0023] It is particularly preferable to directly apply the resin composition of the present invention and use it on FRP that has been puttied or sanded or sandblasted to such an extent that the fibers are not damaged against the gaps and unevenness generated between the intersecting fibers.

[0024] Component (A) Component (A) in the above resin composition contains acrylic polyol, and has adhesiveness to the matrix resin and can withstand the characteristic behavior of the material over a long period of time with respect to FRP having extremely high property (hereinafter referred to as "elasticity") that the deformation generated by an external force returns to the original state when the external force is lost.

[0025] The 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. The weight average molecular weight of the component (A) is 25,000 to 65,000, preferably 35,000 to 55,000, more preferably 40,000 to 50,000. When the weight average molecular weight is less than 25,000, cracking and peeling are likely to occur in impact tests and the like. When it is 65,000 or more, atomization during spray coating deteriorates and the coating appearance deteriorates.

[0026] The hydroxyl value of the component (A) is from 30 to 100 mgKOH / g. When the hydroxyl value is less than 30 mgKOH / g, crosslinking with the component (A) is insufficient and physical properties such as water resistance deteriorate. When the hydroxyl value is 100 mgKOH / g or more, the impact resistance deteriorates.

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

[0028] Component (B) Component (B) in the above resin composition: It contains a polyfunctional (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 a photoinitiator of component (D1) and component (D2) upon irradiation with active energy rays, and suppresses pinholes derived from air bubbles encapsulated in the FRP.

[0029] Component (B) in the above resin composition is preferably at least one selected from 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 preferably urethane (meth)acrylate obtained by reacting isocyanurate isocyanate obtained by trimerizing hexamethylene diisocyanate, isophorone diisocyanate, etc. with (meth)acrylic monomers 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, and dipentaerythritol penta(meth)acrylate, and urethane (meth)acrylate obtained by reacting diisocyanates such as hexamethylene diisocyanate and 4,4'-methylenebis(cyclohexyl isocyanate) with (meth)acrylic monomers having a hydroxyl group such as trimethylolpropane di(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate.

[0031] From the viewpoint of the 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 without a urethane bond are more preferably selected.

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

[0033] Component (C) The viscosity regulator composed of at least one cellulose ester resin as the component (C) in the resin composition suppresses the suction due to the gaps generated between the intersecting fibers and the capillary phenomenon generated from the recesses, etc., and improves the heat resistance, impact resistance, etc. of the coating film. The cellulose ester resin is preferably selected from a cellulose acetate resin, a cellulose propionate resin, and a cellulose butyrate resin. Examples of the cellulose acetate resin include CA-398-3, CA-398-6, CA-398-10, CA-398-30 (manufactured by Eastman Chemical Company). Examples of the cellulose propionate resin include CAP-482-20 (manufactured by Eastman Chemical Company). Examples of the cellulose butyrate resin 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, CAB-381-20 BP (manufactured by Eastman Chemical Company).

[0034] The component (C) is 3 to 10 parts by mass with respect to 100 parts by mass in total of the component (A) and the component (B). Preferably, it is 4 to 6 parts by mass.

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

[0036] Component (D1) is a compound selected from at least one or more 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, and it contains 1 to 25 parts by mass with respect to a total of 100 parts by mass of the said component (A) and component (B). When the addition amount of component (D1) is less than 1 part by mass, the suppression of pinholes decreases due to insufficient curing of component (B) by active energy rays, and when it is 25 parts by mass or more, the abrasiveness, water resistance, solvent resistance, etc. decrease.

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

[0038] As the component (D2), it is a compound selected from one or more of benzophenone, 4 - methylbenzophenone, 4 - phenylbenzophenone, 2 - (1,1'-biphenyl - 4 - yl) carbonyl benzoic 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(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 - tetrahydroquinolizinol[9,9a,1 - gh]coumarin, 9 - benzoyl, 3 - benzoyl - 7 - methoxycoumarin, 3 - benzoyl - 5,7 - dimethoxycoumarin, 7 - methoxy - 3 - (4 - methyl - benzoyl)coumarin, 3 - (4 - methylbenzoyl)benzo[f]coumarin, TR - PSS - 202 (manufactured by TRONLY), and ESACURE3644 (manufactured by IGM Resins), and it contains 0.5 to 5 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B). When the addition amount of the component (D2) is less than 0.5 part by mass, the pinhole suppression decreases due to insufficient curing of the component (B) by active energy rays, and when it is 5 parts by mass or more, the abrasiveness and the like decrease.

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

[0040] Component (E) is preferably selected from benzotriazole-based ultraviolet absorbers, hydroxyphenyltriazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, and cyanoacrylate-based ultraviolet absorbers.

[0041] Examples of benzotriazole-based ultraviolet absorbers include 2-(5-tert-butyl-2-hydroxyphenyl)benzotriazole, C7-C9-alkyl-3-[3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl]propionate, 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, 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, the reaction product of 5-[3-(2-ethylhexyloxy)-2-hydroxypropoxy]-2-[4,6-bis(2,4-xylyl)-1,3,5-triazin-2-yl]phenol and 2-{[(2-ethylhexyl)oxy]methyl}oxirane, the reaction product of 5,5'-dibutoxy-2,2'-[6-(2,4-dibutoxyphenyl)-1,3,5-triazine-2,4-diyl]diphenol and 4,4',4''-(1,3,5-triazine-2,4,6-triyl)tris(benzene-1,3-diol) and butyl bromide, Tinuvin 400, Tinuvin 405, Tinuvin 460, Tinuvin 477, Tinuvin 479 (manufactured by BASF).

[0043] Examples of benzophenone-based UV absorbers include octabenzone, dioxybenzone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2’,4,4’-tetrahydroxybenzophenone, 2,2’-dihydroxy-4,4’-dimethoxybenzophenone, KEMISORB11, KEMISORB12, KEMISORB111 (manufactured by Kemipro Kasei Co., Ltd.), Eversorb10, Eversorb11, Eversorb12, Eversorb51, Eversorb52, EversorbCP01, EversorbCP02 (manufactured by Everlight Chemical Co., Ltd.).

[0044] Examples of cyanoacrylate-based UV absorbers include Uvinul 3035, Uvinul 3039, and Uvinul 3030FF.

[0045] Component (E) is contained in an amount of 1 to 20 parts by mass based on a total of 100 parts by mass of the above-mentioned components (A) and (B). When the addition amount of component (E) is less than 1 part by mass, the weather resistance decreases, and when it is 20 parts by mass or more, the water resistance, abrasion resistance, and economy decrease. When the addition amount of component (E) is 1 to 2 parts by mass, even if the film thickness of the coating film is increased, or when it is 15 to 20 parts by mass and the film thickness is decreased, there are no problems with weather resistance and the like.

[0046] Component (E) may be used alone for each UV absorber, but depending on the UV absorption characteristics, it is better to combine two or more kinds, and it is more preferable to combine a benzotriazole-based UV absorber and a hydroxyphenyltriazine-based UV absorber.

[0047] Component (E) may be a combination of light stabilizers. 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, 2,4-bis[N-butyl-N-(1-cyclohexyl-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-(2-hydroxyethylamino)-1,3,5-triazine, 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), and the like.

[0048] Component (F) Component (F) in the above resin composition: The diluting solvent is used for viscosity adjustment when applying to the FRP, and the amount and type can be selected according to coating methods such as air spray method, airless spray method, bell coating method, etc.

[0049] Component (G) Component (G) in the above resin composition: At least one polyisocyanate reacts with the hydroxyl group of the acrylic polyol of component (A) to form a urethane bond, 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. For example, aromatic ones such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, and metaxylylene diisocyanate; aliphatic ones such as hexamethylene diisocyanate; alicyclic ones such as isophorone diisocyanate; its monomers and multimers such as burette type, nurate type, and adduct type can be mentioned.

[0051] Commercially available products of the polyisocyanate of the above component (G) include Duranate 24A-90PX (manufactured by Asahi Kasei Corporation), Sumidule N-3200-90M (manufactured by Sumitomo Bayer Urethane Co., Ltd.), Takenate D165N-90X (manufactured by Mitsui Chemicals, Inc.), Sumidule N-3300, Sumidule N-3500 (manufactured by Sumitomo Bayer Urethane Co., Ltd.), Duranate TPA-100 (manufactured by Asahi Kasei Corporation), etc. Also, blocked isocyanates obtained by blocking these can be used as needed.

[0052] The blending ratio of the polyisocyanate of component (G) and the acrylic polyol of component (A) is preferably such that NCO / OH [the number of moles of isocyanate groups in polyisocyanate (B) / the 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 or less. If it is below the lower limit value, the crosslinking density of the cured coating film is insufficient, resulting in a decrease in water resistance, etc. If it is above the upper limit value, the abrasion resistance after active energy ray irradiation decreases.

[0053] The resin composition of the present invention may adjust the irradiation energy and irradiation time of the active energy ray according to the standard time required to produce one FRP product (hereinafter referred to as "tact time"). When a lot of irradiation time can be ensured, the amounts of components (D1) and (D2) can be reduced, and when the irradiation time is short, the amounts of components (D1) and (D2) can be increased.

[0054] In addition, assuming that the resin composition of the present invention is to be applied to FRP with surface irregularities, the film thickness is 10 to 120 μm. In the case of a thin film, the amounts of component (D1) and component (D2) may be decreased, and in the case of a thick film, the amounts of component (D1) and component (D2) may be increased.

[0055] When the film thickness of the resin composition of the present invention is less than 10 μm, the surface irregularities of the FRP cannot be concealed and film formation cannot be achieved. When it is 120 μm or more, appearance defects such as sagging occur and the amount of paint used increases, resulting in economic disadvantages. Preferably, it is 20 to 80 μm, and more preferably, it is 30 to 60 μm.

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

[0057] When an LED having a peak wavelength of less than 350 nm is used, since it overlaps with the absorption wavelength band of the ultraviolet absorber of component (E) having strong absorption at 280 to 340 nm, the polymerization reaction does not proceed, and the pinhole blocking property, water resistance, abrasion resistance, weather resistance, etc. decrease. In addition, since the resin composition of the present invention is a transparent resin composition, the active energy rays to be irradiated are also irradiated to the FRP. The absorption wavelengths calculated from the bonding energies of carbon and hydrogen and carbon and carbon are 293 nm and 339 nm. Therefore, when an LED having a peak wavelength of less than 350 nm is used, the curing reaction of the coating film and the degradation reaction of the resin composition and the FRP proceed in parallel, and the long-term outdoor weather resistance aimed at by the present invention cannot be obtained. These phenomena are the same even in the curing reaction using a mercury lamp, xenon lamp, etc. having a large number of emission lines at less than 350 nm. E = hc / λ ····(Equation 1) h: Planck's constant (6.626×10 -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, since the photoinitiators of components (D1) and (D2) do not have a high absorption band, the polymerization reaction does not proceed, and the water resistance, abrasion resistance, weather resistance, etc. deteriorate.

[0059] When a mercury lamp, xenon lamp, etc. having a large number of emission lines at 420 nm or more is used, particularly due to the heat from the lamp tube bulb and the infrared rays during light emission, the pinholes generated by the rapid expansion and rupture of the bubbles encapsulated in the FRP cannot be completely suppressed.

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

[0061] As the LED for curing the present resin composition with active energy rays, the peak wavelength is 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 a special illuminometer for LEDs, with an integrated light quantity of 250 mJ / cm 2 or more, and a peak illuminance of 15 mW / cm 2 or more. There is no limitation on the irradiation time, etc., but from the viewpoint of productivity, it is preferable to adjust so as to irradiate for a longer time in accordance with the tact time.

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

[0064] An amine synergist may be added to the transparent resin composition of the present invention, which has the effect of reducing the irradiation energy or shortening the irradiation time. Examples of the amine synergist include 2-ethylhexyl-4-(dimethylamino)benzoate, ethyl-4-(dimethylamino)benzoate, poly(ethylene glycol) bis(paradimethylaminobenzoate), 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, amino alcohol 2B (manufactured by Nippon Emulsion Co., Ltd.), etc.

[0065] As the urethane curing catalyst, a urethane catalyst selected from acids, bases, transition metals, or tin-based catalysts, titanium-based catalysts, zirconia-based catalysts, bismuth-based catalysts, and organic amine-based catalysts may be added. Examples 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, etc.

[0066] A fluorescent brightening agent may be added to the transparent resin composition of the present invention, which has the effect of reducing the irradiation energy or shortening the irradiation time by changing the unused active energy ray to a wavelength that can be utilized.

[0067] Examples of the fluorescent brightener include those 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), and the like.

[0068] The resin composition of the present invention can be suitably used as a putty and a primer for an automobile FRP painted part that shows a fiber pattern as a design and is protected with a transparent paint. Hereinafter, the use as a putty will be described in detail.

[0069] The reinforcing fiber having irregularities derived from the weave of the fiber is not particularly limited, and examples thereof include FRP using fibers such as carbon, boron, aramid, glass, Kevlar, Dyneema, Zylon, cellulose, gold, and silver, which are woven alone or in combination.

[0070] The matrix resin encapsulating the fabric of the above fiber is not particularly limited, and can also be applied to materials such as epoxy, acrylic, nylon, ABS, ASA, PET, PBT-PET, PMMA, polycarbonate, and polydicyclopentadiene. These materials are used for vehicle members such as roofs, bonnets, fenders, door panels, wings, bumpers, rocker moldings, pillars, luggage doors, spoilers, grills, and windshields. 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 polished with sandblasting or sandpaper before coating.

[0072] The coating method of the photocurable resin composition of the present invention is not particularly limited. For example, after washing an FRP molded product with a wiping solvent or an aqueous cleaning agent, the above resin composition is applied to the surface of the molded product, and then irradiated with active energy rays to form a coating film. Further, after coating, in order to remove the solvent remaining in the paint, air drying or a solvent removal step may be added before the active energy ray irradiation for shortening the process.

[0073] The application of the above resin composition is not particularly limited, and for example, it can be carried out by a known method such as air spray coating, electrostatic coating, dipping coating or the like.

[0074] In the above application, it is carried out so that the dry film thickness becomes 10 to 120 μm, and before the above ultraviolet irradiation, it is preferably air dried or preheated at normal temperature to 100 ° C for 1 to 25 minutes, preferably 3 to 20 minutes, to evaporate the solvent. When the temperature of the above preheating exceeds 100 ° C, although there is no influence on the performance, the smoothness of the coating film decreases.

[0075] The irradiation of active energy rays to the above resin composition is carried out with an LED light source device having a peak wavelength of 350 to 420 nm after the above air drying or preheating, and the peak illuminance is 15 mW / cm 2 Under the above conditions, irradiation is carried out until the reaction rate of the coating film reaches 75% or more. When the irradiation time exceeds 1 hour, although there is no influence on the performance, it is disadvantageous in terms of production efficiency.

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

[0077] The coating method of the above topcoat resin composition is not particularly limited, and for example, air spray coating, airless spray coating, bell coating or the like can be adopted.

[0078] The baking temperature of the above topcoat resin composition is preferably, for example, 70 to 130°C in view of the balance between rapid curing and prevention of deformation of the FRP molded product. More preferably, it is 80 to 120°C. The baking time is usually 10 to 60 minutes, preferably 15 to 50 minutes, and more preferably 20 to 40 minutes. If the baking time is less than 10 minutes, the curing of the coating film is insufficient, and the performance such as water resistance and solvent resistance of the cured coating film deteriorates. On the other hand, if the baking time exceeds 60 minutes, the adhesion in recoating decreases, the total time of the coating process becomes long, and the energy cost increases. Note that this baking time means the time during which the surface of the substrate actually continues to maintain the target baking temperature. More specifically, it does not consider the time until the target baking temperature is reached, but means the time when the temperature is maintained after reaching the target temperature.

[0079] Examples of the heating device used for simultaneously baking the uncured film of the paint include, for example, a drying oven using a heat source such as hot air, electricity, gas, or infrared rays. Further, it is preferable to use a drying oven in which two or more of these heat sources are used in combination because the drying time is shortened.

Examples

[0080] Hereinafter, the present invention will be described with reference to examples. In the examples, “%” and “parts” in the blending ratio mean “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 Into a four-necked flask equipped with a heating device, a stirring device, a thermometer, a reflux condenser, a nitrogen inlet tube, and a dropping device, 100 parts of n-butyl acetate were charged, and the temperature was raised to 120 °C while stirring and introducing nitrogen. Next, from the dropping device, 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 part of acrylic acid, and 0.2 part of Kayacel-O as a polymerization initiator was added dropwise over 3 hours. Subsequently, stirring was continued for 120 minutes to complete the reaction, and the target acrylic polyol A-1 was obtained (resin solid 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 equipment similar to that used in the synthesis of acrylic polyol A-1, except that the solvent, monomer, and polymerization initiator were changed to the blending amounts shown in Table 1, the same synthesis procedure and operations as those for acrylic polyol A-1 were carried out to obtain acrylic polyols A-2 to A-11 shown in Table 1. The characteristics are also shown in Table 1.

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

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

[0085] (Weight Average Molecular Weight (Mw)) The weight average molecular weight is the value measured by GPC (gel permeation chromatography) and is the weight average molecular weight in terms of polystyrene.

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

[0087]

Table 1

[0088] Component (B) B-1: SR368NS (Tris(2-acryloyloxyethyl) isocyanurate manufactured by Arkema Co., Ltd.) 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 Co., Ltd.) 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 Co., Ltd.)

[0090] Component (D1) Component (D1-1): Omnirad TPO (Acylphosphine-based photoinitiator manufactured by IGM Resins B.V.) Component (D1-2): Omnirad TPO-L (Acylphosphine-based photoinitiator manufactured by IGM Resins B.V.) Component (D1-3): Omnirad 819 (Acylphosphine-based photoinitiator manufactured by IGM Resins B.V.) Component (D1-4): Omnirad 184 (an alkylphenone-based photoinitiator manufactured by IGM Resins) Component (D1-5): Omnirad 379 (an alkylphenone-based photoinitiator manufactured by IGM Resins)

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

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

[0093] Component (F) Component (F): T-6500 Thinner (a thinner manufactured by Nippon Paint Automotive Coatings)

[0094] Component (G) Component (G): As the polyisocyanate, Duranate TPA-100, hexamethylene isocyanurate manufactured by Asahi Kasei Corporation, with NCO(%) = 23.0% was used. The mixing ratio with component (A) acrylic polyol was such that NCO / OH [the number of moles of isocyanate groups in polyisocyanate (B) / the 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] As additives and adjuvants known to be used in the resin composition of the present invention, Light stabilizer: Tinuvin 292 (manufactured by BASF SE) Surface conditioner: BYK - 320 (manufactured by BYK - Chemie GmbH) Amine synergist: Omnipol ASA (manufactured by IGM Resins B.V.) Fluorescent brightening agent: Tinopal OB CO (manufactured by BASF SE) Examples of the urethane curing catalyst include DBTDL (dibutyltin dilaurate).

[0097] As the top - coat clear paint to be applied after curing the resin composition of the present invention, Clear paint: R - 2830 Clear (manufactured by Nippon Paint Automotive Coatings Co., Ltd.) can be mentioned.

[0098] Calculation of Reactive Energy Ray Reaction Rate Using FT-IR Peak wavelength A: 1730 cm -1 Carbon-oxygen double bond derived from ester bond Peak wavelength B: 810 cm -1 Carbon-carbon double bond derived from acrylate Peak B is due to the decrease of the carbon-carbon double bond derived from acrylate by radical polymerization upon irradiation with reactive energy rays. Therefore, the reaction rate can be calculated from the area ratio of Peak A and Peak B before and after irradiation with reactive energy rays. Irradiation with reactive energy rays was carried out under the condition that the reaction rate was 75% or more.

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

[0100] Example 1 Into a container equipped with a stirrer, each component shown in Table 2-1 was put, and while stirring, component (F) in an amount such that the solid content of the paint became 40% was put, and stirred for 30 minutes to obtain a reactive energy ray curable resin composition. The obtained resin composition was spray-coated so that the dry film thickness became 10 μm, and left standing 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, at a peak illuminance of 200 mW / cm 2 it was irradiated for 10 minutes. The reaction rate of the coating film was measured and confirmed to be 75% or more. The peak illuminance in the irradiation with reactive energy rays was measured using an Eye Graphics Inc. Eye ultraviolet integrated illuminance meter UV METER UVPF-A2 (light receiving part: PD-3040A2).

[0101] Examples 2 - 37, Comparative Examples 1 - 23 Except for changing to the formulations described in Tables 2-1, 3-1, 4-1, and 5-1, coating films of Examples 2 - 37 and Comparative Examples 1 - 23 were formed in the same manner as in Example 1 to obtain final coated plates.

[0102] FRP Coated Object The FRP to be coated was the carbon composite ZC-60 manufactured by TIP Composite Co., Ltd. using plain-woven carbon fibers. It was polished with #800 sandpaper, degreased with isopropyl alcohol, and then used.

[0103] Formation of the laminated film After the transparent resin compositions of the above Examples and Comparative Examples were coated and cured, the 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 (manufactured by Nippon Paint Automotive Coatings Co., Ltd.: R-2830 Clear) was coated so that the dry film thickness was 50 μm. After completion of the coating, the test pieces were allowed to stand for 10 minutes and then heat-cured at 80 °C for 30 minutes to obtain test pieces having a multi-layer coating film.

[0104] In the Examples and Comparative Examples, the following evaluations were performed: blocking property, smoothness, adhesion, adhesion after the 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 blocking property]: The effect of suppressing the inflow of the paint into the recesses on the FRP material and suppressing pinholes due to foaming The state of the recesses and pinholes on the coating film of the coated FRP was evaluated according to the following criteria. ◎: When the recesses and pinholes are hidden and there are no defects visible to the naked eye ○: When slight recesses and pinholes are recognized △: When either the recess or the pinhole is not hidden ×: When the recesses and pinholes are not hidden

[0106] 〔Appearance evaluation of the coating film (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 using an evaluation type surface roughness measuring machine (manufactured by Mitutoyo Corporation, SURFTEST SJ-201P) in accordance with JIS-B0601. Seven measurements were taken using a sample with a 2.5 mm width cut-off (number of sections 5), and the Ra value was obtained by the upper and lower elimination average. The obtained Ra value was evaluated according to the following criteria. ◎: Ra value less than 0.2 μm 〇: Ra value of 0.2 μm or more and less than 0.4 μm △: Ra value of 0.4 μm or more and less than 1.0 μm ×: Ra value of 1.0 μm or more

[0107] [Adhesion] On the evaluation plate of the painted FRP, 100 grid marks were made at 2 mm intervals with a single-edge razor, and cellophane adhesive tape (JIS Z 1522) was sufficiently crimped thereon, and then quickly peeled off in the 90° direction. The peeling state of the coating film was evaluated by the number of grid marks of the remaining coating film. 〇: When 100 remain as they are △: When 60 - 99 remain ×: When less than 60

[0108] [Adhesion after hot water test] The test piece prepared in the same manner as above was immersed in warm water at 40°C for 240 hours, pulled out of the water, and dried at room temperature for 24 hours. Then, the adhesion to the material was examined in the same manner as the initial adhesion evaluation. ○: When 100 remain as they are △: When 60 - 99 remain ×: When less than 60

[0109] [Impact resistance test] The test piece prepared in the same manner as above was examined for cracking and adhesion of the coating film near the impact core when a 300 g hammer was dropped from a height of 30 cm with a 1 / 2 inch impact core at room temperature of 25°C using a DuPont type impact tester. (JIS K5600-5-3) ○: When the coating film has no cracks and is adhered △: There are cracks in the coating film when it is attached ×: There are cracks in the coating film and it is peeled off

[0110] [Accelerated weathering test] The test pieces prepared in the same manner as above were subjected to accelerated exposure using an Iwasaki Electric Co., Ltd. Eye Super UV Tester SUV-W161 to examine defects such as cracks and adhesion on the coating film surface. (JIS A1501 Method A) Light quantity (300 - 400 nm) for 1 year of sunlight exposure = 300 MJ / m 2 When ◎: 1500 MJ / m 2 When there are no cracks etc. and it is attached after exposure ○: 1200 MJ / m 2 When there are no cracks etc. and it is attached after exposure △: 1200 MJ / m 2 When defects such as cracks have occurred after exposure but it is attached ×: 1200 MJ / m 2 When it is peeled off after exposure

[0111]

Table 2-1

[0112]

Table 2-2

[0113]

Table 3-1

[0114]

Table 3-2

[0115]

Table 4-1

[0116]

Table 4-2

[0117]

Table 5-1

[0118]

Table 5-2

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

Industrial Applicability

[0120] The photocurable resin composition of the present invention can be suitably used as a resin composition for directly coating on a resin member having unevenness on its 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 functional (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 diluting solvent, Component (G): a polyisocyanate, and 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-diethylthioxanthone-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), The active energy ray-curable resin composition according to claim 1, wherein 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).

3. The component (G) includes at least one selected from the group consisting of the following biuret type, isocyanurate type, and adduct type, 【Chemical 1】 The active energy ray-curable resin composition according to claim 1, wherein the ratio of the number of moles of the isocyanate group of the component (G) to the number of moles of the hydroxyl group of the component (A) ([isocyanate group mole number] / [hydroxyl group mole number]) 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. It has an object to be coated 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 object to be coated, A laminate having at least one layer of the coating film.

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

7. the object to be coated contains reinforcing fibers, The laminate according to claim 5, wherein the reinforcing fiber is at least one selected from the group consisting of carbon fiber, boron fiber, aramid fiber, glass fiber, Kevlar fiber, Dyneema fiber, Zylon fiber, cellulose-based fiber, gold thread, and silver thread.

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