Active-energy-ray-curable resin composition, cured product, and laminate

Abstract

Provided is an active-energy-ray-curable resin composition containing component (a1) and / or component (a2), the total of the component (a1) and the component (a2) being 5-70 wt% per 100 wt% total of the active-energy-ray-curable resin composition, the absorbance values (A0) and (A1) in an IR spectrum obtained by FT-IR measurement satisfying (A1) / (A0)<7.9, and the refractive index being at least 1.405 and less than 1.505.　Component (a1): compound having a molecular weight of at least 0 and less than 300, and containing one ethylenically unsaturated group. Component (a2): 1,6-diene-type divinyl compound having a molecular weight of at least 90 and less than 300. (A0): maximum absorbance in a wavenumber range of 2900-2960 cm−1. (A1): maximum absorbance in wavenumber ranges of 1610-1700 cm−1 and 1750-1780 cm−1.

Description

Active energy ray-curable resin composition, cured product, and laminate

[0001] The present invention relates to an active energy ray-curable resin composition that has excellent transparency, effectively suppresses changes in hue due to light guide distance, and is suitable for optical applications.

[0002] Liquid crystal display devices are widely used as display devices for various electronic devices. In recent years, such electronic devices have become increasingly smaller, and there is a demand for smaller and lighter liquid crystal display devices as well.

[0003] Such liquid crystal display devices mainly use optical functional sheets that utilize the effects of reflection, refraction, scattering, etc., or sheets that combine these. Such optical functional sheets are imparted with various optical properties by forming an active energy ray-curable resin layer, such as a UV-curable resin layer, on the surface of a resin film.

[0004] For example, Patent Document 1 states that by adding 0.1 ppm to 10 ppm of fluorescent bleach to methacrylic resin for light guide plates, it is possible to obtain excellent side-light type surface lighting with an appropriate improvement in color tone, less unevenness, and no reduction in light utilization efficiency.

[0005] Japanese Patent Application Publication No. 8-231808

[0006] On the other hand, the inventors' investigations revealed that integrating the above-mentioned optical functional sheet with a light guide plate significantly affects the chromaticity distribution of light extracted from the light guide plate when the light is guided through a UV-curable resin layer. Specifically, they found that the photopolymerization initiator and the polymer-derived structure of the UV-curable resin layer attenuate light in the 400-500 nm wavelength range, causing yellowing of the light emitted from the light guide. In particular, in single-sided input surface light source devices, when a light guide with a distance between the light incident end face and the surface facing the light incident end face of 350 mm or more (a light guide with a light guide distance of 350 mm or more) is used, this increase in yellowing is particularly pronounced in areas with long light guide distances. In other words, the yellowing of the light emitted from the light guide does not occur uniformly across the entire light guide surface, but occurs in areas with long light guide distances.

[0007] In response to this, the present inventors conducted research and found that the bleaching agent used in the technology described in Patent Document 1 typically absorbs light in the wavelength range of 300 nm to 400 nm and emits light in the wavelength range of 400 nm to 500 nm. Therefore, in the case of white light-emitting LEDs, the light emission range does not substantially include the wavelength range described above (300 nm to 400 nm). As a result, even if a fluorescent bleaching agent is added to the methacrylic resin for the light guide, as in the technology of Patent Document 1, no fluorescence will be emitted.

[0008] An object of the present invention is to provide an active energy ray-curable resin composition that has excellent transparency, effectively suppresses changes in hue due to light guide distance, and thus exhibits little decrease in transmittance even when used in combination with a primary light source consisting of a white LED, and can suppress yellowing of emitted light at the light exit surface.

[0009] As a result of intensive research conducted by the present inventors to achieve the above-mentioned object, they found that the above-mentioned object can be achieved by an active energy ray-curable resin composition that contains component (a1): a compound containing one ethylenically unsaturated group having a molecular weight of 90 or more and less than 300, and / or component (a2): a 1,6-diene-type divinyl compound having a molecular weight of 90 or more and less than 300, and that has an absorbance in an IR spectrum obtained by FT-IR measurement controlled to fall within a specific range, and thus they have completed the present invention.

[0010] That is, according to the present invention, the active energy ray-curable resin composition contains the following component (a1) and / or component (a2), the total amount of the component (a1) and the component (a2) being 5% by weight or more and 70% by weight or less relative to 100% by weight of the entire active energy ray-curable resin composition, and the absorbance value (A ０ ), (A １ ) but (A １ ) / (A ０ Component (a1): a compound containing one ethylenically unsaturated group and having a molecular weight of 90 or more and less than 300; Component (a2): a 1,6-diene type divinyl compound having a molecular weight of 90 or more and less than 300 (A ０ ): wave number 2900-2960cm－１ The maximum absorbance in the range (A １ ): wave number 1610-1700cm －１ and 1750-1780 cm －１ Maximum absorbance in the range

[0011] In the active energy ray-curable resin composition of the present invention, the component (a1) is preferably at least one selected from a (meth)acrylic acid ester having an oxygen-containing heterocyclic structure, a (meth)acrylic acid ester having an aromatic ring, a chain (meth)acrylamide, and a (meth)acrylic acid ester having a hydroxyl group. In the active energy ray-curable resin composition of the present invention, the component (a2) is preferably an α-allyloxymethyl acrylic acid ester. The active energy ray-curable resin composition of the present invention preferably further contains at least one of the following components (b1), (b2), and (b3): ​​Component (b1): a compound containing two or more ethylenically unsaturated groups and having a molecular weight of 300 or more but less than 1000; Component (b2): a compound containing two or more ethylenically unsaturated groups and having a weight average molecular weight of 1000 or more but less than 150000; Component (b3): ​​an acrylic polymer with a weight average molecular weight of 1000 or more but less than 150000.

[0012] In the active energy ray-curable resin composition of the present invention, it is preferable that the component (b2) is at least one selected from polyester (meth)acrylate, polyether (meth)acrylate, epoxy (meth)acrylate, urethane (meth)acrylate, and acrylic (meth)acrylate. The active energy ray-curable resin composition of the present invention preferably further contains an α-hydroxyketone compound as a photoinitiator. The active energy ray-curable resin composition of the present invention preferably has a viscosity of 4 mPa·s or more at 25°C. The active energy ray-curable resin composition of the present invention preferably has a refractive index of 1.405 or more and less than 1.505. The active energy ray-curable resin composition of the present invention is preferably used to form a cured product layer on a resin substrate.

[0013] According to the present invention, there is provided a cured product formed from the above-described active energy ray-curable resin composition. The cured product of the present invention has an absorbance value (A ０ ), (A １ ) but (A １ ) / (A ０ )<4.9. The cured product of the present invention preferably has a refractive index of 1.441 or more and less than 1.541.

[0014] The present invention also provides a laminate comprising a resin substrate and a cured material layer made of the above-described cured material. In the laminate of the present invention, the resin substrate is preferably any one of an acrylic resin substrate, a carbonate resin substrate, a cyclic olefin resin substrate, and a cellulose resin substrate. The laminate of the present invention preferably has a primer layer between the resin substrate and the cured material layer. In the laminate of the present invention, the primer layer is preferably a urethane resin layer. In the laminate of the present invention, the primer layer preferably has a thickness of 0.05 to 1 μm. In the laminate of the present invention, the resin substrate preferably further comprises a diffusion region having a thickness of 1 μm or more, in which a component of the cured material is present.

[0015] In the laminate of the present invention, the 90-degree peel strength between each of the layers constituting the laminate is preferably 0.3 N / 25 mm or more. In the laminate of the present invention, the thickness of the resin substrate is preferably 10 to 100 μm. In the laminate of the present invention, the thickness of the cured material layer is preferably 1 to 50 μm. In the laminate of the present invention, the total light transmittance is preferably 90% or more. In the laminate of the present invention, the refractive index of the cured material layer is preferably 1.441 or more and less than 1.541. In the laminate of the present invention, the indentation hardness of the surface of the cured material layer is preferably 30 N / mm ２ In the laminate of the present invention, a fine pattern is preferably formed on the surface of the cured product layer.

[0016] According to the present invention, there is also provided a cured product formed from an active energy ray-curable resin composition containing the following component (a1) and / or component (a2), wherein the cured product has an absorbance value (A ０ ), (A １ ) but (A １ ) / (A ０ )<4.9 and having a refractive index of 1.441 or more and less than 1.541. Component (a1): A compound containing one ethylenically unsaturated group and having a molecular weight of 90 or more and less than 300. Component (a2): A 1,6-diene type divinyl compound (A ０ ): wave number 2900-2960cm －１ The maximum absorbance in the range (A １ ): wave number 1610-1700cm －１ and 1750-1780 cm －１ Maximum absorbance in the range

[0017] According to the present invention, it is possible to provide an active energy ray-curable resin composition that is excellent in transparency, effectively suppresses changes in hue depending on the light guide distance, and is suitable for optical applications.

[0018] Fig. 1 is a cross-sectional view showing the configuration of a laminate according to an embodiment of the present invention. Fig. 2 is a diagram showing an example of a manufacturing apparatus using a film mold for a laminate according to an embodiment of the present invention. Fig. 3 is a diagram showing another example of a manufacturing apparatus for a laminate according to an embodiment of the present invention. Fig. 4 is a diagram for explaining a shaped film according to an example of the present invention. Fig. 5 is a diagram for explaining a method for measuring Δxy.

[0019] <Active Energy Ray-Curable Resin Composition> The active energy ray-curable resin composition of the present invention contains the component (a1) and / or the component (a2), and the total amount of the component (a1) and the component (a2) is 5% by weight or more and 70% by weight or less relative to 100% by weight of the entire active energy ray-curable resin composition, and the absorbance value (A ０ ), (A １ ) but (A １) / (A ０ )<7.9. Component (a1): A compound containing one ethylenically unsaturated group and having a molecular weight of 90 or more and less than 300. Component (a2): A 1,6-diene type divinyl compound having a molecular weight of 90 or more and less than 300. ０ ): wave number 2900-2960cm －１ The maximum absorbance in the range (A １ ): wave number 1610-1700cm －１ and 1750-1780 cm －１ Maximum absorbance in the range

[0020] Component (a1) is a compound containing one ethylenically unsaturated group and having a molecular weight of 90 or more but less than 300. Component (a1) may have a molecular weight in the range of 90 or more but less than 300, preferably a molecular weight of 100 to 250, and more preferably a molecular weight of 140 to 210. Component (a1) is preferably one selected from a (meth)acrylic acid ester having an oxygen-containing heterocyclic structure, a (meth)acrylic acid ester having an aromatic ring, a chain (meth)acrylamide, and a (meth)acrylic acid ester having a hydroxyl group.

[0021] Specific examples of component (a1) include tetrahydrofurfuryl acrylate (for example, Viscoat #150 THFA manufactured by Osaka Organic Chemical Industry Co., Ltd.); acrylates having a non-aromatic heteroatom-containing cyclic structure such as β-hydroxy-γ-butyrolactone methacrylate; benzyl acrylate (for example, Viscoat #160 BZA manufactured by Osaka Organic Chemical Industry Co., Ltd.); phenol EO-modified acrylates (for example, Aronix M-101A manufactured by Toagosei Co., Ltd.); isobornyl (meth)acrylate; cyclohexyl acrylate; dicyclopentanyl acrylate; 4-t-butylcyclohexyl acrylate; cyclic trimethylolpropane formal acrylates (for example, Viscoat #200 manufactured by Osaka Organic Chemical Industry Co., Ltd.); CTFA, etc.); tetrahydrodicyclopentadienyl methacrylate; 4-hydroxybutyl acrylate (for example, "4HBA" manufactured by Shinryo Corporation, etc.); 4-hydroxybutyl acrylate glycidyl ether (for example, "4HBAGE" manufactured by Shinryo Corporation, etc.); 2-hydroxybutyl methacrylate (for example, "Light Ester HOB(N)" manufactured by Kyoeisha Chemical Co., Ltd.); (3,4-epoxycyclohexyl)methyl acrylate; 3-methoxypropyl acrylate; dicyclopentenyl acrylate (for example, "FA-511AS" manufactured by Showa Denko Materials Co., Ltd., etc.); Examples of the acrylate include dicyclopentenyloxyethyl acrylate (for example, "FA-512AS" manufactured by Showa Denko Materials Co., Ltd.); dicyclopentanyl acrylate (for example, "FA-513AS" manufactured by Showa Denko Materials Co., Ltd.); dicyclopentanyl methacrylate (for example, "FA-513M" manufactured by Showa Denko Materials Co., Ltd.); acryloylmorpholine (for example, "ACMO" manufactured by KJ Chemicals Co., Ltd.); 2-hydroxybutyl methacrylate; benzyl acrylate (for example, "Viscoat #160 BZA" manufactured by Osaka Organic Chemical Industry Co., Ltd.); diethylacrylamide (for example, "DEAA" manufactured by KJ Chemicals Co., Ltd.); and dimethylacrylamide (for example, "DMAA" manufactured by KJ Chemicals Co., Ltd.).

[0022] Component (a2) is a 1,6-diene type divinyl compound having a molecular weight of 90 or more but less than 300, and the molecular weight may be in the range of 90 or more but less than 300, but preferably has a molecular weight of 100 to 250, and more preferably has a molecular weight of 120 to 180. Component (a2) is preferably an α-allyloxymethyl acrylic acid ester (for example, "AOMA" manufactured by Nippon Shokubai Co., Ltd.).

[0023] The content of components (a1) and (a2) in the active energy ray-curable resin composition of the present invention, as the total content of components (a1) and (a2), is 5 wt% or more and 70 wt% or less, preferably 10 to 60 wt%, and more preferably 15 to 55 wt%, based on 100 wt% of the total active energy ray-curable resin composition. If the total content of components (a1) and (a2) is too low, the viscosity of the active energy ray-curable resin composition may increase too much, resulting in an increase in bubbles and a decrease in the transferability of fine patterns. Furthermore, adhesion to the resin substrate may be insufficient, resulting in the formation of voids at the interface. This increases light scattering in the cured product, leading to a decrease in transparency and a deterioration in hue due to the light guide distance. On the other hand, if the total content of components (a1) and (a2) is too high, the viscosity of the active energy ray-curable resin composition may decrease too much, making it difficult to obtain the desired thickness and to handle the composition. Furthermore, the film-forming properties of the cured product may be reduced.

[0024] Furthermore, the active energy ray-curable resin composition of the present invention contains the component (a1) and / or the component (a2) in the above-mentioned specific amounts, and in addition, has an absorbance value (A ０ ), (A １ ) but (A １ ) / (A ０ ) < 7.9. ０ ): wave number 2900-2960cm －１ The maximum absorbance in the range (A １ ): wave number 1610-1700cm －１ and 1750-1780 cm －１ Maximum absorbance in the range

[0025] The absorbance value (A ０ ) is the absorbance value due to the C-H stretching vibration of the methylene group. １ ) is the absorbance (wavenumber 1610 to 1700 cm) derived from the stretching vibration of the carbonyl group of the amide group and / or the stretching vibration of the ethylenically unsaturated bond. －１ ) and absorbance due to the stretching vibration of the carbonyl group of the amide group (wave number 1750 to 1780 cm －１ In other words, the active energy ray-curable resin composition of the present invention is one in which the amount of amide groups is controlled to a specific amount or less. According to the present invention, the active energy ray-curable resin composition contains the component (a1) and / or the component (a2) in the above-mentioned specific amounts, and has an absorbance value (A ０ ), (A １ ) but (A １ ) / (A ０ )<7.9, excellent transparency can be achieved, and changes in hue due to the light guide distance can be effectively suppressed.

[0026] The absorbance value (A ０ ), (A １ ) is (A １ ) / (A ０ ) < 7.9 is sufficient, but preferably (A １ ) / (A ０ ) < 7.1, and more preferably (A １ ) / (A ０ ) <6.1. (A １ ) / (A ０ The lower limit of (A) is not particularly limited, but is usually １ ) / (A ０ ) > 0.1. １ ) / (A ０ ) can be controlled, for example, by adjusting the type and amount of the amide group-containing compound in the active energy ray-curable resin composition.

[0027] The refractive index of the active energy ray-curable resin composition of the present invention is preferably 1.405 or more and less than 1.505, more preferably 1.415 to 1.495.

[0028] Furthermore, the active energy ray-curable resin composition of the present invention preferably contains at least one of the following components (b1), (b2) and (b3) in addition to component (a1) and / or component (a2). By containing at least one of component (b1), (b2) and (b3), it is possible to ensure a good viscosity for maintaining the coating film before curing, resulting in excellent coating film stability and improved film-forming properties. Component (b1): A compound containing two or more ethylenically unsaturated groups with a molecular weight of 300 or more and less than 1000. Component (b2): A compound containing two or more ethylenically unsaturated groups with a weight-average molecular weight of 1000 or more and less than 150000. Component (b3): ​​An acrylic polymer with a weight-average molecular weight of 1000 or more and less than 150000.

[0029] Component (b1) is a compound containing two or more ethylenically unsaturated groups and having a molecular weight of 300 or more but less than 1,000. The molecular weight may be in the range of 300 or more but less than 1,000, but a molecular weight of 300 to 900 is preferred, and a molecular weight of 300 to 800 is more preferred. Specific examples of component (b1) include polyether acrylates such as polypropylene glycol diacrylate and polyethylene glycol diacrylate (for example, "Aronix M-220" and "Aronix M-240" manufactured by Toagosei Co., Ltd.); glycol acrylic acid adducts such as hydroxypivalic acid neopentyl glycol acrylic acid adduct (for example, "Light Acrylate HPP-A" manufactured by Kyoeisha Chemical Co., Ltd.); pentaerythritol tri- and tetraacrylates (for example, "Aronix M-450" manufactured by Toagosei Co., Ltd.); dipentaerythritol penta- and hexaacrylates (for example, "Aronix M-400" and "Aronix M-402" manufactured by Toagosei Co., Ltd.); diglycerin EO-modified acrylates (for example, "Aronix M-400" manufactured by Toagosei Co., Ltd.); tricyclodecane dimethanol diacrylate (for example, "EBECRYL 130" manufactured by Daicel Allnex Co., Ltd.); bisphenol A type epoxy acrylate; and the like.

[0030] Component (b2) is a compound containing two or more ethylenically unsaturated groups and having a weight-average molecular weight of 1,000 or more but less than 150,000. The weight-average molecular weight may be in the range of 1,000 or more but less than 150,000, but a weight-average molecular weight of 1,000 to 140,000 is preferred, and a weight-average molecular weight of 1,000 to 130,000 is more preferred. The weight-average molecular weight is a value determined by GPC measurement in terms of polystyrene. Component (b2) is preferably at least one selected from polyester (meth)acrylate, polyether (meth)acrylate, epoxy (meth)acrylate, urethane (meth)acrylate, and acrylic (meth)acrylate.

[0031] Specific examples of component (b2) include polyester acrylates (for example, "Aronix M-8060," "Aronix M-9050," and "Aronix M-6100" manufactured by Toagosei Co., Ltd., "EBECRYL 1830" manufactured by Daicel Allnex Corporation, and "MIRAMER PS6430" and "MIRAMER PS9600F" manufactured by MIWON Corporation); acrylic acid adducts of epoxy esters (for example, "EPOXY ESTER 80MFA" manufactured by Kyoeisha Chemical Co., Ltd.); urethane acrylates (for example, "UV-7000B" manufactured by Mitsubishi Chemical Corporation); and polyacrylic acrylates (for example, "OAP-2531," "MAP-2801," and "AHC-9206AC80" manufactured by Negami Chemical Industrial Co., Ltd.).

[0032] Component (b3) is an acrylic polymer having a weight-average molecular weight of 1,000 or more and less than 150,000. The weight-average molecular weight may be in the range of 1,000 or more and less than 150,000, but the weight-average molecular weight is preferably 1,000 to 140,000, and more preferably 1,000 to 130,000. The weight-average molecular weight is a value determined by GPC measurement in terms of polystyrene. Specific examples of the component (b3) include acrylic polymers (for example, "EBECRYL 1710," "EBECRYL 303," "EBECRYL 767," and "EBECRYL 305" manufactured by Daicel Allnex Co., Ltd.; "MIRAMER SC9213" manufactured by MIWON Co., Ltd.; "DIANAL BR-50," "DIANAL BR-80," "DIANAL BR-105," "DIANAL BR-106," "DIANAL BR-107," "DIANAL BR-115," "DIANAL MB-2539," "DIANAL MB-2660," and "DIANAL MB-7497" manufactured by Mitsubishi Chemical Corporation; "DEGALAN LP64 / 12," "DEGALAN PM381N," and "DEGALAN 64 / 12N").

[0033] The content of components (b1), (b2), and (b3) in the active energy ray-curable resin composition of the present invention, as the total content of components (b1), (b2), and (b3), is 30% by weight or more, preferably 40 to 95% by weight, and more preferably 45 to 90% by weight, relative to 100% by weight of the entire active energy ray-curable resin composition. By setting the total content of components (b1), (b2), and (b3) within the above range, a good viscosity for maintaining a coating film before curing can be ensured, resulting in a coating film with better stability and improved film-forming properties.

[0034] The active energy ray-curable resin composition of the present invention may also contain other curable monomers in addition to component (a1) and / or component (a2), and components (b1), (b2), and (b3) that are used as needed. Examples of other curable monomers include compounds containing two or more ethylenically unsaturated groups and having a molecular weight of less than 300, such as 1,6-hexanediol diacrylate (e.g., "HDDA" manufactured by Daicel Allnex Corporation), dipropylene glycol diacrylate (e.g., "M222" manufactured by MIWON Corporation), and trimethylolpropane triacrylate (e.g., "M-309" manufactured by Toagosei Co., Ltd.).

[0035] The content of the other curable monomer in the active energy ray-curable resin composition of the present invention is preferably 0 to 60% by weight, more preferably 0 to 55% by weight, and even more preferably 0 to 50% by weight, relative to 100% by weight of the entire active energy ray-curable resin composition.

[0036] The molecular weight of each component in the active energy ray-curable resin composition of the present invention is identified by mass spectrometry (MS) for those having a molecular weight of less than 1,000, and is the weight-average molecular weight (Mw) calculated as a standard polystyrene equivalent by gel permeation chromatography (GPC) for those having a molecular weight of 1,000 or more. The weight-average molecular weight (Mw) can be measured, for example, using a GPC device (product name "HLC-8320 GPC with built-in RI detector / UV-8320", manufactured by Tosoh Corporation) under the following conditions: analytical column: two TSKgel SuperMultiporeHZ-M columns, reference column: two TSKgel SuperHM-H columns, detector: RI detector, sample injection amount: 10 μL, sample concentration: 0.1 w / v%, eluent: chloroform, measurement temperature: 40° C., flow rate: 0.35 mL / min. The calibration curve can be created, for example, by using a standard polystyrene of known molecular weight (product name "PStQuick MP-M", manufactured by Tosoh Corporation), plotting the elution time of each peak from the measured standard polystyrene against the molecular weight value, and performing approximation using a cubic equation. It should be noted that, even after curing of the active energy ray-curable resin composition of the present invention, unreacted components can be detected by techniques such as gas chromatography-mass spectrometry (GC-MS) and NMR.

[0037]

[0043] Furthermore, the active energy ray-curable resin composition of the present invention preferably contains a photoinitiator. Examples of the photoinitiator include acylphosphine oxide compounds, α-hydroxyketone compounds, intramolecular hydrogen abstraction compounds, α-aminoketone compounds, and oxime ester compounds. Among these, α-hydroxyketone compounds are preferred.

[0038] Specific examples of the acylphosphine oxide compound include bis-2,6-dimethoxybenzoyl-2,4,4-trimethylpentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (for example, "Omnirad TPO" manufactured by IGM Resins), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (for example, "Omnirad 819" manufactured by IGM Resins), and ethoxy(2,4,6-trimethylbenzoyl)phenylphosphine oxide (for example, "Omnirad TPO-L" manufactured by IGM Resins).

[0039] Specific examples of the α-hydroxyketone compound include 2-hydroxy-2-methylpropiophenone (e.g., "Omnirad 1173" manufactured by IGM Resins), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propan-1-one (e.g., "Omnirad 127" manufactured by IGM Resins), 2-hydroxy-4'-hydroxyethoxy-2-methylpropiophenone (e.g., "Omnirad 2959" manufactured by IGM Resins), 1-hydroxycyclohexylphenyl ketone (e.g., "Omnirad 184" manufactured by IGM Resins), oligo{2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone} (e.g., "Omnirad 184" manufactured by IGM Resins), and methyl-2-hydroxy-4'-hydroxyethoxy-2-methylpropiophenone (e.g., "Omnirad 184" manufactured by IGM Resins). Resins' "ESACURE ONE" and the like.

[0040] Specific examples of the intramolecular hydrogen abstraction compound include phenyl glyoxylic acid methyl ester (for example, "Omnirad MBF" manufactured by IGM Resins), bis(η5-2,4-cyclopentadien-1-yl)bis[2,6-difluoro-3-(1H-pyrrol-1-yl)phenyltitanium] (for example, "Omnirad 784" manufactured by IGM Resins), and 2,2-dimethoxy-1,2-diphenylethan-1-one (for example, "Omnirad 651" manufactured by IGM Resins).

[0041] Specific examples of the α-aminoketone compound include 2-methyl-4′-methylthio-2-morpholinopropiophenone (for example, “Omnirad 907” manufactured by IGM Resins), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (for example, “Omnirad 369” manufactured by IGM Resins), and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (for example, “Omnirad 379EG” manufactured by IGM Resins).

[0042] Specific examples of the oxime ester compound include 1-[4-(phenylthio)-2-(O-benzoyloxime)] (Irgacure OXE01), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime) (Irgacure OXE02), Irgacure OXE03, and Irgacure OXE04 (all manufactured by BASF).

[0043] The content of the photoinitiator is preferably 0.2 to 8 wt %, more preferably 1 to 5 wt %, and even more preferably 1.5 to 4 wt %, based on 100 wt % of the total active energy ray-curable resin composition of the present invention. By setting the content of the photoinitiator within the above range, it is possible to obtain excellent transparency, effectively suppress changes in hue due to light guide distance, and ensure sufficient curability of the active energy ray-curable resin composition.

[0044] The active energy ray-curable resin composition of the present invention may further contain additives such as antioxidants, light stabilizers, and polymerization inhibitors, as long as the effects of the present invention are not impaired.

[0045] Specific examples of antioxidants include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate ("IRGANOX 1010"), thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate ("IRGANOX 1035"), octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate ("IRGANOX 1076"), "IRGANOX 1135", "IRGANOX 1330", 4,6-bis(octylthiomethyl)-o-cresol ("IRGANOX 1520L"), and "IRGANOX 1726". "IRGANOX245", "IRGANOX259", "IRGANOX3114", "IRGANOX3790", "IRGANOX5057", and "IRGANOX565" (all manufactured by BASF); "ADK STAB AO-20", "ADK STAB AO-30", "ADK STAB AO-40", "ADK STAB AO-50", "ADK STAB AO-60", and "ADK STAB AO-80" (all manufactured by ADEKA Corporation); "JP-360", "JP-308E", and "JPE-10" (all manufactured by Johoku Chemical Industry Co., Ltd.); and "Sumilizer BHT", "Sumilizer BBM-S", and "Sumilizer GA-80" (all manufactured by Sumitomo Chemical Co., Ltd.).

[0046] Specific examples of light stabilizers include "TINUVIN 111FDL", "TINUVIN 123", "TINUVIN 144", "TINUVIN 152", "TINUVIN 292", "TINUVIN 622", "TINUVIN 770", "TINUVIN 765", "TINUVIN 780", "TINUVIN 905", "TINUVIN 5100", "TINUVIN 5050", "TINUVIN 5060", "TINUVIN 5151", "CHIMASSORB 119FL", "CHIMASSORB 944FL", and "CHIMASSORB 944LD" (all manufactured by BASF Corporation), "ADK STAB LA-52", "ADK STAB LA-57", "ADK STAB LA-62", "ADK STAB LA-67", "ADK STAB LA-63P", "ADK STAB LA-68LD", "ADK STAB LA-77", "ADK STAB LA-82", and "ADK STAB LA-87" (all manufactured by ADEKA Corporation).

[0047] Specific examples of the polymerization inhibitor include quinones such as hydroquinone, parabenzoquinone, and 2,5-di-tert-butylbenzoquinone; phenols such as 4-methoxyphenol and 6-tert-butyl-2,4-xylenol; sulfur-containing compounds such as phenothiazine, thiourea, and N,N-diethyldithiocarbamate sodium; nitroso compounds such as N-nitrosodiphenylamine and N-nitrosophenylhydroxylamine aluminum salt; piperidine-1-oxyls such as 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl; phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, and tribenzylphosphine; phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide; and phosphite compounds such as triphenyl phosphite and trisnonylphenyl phosphite.

[0048] The content of additives such as antioxidants, light stabilizers, and polymerization inhibitors is preferably 0.001 to 3 wt %, more preferably 0.01 to 1.5 wt %, even more preferably 0.02 to 1 wt %, and most preferably 0.03 to 0.3 wt %, based on 100 wt % of the total active energy ray-curable resin composition of the present invention. By setting the content of additives within the above ranges, it is possible to achieve excellent transparency, effectively suppress change in hue due to light guide distance, and ensure sufficient curability of the active energy ray-curable resin composition.

[0049] The active energy ray-curable resin composition of the present invention preferably has a viscosity at 25°C of 4 mPa·s or more, more preferably 7 mPa·s or more, and even more preferably 10 mPa·s or more. When the viscosity is in the above range, good coatability can be achieved. The viscosity at 25°C can be measured, for example, using a B-type viscometer.

[0050] The active energy ray-curable resin composition of the present invention has excellent transparency and effectively suppresses hue change due to light guide distance, and therefore can be suitably used for forming a cured product layer on various resin substrates. In particular, the active energy ray-curable resin composition of the present invention can suppress the hue change Δxy over the distance between two points, and particularly can suppress the hue change Δxy even when the light guide distance is relatively long. As a result, even when used in combination with a primary light source consisting of a white LED, the decrease in transmittance is small and yellowing of emitted light at the light exit surface can be suppressed. Therefore, the active energy ray-curable resin composition of the present invention can be suitably used for light guide plates of various liquid crystal display devices and lighting devices, such as liquid crystal display devices using white LEDs, and can effectively suppress color change even when used as a light guide plate of various liquid crystal display devices and lighting devices.

[0051] <Cured Product> The cured product of the present invention is formed from the active energy ray-curable resin composition of the present invention.

[0052] The cured product of the present invention can be formed by irradiating the active energy ray-curable resin composition of the present invention with active energy rays, such as ultraviolet rays, to cure the active energy ray-curable resin composition.

[0053] The cured product of the present invention has the above absorbance value (A ０ ), (A １ ) but (A １ ) / (A ０ ) < 4.9, and more preferably (A １ ) / (A ０ ) < 4.8, and more preferably (A １ ) / (A ０ ) <4.2. (A １ ) / (A ０ The lower limit of (A) is not particularly limited, but is usually １ ) / (A ０ )>0.1. １ ) / (A ０ ) is the (A) of the active energy ray-curable resin composition of the present invention. １ ) / (A ０ The content of the components can be controlled by adjusting the viscosity of the cured product of the present invention, adjusting the curing conditions, or the like. The content of the components in the cured product of the present invention can be confirmed, for example, by performing solvent extraction and analyzing the resulting extract with GC-MS, NMR, or the like. The chemical structure of the cured product of the present invention can be clarified by analyzing it with pyrolysis GC-MS, solid-state NMR, or the like.

[0054] <Laminate> The laminate of the present invention comprises, on a resin substrate, a cured product layer made of a cured product formed using the active energy ray-curable resin composition of the present invention.

[0055] The laminate of the present invention may be one in which a cured product layer made of a cured product formed using the active energy ray-curable resin composition of the present invention is formed directly on a resin substrate, but it is preferable that these are formed via a primer layer, i.e., the primer layer and the cured product layer are formed in this order on the resin substrate.

[0056] Here, Fig. 1 is a cross-sectional view showing the configuration of a laminate according to one embodiment of the present invention. As shown in Fig. 1, the laminate according to one embodiment has a laminate structure in which an active energy ray-curable resin layer 20 is formed on a substrate film 10. In the laminate according to one embodiment, the substrate film 10 is formed by forming a primer layer 12 on a resin substrate 11, and as shown in Fig. 1, the cured product layer 20 is formed on the resin substrate 11 via the primer layer 12. The following description will be given using the laminate according to one embodiment shown in Fig. 1 as an example.

[0057] <Resin substrate 11> The resin substrate 11 is not particularly limited, but examples thereof include an acrylic resin substrate, a carbonate resin substrate, a cyclic olefin resin substrate, and a cellulose resin substrate. Among these, an acrylic resin substrate is preferred from the viewpoint of excellent optical properties.

[0058] The acrylic resin substrate is not particularly limited as long as it is a film-like substrate containing an acrylic resin. Examples of acrylic resins include poly(meth)acrylic acid esters such as polymethyl methacrylate, methyl methacrylate-(meth)acrylic acid copolymers, methyl methacrylate-(meth)acrylic acid ester copolymers, methyl methacrylate-acrylic acid ester-(meth)acrylic acid copolymers, methyl (meth)acrylate-styrene copolymers, and polymers having alicyclic hydrocarbon groups (for example, methyl methacrylate-cyclohexyl methacrylate copolymers, methyl methacrylate-norbornyl (meth)acrylate copolymers, etc.). Note that "(meth)acrylic" means acrylic and / or methacrylic.

[0059] The acrylic resin substrate may contain, in addition to the acrylic resin, a thermoplastic resin other than the acrylic resin. Examples of the thermoplastic resin other than the acrylic resin include olefin polymers, halogenated vinyl polymers, polyesters, polyacetals, polycarbonates, polyether ether ketones, polysulfones, polyether sulfones, polyoxybenzylene, polyamide imides, and rubber polymers. The content of the acrylic resin in the resin substrate 11 is preferably 80% by weight or more, more preferably 90% by weight or more, and even more preferably 95% by weight or more. It is particularly preferred that the resin substrate 11 is substantially 100% by weight of the acrylic resin.

[0060] The thickness of the resin substrate 11 is not particularly limited, but from the viewpoint of strength and optical properties, it is preferably 10 to 100 μm, more preferably 18 to 42 μm. The resin substrate 11 may be a stretched film of a resin such as an acrylic resin, and for example, the optical properties may be adjusted by stretching, and the thickness may be set within the above range.

[0061] <Primer Layer 12> The primer layer 12 is a layer formed on the resin substrate 11, and is usually a layer formed to improve adhesion between the resin substrate 11 and the cured product layer 20 formed from the active energy ray-curable resin composition of the present invention. The primer layer 12 is not particularly limited, but is preferably a layer containing a urethane-based resin from the viewpoint of being able to further improve adhesion. In other words, it is preferably a urethane-based resin layer.

[0062] Urethane resins are reaction products of polyols and polyisocyanates. Examples of polyols include polymer polyols such as polyacrylic polyols, polyester polyols, and polyether polyols. Examples of polyisocyanates include aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, and araliphatic diisocyanates.

[0063] Furthermore, the urethane-based resin layer may contain inorganic fine particles in addition to the urethane-based resin. Examples of the inorganic fine particles include titania, alumina, calcium carbonate, talc, silica, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate, and calcium phosphate.

[0064] The urethane-based resin layer can be formed, for example, by using an aqueous dispersion of urethane-based resin particles, in which urethane-based resin particles are dispersed in an aqueous medium such as water, applying the aqueous dispersion of urethane-based resin particles to the resin substrate 11, and then drying the applied dispersion. In this case, the aqueous dispersion of urethane-based resin particles may contain the inorganic fine particles described above, and may also contain a crosslinking agent. When a crosslinking agent is added, a crosslinked structure can be introduced by crosslinking the urethane-based resin particles, thereby improving adhesion durability. Examples of crosslinking agents that can be used include those containing an amino group, an oxazoline group, an epoxy group, a carbodiimide group, or the like.

[0065] The thickness of the primer layer 12 is not particularly limited, but from the viewpoint of adhesion to the cured product layer 20 and optical properties, it is preferably 0.05 to 1 μm, more preferably 0.1 to 0.6 μm, and even more preferably 0.15 to 0.4 μm.

[0066] Furthermore, from the viewpoint of reliability, the 90-degree peel strength of the primer layer 12 from the resin substrate 11 is preferably 0.3 N / 25 mm or more, more preferably 1.0 N / 25 mm or more, and even more preferably 2.0 N / 25 mm or more.

[0067] <Cured Material Layer 20> The cured material layer 20 is a layer made of a cured product formed from the active energy ray-curable resin composition of the present invention. The cured material layer 20 is a cured resin layer formed by applying the active energy ray-curable resin composition of the present invention onto the primer layer 12 formed on the resin substrate 11 to form a layer made of the active energy ray-curable resin composition, and curing the layer using active energy rays such as ultraviolet rays.

[0068] 1, the cured material layer 20 may have a fine uneven shape (fine pattern) on its surface, and by providing such a fine uneven shape, optical properties attributable to the fine uneven shape can be realized. More specifically, by causing the fine uneven shape to cause actions such as reflection, refraction, scattering, etc., optical properties utilizing the actions of reflection, refraction, scattering, etc. can be realized.

[0069] The method for imparting a fine unevenness to the surface of the cured material layer 20 is not particularly limited, but as described below, a suitable method is to press a release film for forming a fine pattern (hereinafter referred to as a "film mold") against the surface of a layer made of an active energy ray-curable resin composition before curing, irradiate with active energy rays, cure the layer, and then peel off the film mold. In this method, since it is necessary to successfully peel off the film mold after curing the layer made of the active energy ray-curable resin composition to form the cured material layer 20, the 90-degree peel strength of the surface of the cured material layer 20 from the film mold is preferably less than 1.9 N / 25 mm, more preferably 0.9 N / 25 mm or less, and even more preferably 0.2 N / 25 mm or less. The method for imparting a fine unevenness is not limited to the method using a film mold, but also includes a method using a mold engraved with a fine unevenness.

[0070] Although FIG. 1 illustrates an example in which a fine unevenness is formed on the surface of the cured material layer 20, the present invention is not particularly limited to this example, and the cured material layer 20 may have an example in which a fine unevenness is not formed on the surface of the cured material layer 20.

[0071] From the viewpoints of strength and optical properties, the thickness of the cured material layer 20 is preferably 1 to 50 μm, more preferably 5 to 30 μm, and even more preferably 7 to 20 μm. When the cured material layer 20 has a fine unevenness on its surface as shown in Fig. 1, the thickness of the cured material layer 20 may be the thickness from the convex portion of the fine unevenness to the interface between the cured material layer 20 and the primer layer 12.

[0072] From the viewpoint of reliability, the 90-degree peel strength of the cured material layer 20 from the primer layer 12 is preferably 0.3 N / 25 mm or more, more preferably 1.0 N / 25 mm or more, and even more preferably 2.0 N / 25 mm or more.

[0073] The indentation hardness of the surface of the cured material layer 20 is preferably 30 N / mm ２ More preferably, it is 40 N / mm ２ More preferably, 60 N / mm ２ That's all.

[0074] 1 illustrates an embodiment in which the cured product layer 20 is formed directly on the primer layer 12, but a diffusion region in which the components of the primer layer 12 are present may be formed in the primer layer 12 and the resin substrate 11. The thickness of the diffusion region is preferably 1 μm or more, more preferably 1.5 μm or more, and even more preferably 2.0 μm or more.

[0075] When a diffusion region is formed, from the viewpoint of reliability, the 90-degree peel strength of the diffusion region from the primer layer 12 is preferably 0.3 N / 25 mm or more, more preferably 1.0 N / 25 mm or more, and even more preferably 2.0 N / 25 mm or more. Similarly, when a diffusion region is formed, from the viewpoint of reliability, the 90-degree peel strength of the cured material layer 20 from the diffusion region is preferably 0.3 N / 25 mm or more, more preferably 1.0 N / 25 mm or more, and even more preferably 2.0 N / 25 mm or more.

[0076] The laminate of the present invention preferably has a total light transmittance of 90% or more, more preferably 90.5% or more, and even more preferably 91% or more. The laminate of the present embodiment also preferably has a refractive index of 1.441 or more and less than 1.541, and more preferably 1.47 or more and less than 1.530.

[0077] <Method for producing laminate> Next, a method for producing the laminate of the present invention will be described. In the following, a production method will be described for the case where the cured product layer 20 has a fine uneven shape (fine pattern) on its surface as shown in FIG.

[0078] First, a primer layer 12 is formed on a resin substrate 11, thereby obtaining a substrate film 10 having the primer layer 12 formed on the resin substrate 11. When the primer layer 12 is a urethane-based resin layer, the substrate film 10 can be obtained by applying an aqueous dispersion of urethane-based resin particles, in which urethane-based resin particles are dispersed in an aqueous medium such as water, to the resin substrate 11 and drying the dispersion to form a urethane-based resin layer as the primer layer 12. At this time, if the aqueous dispersion of urethane-based resin particles contains a crosslinking agent, the drying is followed by heating to cause a crosslinking reaction. Furthermore, after forming the primer layer 12, the substrate film 10 having the primer layer 12 formed on the resin substrate 11 may be stretched as necessary.

[0079] Next, a cured material layer 20 is formed on the thus obtained substrate film 10. The cured material layer 20 can be formed, for example, using a production apparatus shown in FIG.

[0080] In the production apparatus shown in Fig. 2, first, a substrate film 10 is continuously unwound from a substrate unwind roll 30, and the substrate film 10 passes through a guide roll 31 and is then coated on its surface in a T-die 40 with the active energy ray-curable resin composition of the present invention to form a cured product layer 20, thereby forming a layer 20a made of the active energy ray-curable resin composition on the surface. The thickness of the layer 20a made of the active energy ray-curable resin composition is controlled by adjusting the clearance formed between the T-die 40 and nip rolls 32 and the unwinding speed.

[0081] 2 is configured so that a film mold 60 is continuously unwound from a film mold unwind roll 33. The substrate film 10 on which the layer 20a made of the active energy ray-curable resin composition is formed and the film mold 60 are superimposed by a laminating roll 35 and an upstream backup roll 36. Here, the film mold 60 has a predetermined fine irregular shape on the surface facing the layer 20a made of the active energy ray-curable resin composition, and a laminate is formed in which the substrate film 10, the layer 20a made of the active energy ray-curable resin composition, and the film mold 60 are superimposed in this order such that the surface having the predetermined fine irregular shape is in contact with the layer 20a made of the active energy ray-curable resin composition.

[0082] Then, a laminate obtained by stacking the substrate film 10, the layer 20a made of the active energy ray-curable resin composition, and the film mold 60 in this order is irradiated with active energy rays such as ultraviolet rays using an active energy ray irradiation device 50 such as an ultraviolet ray irradiation device, whereby the curable resin component constituting the layer 20a made of the active energy ray-curable resin composition is cured in a state in which the predetermined fine unevenness formed on the surface of the film mold 60 is transferred, thereby forming a cured product layer 20 having the desired fine unevenness on its surface, as shown in Fig. 1. Next, after undergoing a curing reaction by irradiation with active energy rays such as ultraviolet rays, the film passes between a laminating roll 35 and a downstream backup roll 37, and the film mold 60 is peeled from the substrate film 10 on which the cured product layer 20 is formed. The film mold 60 is then taken up by a film mold take-up roll 34, and the substrate film 10 on which the cured product layer 20 is formed is taken up by a substrate take-up roll 39 via a guide roll 38. Furthermore, if necessary, the film mold 60 may be used as a protective film by not peeling the film mold 60 from the substrate film 10 on which the cured material layer 20 is formed, but by winding the substrate film 10 on which the cured material layer 20 is formed and the film mold 60 via a guide roll 38 onto a substrate winding roll 39, or alternatively, after the film mold 60 is peeled from the substrate film 10 on which the cured material layer 20 is formed, a protective film may be attached to the surface of the cured material layer 20, and then the film mold 60 may be wound up onto the substrate winding roll 39.

[0083] 2, a laminate in which the cured material layer 20 is formed on the substrate film 10 is continuously produced as described above. The laminate in which the cured material layer 20 is formed on the substrate film 10 has the predetermined fine concave-convex shape formed on the film mold 60 transferred thereto, so that the laminate has the desired fine concave-convex shape on its surface.

[0084] The resin material constituting the resin film forming the film mold 60 is not particularly limited, but is preferably a thermoplastic resin, and examples thereof include polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), acrylic resins such as polymethyl methacrylate (PMMA), carbonate resins such as polycarbonate (PC), amide resins such as nylon 6, cyclic olefin resin (COP), ethylene-vinyl alcohol copolymer (EVOH), polyphenylene sulfide (PPS), etc. Two or more of these may be laminated or mixed for use.

[0085] The resin material of the protective film is not particularly limited, but examples thereof include polyethylene (PE), polypropylene (PP), etc. Two or more of these may be laminated or mixed together.

[0086] 3, a cured product layer 20 having a desired fine unevenness on its surface can also be produced by using a laminating roll 35' having a predetermined fine unevenness on its surface, without using a film mold 60, so that the roll comes into direct contact with the layer 20a made of the active energy ray-curable resin composition formed on the substrate film 10. A schematic diagram of the production apparatus is shown in FIG.

[0087] The laminate of the present invention has a cured layer formed from the active energy ray-curable resin composition of the present invention described above, and therefore has excellent transparency and effectively suppresses changes in hue due to light guide distance. In particular, the laminate of the present invention can suppress the hue change Δxy over the distance between two points, and particularly, can suppress the hue change Δxy even when the light guide distance is relatively long. As a result, even when used in combination with a primary light source consisting of a white LED, the decrease in transmittance is small and yellowing of the emitted light at the light exit surface can be suppressed. Therefore, the laminate of the present invention can be suitably used as a light guide plate for various liquid crystal display devices and lighting devices, such as liquid crystal display devices using white LEDs, and can effectively suppress changes in color even when used as a light guide plate for various liquid crystal display devices and lighting devices.

[0088] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The methods for evaluating each property are as follows.

[0089] <Viscosity of active energy ray-curable resin composition> The viscosity of the active energy ray-curable resin composition was measured using a Brookfield type viscometer (product name "Analog Viscometer LVT", manufactured by Brookfield Corporation) at a temperature of 25°C using a small amount sample adapter (sample chamber SC4-13R(P)) and a spindle SC4-18 at a rotation speed of 3 to 60 rpm.

[0090] <Absorbance Ratio> The active energy ray-curable resin composition and the cured product of the active energy ray-curable resin composition were subjected to FT-IR measurement by the single reflection ATR method using a Fourier transform infrared spectrophotometer (product name "FT / IR-6600" manufactured by JASCO Corporation). The measurement was carried out under the following conditions: Number of accumulations: 16 (same for background measurement) Wavenumber resolution: 4 cm －１ Measurement wave number range: 600 to 4000 cm －１ ATR crystal: diamond Incident angle: 45° In the obtained IR spectrum, the wave number was 2000 cm －１When the baseline is corrected at one point so that the absorbance of －１ The maximum absorbance in the range (A ０ ), wave number 1610-1700cm －１ and 1750-1780 cm －１ The maximum absorbance in the range (A １ ) and the absorbance ratio (A １ ) / (A ０ ) was sought.

[0091] <Reaction rate of cured product> The active energy ray-curable resin composition and the cured product of the active energy ray-curable resin composition were subjected to FT-IR measurement by the single reflection ATR method using a Fourier transform infrared spectrophotometer (product name "FT / IR-6600" manufactured by JASCO Corporation). The measurement was carried out under the following conditions: Number of accumulations: 16 (same for background measurement) Wavenumber resolution: 4 cm －１ Measurement wave number range: 600 to 4000 cm －１ ATR crystal: diamond Incident angle: 45° In the IR spectrum of the obtained active energy ray-curable resin composition, a wave number of 1720 cm －１ The line connecting the bases on both sides of the absorption peak resulting from the stretching vibration of the carbonyl group of the ester in the vicinity was used as the baseline, and the length from the intersection point of a line drawn perpendicular to the baseline from the peak to the peak was defined as the peak height (A ０＿１７２０ ) Then, the wave number was 810 cm －１ The line connecting the bases on both sides of the absorption peak resulting from the C-H out-of-plane bending vibration of the ethylenically unsaturated group in the vicinity of the peak is taken as the baseline, and the length from the intersection point of a line drawn perpendicular to the baseline from the peak to the peak is taken as the peak height (A ０＿８１０ In addition, in the IR spectrum of the cured product of the active energy ray-curable resin composition, the peak height (A ＿１７２０ ), (A ＿８１０ Using the value thus obtained, the reaction rate of the curable component constituting the active energy ray-curable resin composition was measured according to the following formula: Reaction rate (%) = (1 - ((A ＿８１０) / (A ＿１７２０ )) / ((A ０＿８１０ ) / (A ０＿１７２０ ))) x 100

[0092] <Total Light Transmittance, Haze Value> The total light transmittance and haze value of the laminate were measured in accordance with JIS K 7105 and JIS K 7136 using a turbidity meter (product name "Haze Meter NDH2000", manufactured by Nippon Denshoku Industries Co., Ltd.).

[0093] <Refractive Index> The refractive index of the active energy ray-curable resin composition was measured at 589 nm (D line) using an Abbe refractometer (product name "NAR-1T SOLID", manufactured by Atago Co., Ltd.) at a measurement temperature of 20° C. The refractive index of the cured product of the active energy ray-curable resin composition was measured in the same manner as above, except that diiodomethane was used as the contact liquid.

[0094] <Indentation Hardness of Cured Layer 20> The indentation hardness of the laminate was measured using an ultra-microindentation hardness tester (product name "ENT-5", manufactured by ELIONIX) with a Berkovich indenter under an indentation load of 0.1 mN, and this was taken as the indentation hardness of the cured layer.

[0095] <Thickness of Diffusion Region> A cross section of the laminate was prepared using an ultramicrotome, and line analysis was performed on the cured layer, the urethane resin layer, and the acrylic resin substrate in this order using a Raman spectrophotometer (product name "NRS-5500", manufactured by JASCO Corporation) under the following conditions: Exposure time: 60 sec, Number of integrations: 1, Range: 600 to 3000 cm －１ Grating: L600 / B500nm Laser: 532.31nm Slit: φ25mm In the obtained Raman spectrum, 2800-3000cm －１ After normalization by the maximum peak intensity of the hardened layer, the distance from the start point to the end point of attenuation of the peak intensity derived from the components of the hardened layer was determined as the thickness of the diffusion region.

[0096] Example 1 An easy-adhesion composition prepared by mixing 20.6 parts by weight of an aqueous polyurethane (product name "Superflex 210R, solids content: 34 wt %, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), 5.2 parts by weight of an oxoxalin-containing aqueous polymer solution (product name "Epocross WS-700, solids content: 25 wt %, manufactured by Nippon Shokubai Co., Ltd.), 2.8 parts by weight of 1 wt % ammonia water, 7.5 parts by weight of a 20% aqueous dispersion of colloidal silica (product name "Quattron PL-3", manufactured by Fuso Chemical Co., Ltd.), and 63.9 parts by weight of pure water was applied to the surface of an acrylic resin film, and the film was stretched to twice its original size in both the longitudinal direction (MD) and the width direction (TD) using a simultaneous biaxial stretching tenter in a heating furnace at 140°C, to obtain a substrate film 10 having a 0.3 μm-thick urethane resin layer (primer layer 12) formed on a 40 μm-thick acrylic resin substrate (resin substrate 11).

[0097] Next, an active energy ray-curable resin composition having the following composition was applied to the obtained substrate film 10, and a smooth polyethylene terephthalate film (product name "Emblet S-25", manufactured by Unitika Ltd.) was laminated thereon. Next, a UV irradiation amount of 971 mJ / cm was applied using a UV irradiation device. ２ The active energy ray-curable resin composition was cured at 150°C under the conditions described above, thereby obtaining a laminate in which a cured layer 20 (thickness of the cured layer 20: 15 μm) made of the active energy ray-curable resin composition was formed on the substrate film 10. The polyethylene terephthalate film was then peeled off to obtain a laminate, and various measurements were carried out according to the above-mentioned methods. The results are shown in Table 1. The refractive index of the cured product constituting the cured layer 20 was evaluated by applying an active energy ray-curable resin composition having the following composition to a smooth polyethylene terephthalate film, laminating the smooth polyethylene terephthalate film, and then using a UV irradiation device, applying a UV irradiation dose of 971 mJ / cm. ２By curing the composition at 400°C, a laminate was obtained in which a cured layer 20 (thickness of the cured layer 20: 40 μm) made of the active energy ray-curable resin composition was formed on a polyethylene terephthalate film. Then, measurements were performed on the active energy ray-curable resin composition obtained by peeling off the polyethylene terephthalate films on both sides. In addition, the 90-degree peel strength and Δxy of the cured layer 20 were measured by preparing a measurement sample using the following method.

[0098] <Composition of active energy ray-curable resin composition> Tetrahydrofurfuryl acrylate (product name "Viscoat #150", manufactured by Osaka Organic Chemical Industry, Ltd., molecular weight 156.2, component (a1)): 40 parts by weight Polypropylene glycol diacrylate (product name "Aronix M-220", manufactured by Toagosei Co., Ltd., molecular weight 300.3, component (b1)): 50 parts by weight Bifunctional polyacrylic acrylate (product name "EBECRYL 1710", manufactured by Daicel Allnex Corporation, weight-average molecular weight 39429, component (b3)): 10 parts by weight 1-hydroxycyclohexyl phenyl ketone (product name "Omnirad 184", manufactured by IGM Resins, α-hydroxyketone-based photopolymerization initiator): 2 parts by weight

[0099] <90-degree peel strength of cured layer 20> In the above procedure, instead of the polyethylene terephthalate film, an easy-adhesion PET film (38 μm, Cosmoshine A4300, manufactured by Toyobo Co., Ltd.) was laminated, and the active energy ray-curable resin composition was cured to obtain a laminate in which a cured layer 20 was formed on a substrate film 10. A sample measuring 25 mm wide x 150 mm long was prepared from the laminate with the easy-adhesion PET film superimposed thereon, and the acrylic resin substrate surface of the laminate was attached and fixed to a test plate with double-sided tape. Next, a tensile tester (product name "Tensilon Universal Material Tester RTC-1210A", manufactured by ORIENTEC Co., Ltd.) was used to pinch the edge of the easy-adhesion PET film at the contact surface between the urethane resin layer and the cured layer 20, and a 90-degree peel test was performed at a pulling rate of 200 mm / min to measure the 90-degree peel strength (unit: N / 25 mm). The results are shown in Table 1.

[0100] <Measurement of Δxy> First, a film (shape-transfer film) having a fine pattern imparted thereto was produced according to the method described in JP-A-2013-524288. Specifically, an active energy ray-curable resin composition was applied to the surface of a film made of polymethyl methacrylate (PMMA), and then an optical pattern was embossed and irradiated with ultraviolet light to produce the desired shape-transfer film. The total thickness of the shape-transfer film was 55 μm. FIG. 4(A) shows a plan view of a portion of the produced shape-transfer film from the side. FIG. 4(B) also shows the 4B-4B' cross section of FIG. 4(A). A plurality of recesses having a triangular cross section with a length L of 80 μm, a width W of 14 μm, and a depth H of 10 μm were arranged at intervals of 155 μm in the X-axis direction. Furthermore, such recess patterns were arranged at intervals of 100 μm in the Y-axis direction with a width D. The density of the recesses on the surface of the produced shaped film was 3612 / cm ２ In FIG. 4B, θa and θb were 41°, and the occupied area ratio of the recesses when the manufactured shaped film was viewed in plan from the fine pattern surface side was 4.05%.

[0101] Then, one release film of a 50 μm thick optical adhesive tape (product name "CS9862" manufactured by Nitto Denko Corporation) was peeled off and bonded to the surface opposite the fine pattern-forming surface of the shaped film obtained above, to obtain test piece A. Next, test piece A was cut to a size of 150 mm wide and 800 mm long, and the other release film of the optical adhesive tape was peeled off, and the surface of the adhesive layer of the exposed optical adhesive tape was attached to a polymethyl methacrylate (PMMA) plate (width 150 mm, length 1000 mm, thickness 5 mm, product name "Acrylite", manufactured by Mitsubishi Chemical Corporation) with an opening of 200 mm from the end to obtain test piece B. Then, as shown in Figure 5, light was incident from an end of test piece A 200 mm apart using an LED light source (color temperature 5000K), and measurement was performed on the entire test piece B using a two-dimensional spectroluminometer (product name "SR-5000", manufactured by TOPCON Corporation). Chromaticity (xy, CIE1931) was extracted at 250 mm and 950 mm from the light incident end, and Δxy was calculated according to the following formula. The smaller the Δxy value, the more effectively the change in hue due to the light guide distance is suppressed, and it can be determined that the color change due to the light guide distance is small.

[0102] Examples 2 to 30 Laminates and the like having the cured layer 20 formed thereon were obtained in the same manner as in Example 1, except that active energy ray-curable resin compositions having the formulations shown in Tables 1 to 3 were used as the active energy ray-curable resin compositions, and various measurements were similarly carried out. The results are shown in Tables 1 to 3.

[0103] Comparative Examples 1 to 8 Laminates and the like having the cured layer 20 formed thereon were obtained in the same manner as in Example 1, except that active energy ray-curable resin compositions having the formulations shown in Table 4 were used as the active energy ray-curable resin compositions, and various measurements were similarly carried out. The results are shown in Table 4.

[0104]

[0105]

[0106]

[0107]

[0108] The compounds used in each of the Examples and Comparative Examples are as follows. Here, when the following products consist of multiple components, the molecular weight indicates that of the component with the larger molecular weight. THFA: tetrahydrofurfuryl acrylate (product name "Viscoat #150", manufactured by Osaka Organic Chemical Industry Co., Ltd., molecular weight 156.2) ACMO: acryloylmorpholine (product name "ACMO", manufactured by KJ Chemicals, molecular weight 141.2) DEAA: diethylacrylamide (product name "DEAA", manufactured by KJ Chemicals, molecular weight 127.1) DMAA: dimethylacrylamide (product name "DMAA", manufactured by KJ Chemicals, molecular weight 99.1) 2HBMA: 2-hydroxybutyl methacrylate (product name "2-Hydroxybutyl Methacrylate", manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 158.2) M-101A: phenol EO-modified acrylate (product name "Aronix M-101A, manufactured by Toagosei Co., Ltd., molecular weight 236.3) BZA: benzyl acrylate (product name "Viscoat #160 BZA", manufactured by Osaka Organic Chemical Industry Co., Ltd., molecular weight 162.2) AOMA: α-allyloxymethyl acrylate (product name "AOMA", manufactured by Nippon Shokubai Co., Ltd., molecular weight 156.2) M-220: polypropylene glycol diacrylate (product name "Aronix M-220", manufactured by Toagosei Co., Ltd., molecular weight 300.3) VMOX: vinylmethyl oxazolidinone (product name "VMOX", manufactured by BASF, molecular weight 127.1) NVP: N-vinylpyrrolidone (product name "1-Vinyl-2-pyrrolidone", manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 111.1) IBOA: isobornyl acrylate (product name "IBOA-B", manufactured by Daicel-Allnex Corporation, molecular weight 208.3) HPP-A: hydroxypivalic acid neopentyl glycol acrylic acid adduct (product name "Light Acrylate HPP-A", manufactured by Kyoeisha Chemical Co., Ltd., molecular weight 312.4) M-8060: polyester acrylate (product name "Aronix M-8060", manufactured by Toagosei Co., Ltd., weight average molecular weight 2479) EBECRYL 1830: polyester acrylate (product name "EBECRYL 1830", manufactured by Daicel-Allnex Corporation, weight average molecular weight 3698)EBECRYL 1710: Acrylic polymer-containing solution (product name "EBECRYL 1710", manufactured by Daicel Allnex Co., Ltd., weight average molecular weight 39429) BR-107: Acrylic polymer powder (product name "DIANAL BR-107", manufactured by Mitsubishi Chemical Corporation, weight average molecular weight 74660) DEGALAN 64 / 12N: Acrylic polymer powder (product name "DEGALAN 64 / 12N", manufactured by Rohm Co., Ltd., weight average molecular weight 64716) MB-7497: Acrylic polymer powder (product name "DIANAL MB-7497", manufactured by Mitsubishi Chemical Corporation, weight average molecular weight 56353) M-6100: Polyester acrylate (product name "ARONIX M-6100", manufactured by Toagosei Co., Ltd., weight average molecular weight 1662) EBECRYL 130: tricyclodecane dimethanol diacrylate (product name "EBECRYL 130", manufactured by Daicel-Allnex Corporation, molecular weight 304.4) 3000A: bisphenol A diglycidyl ether acrylic acid adduct (product name "epoxy ester 3000A", manufactured by Kyoeisha Chemical Co., Ltd., weight average molecular weight 1160) EBECRYL 767: acrylic polymer-containing solution (product name "EBECRYL 767", manufactured by Daicel-Allnex Corporation, weight average molecular weight 19447) HDDA: 1,6-hexanediol diacrylate (product name "HDDA", manufactured by Daicel-Allnex Corporation, molecular weight 226.3) DPGDA: dipropylene glycol diacrylate (product name "M222", manufactured by MIWON Corporation, molecular weight 242.3) TMPTA: trimethylolpropane triacrylate (product name "M-309", manufactured by Toagosei Co., Ltd., molecular weight 296.3) HCPK: 1-hydroxycyclohexylphenyl ketone (product name "Omnirad 184", manufactured by IGM Resins, α-hydroxyketone-based photopolymerization initiator) TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (product name "Diphenyl(2,4,6-trimethylbenzoyl)phosphine Oxide", manufactured by Tokyo Chemical Industry Co., Ltd., acylphosphine oxide-based photopolymerization initiator)BAPO: bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (product name "Phenylbis(2,4,6-trimethylbenzoyl)phosphine Oxide", manufactured by Tokyo Chemical Industry Co., Ltd., acylphosphine oxide-based photopolymerization initiator) HMPP: 2-hydroxy-2-methylpropiophenone (product name "2-Hydroxy-2-methylpropiophenone", manufactured by Tokyo Chemical Industry Co., Ltd., α-hydroxyketone-based photopolymerization initiator) AO-60: pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (product name "ADK STAB AO-60", manufactured by ADEKA Corporation, antioxidant) IRGANOX 1035: Thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (product name "IRGANOX 1035", manufactured by BASF, antioxidant)

[0109] As shown in Tables 1 and 2, component (a1): a compound containing one ethylenically unsaturated group having a molecular weight of 90 or more and less than 300 and / or component (a2): a 1,6-diene type divinyl compound having a molecular weight of 90 or more and less than 300 is contained in a total amount of 5 wt % or more and 70 wt % or less, based on 100 wt % of the entire active energy ray-curable resin composition, and the absorbance value (A ０ ), (A １ ) but (A １ ) / (A ０ In the case of an active energy ray-curable resin composition that satisfies the condition of absorbance (A ) < 7.9 and has a refractive index of 1.405 or more and less than 1.505, the value of Δxy was low, and the change in hue due to the light guide distance was effectively suppressed (Examples 1 to 30). ０ ), (A １ ) but (A １ ) / (A ０When the refractive index was 1.505 or greater, the Δxy value was high, resulting in a large change in hue depending on the light guide distance (Comparative Examples 1 to 5). When the content of component (a1) and / or component (a2) was 5 wt % or less or 70 wt % or more, the adhesion to the substrate was insufficient, and film-forming properties were poor, making it impossible to prepare a sample (Comparative Examples 6 to 8).

[0110] REFERENCE SIGNS LIST 10... Substrate film 11... Resin substrate 12... Primer layer 20... Cured layer 20a... Layer made of active energy ray-curable resin composition 30 to 39... Roll 40... T-die 50... Active energy ray irradiation device 60... Film mold

Claims

1. The active energy ray curable resin composition comprises the following component (a1) and / or component (a2), and the following component (b1), wherein the sum of component (a1) and component (a2) is 5% by weight or more and 70% by weight or less based on 100% by weight of the total active energy ray curable resin composition, and the viscosity at 25°C is 4 mPa·s or more and 29 mPa·s or less, and the absorbance value (A) in the IR spectrum obtained by FT-IR measurement is ０ ), (A １ ) but (A １ ) / ( A ０ An active energy ray curable resin composition that satisfies <7.9 and has a refractive index of 1.405 or higher and less than 1.

505. Component (a1): A compound containing one ethylenically unsaturated group with a molecular weight of 90 or more and less than 300. Component (a2): 1,6-diene type divinyl compound with a molecular weight of 90 or more and less than 300 Component (b1): A compound containing two or more ethylenically unsaturated groups with a molecular weight of 300 or more and less than 1000. (A ０ ): wave number 2900-2960cm －１ Maximum absorbance within the range (A １ ): The maximum value of absorbance in the range of wavenumbers 1610 to 1700 cm －１ , and in the range of 1750 to 1780 cm －１ ​

2. The active energy ray curable resin composition according to claim 1, wherein the component (a1) is at least one selected from an oxygen-containing heterocyclic (meth)acrylic acid ester, an aromatic ring (meth)acrylic acid ester, a chain-like (meth)acrylamide, and a hydroxyl group (meth)acrylic acid ester.

3. The active energy ray curable resin composition according to claim 1 or 2, wherein the component (a2) is α-allyloxymethylacrylic acid ester.

4. Furthermore, the active energy ray curable resin composition according to claim 1 or 2, comprising at least one of the following components (b2) and (b3). Component (b2): A compound containing two or more ethylenically unsaturated groups with a weight-average molecular weight of 1,000 or more and less than 150,000. Component (b3): ​​Acrylic polymer with a weight-average molecular weight of 1,000 or more and less than 150,000

5. The active energy ray curable resin composition according to claim 4, wherein the component (b2) is at least one selected from polyester (meth)acrylate, polyether (meth)acrylate, epoxy (meth)acrylate, urethane (meth)acrylate, and acrylic (meth)acrylate.

6. Furthermore, the active energy ray curable resin composition according to claim 1 or 2 further comprises an α-hydroxyketone compound as a photoinitiator.

7. An active energy ray curable resin composition according to claim 1 or 2, used for forming a cured layer on a resin substrate.

8. A cured product formed from the active energy ray curable resin composition according to claim 1 or 2.

9. In the IR spectrum obtained by FT-IR measurement, the absorbance value (A ０ ), (A １ ) but (A １ ) / ( A ０ ) < The cured product according to claim 8, satisfying 4.

9.

10. The cured product according to claim 8, wherein the refractive index of the cured product is 1.441 or more and less than 1.

541.

11. A laminate comprising a cured product layer made of the cured product described in claim 8 on a resin substrate.

12. The laminate according to claim 11, wherein the resin substrate is any one of an acrylic resin substrate, a carbonate resin substrate, a cyclic olefin resin substrate, and a cellulose resin substrate.

13. The laminate according to claim 11, having a primer layer between the resin substrate and the cured material layer.

14. The laminate according to claim 13, wherein the primer layer is a urethane resin layer.

15. The laminate according to claim 13, wherein the thickness of the primer layer is 0.05 to 1 μm.

16. The laminate according to claim 11, further comprising a diffusion region of 1 μm or more in the resin substrate in which components of the cured product are present.

17. The laminate according to claim 11, wherein the 90-degree peel strength between each layer constituting the laminate is 0.3 N / 25 mm or more.

18. The laminate according to claim 11, wherein the thickness of the resin substrate is 10 to 100 μm.

19. The laminate according to claim 11, wherein the thickness of the cured layer is 1 to 50 μm.

20. The laminate according to claim 11, wherein the total light transmittance of the laminate is 90% or more.

21. The indentation hardness of the surface of the hardened layer is 30 N / mm ２ The laminate according to claim 11.

22. The laminate according to claim 11, wherein a fine pattern is formed on the surface of the cured layer.