Active energy ray curable composition and laminate

Abstract

To provide an active energy ray curable composition that can form a cured film that contains conductive particles while possessing excellent properties in terms of transparency, antistatic properties, scratch resistance, and flexibility, and a laminate having the cured film. [Solution] An active energy ray curable composition comprising: a polyfunctional (meth)acrylate (A) having three or more (meth)acryloyl groups in the molecule; conductive particles (B); and a compound (C) having at least one polyoxyalkylene chain selected from the group consisting of polyalkylene glycol, polyalkylene glycol monoalkyl ether, polyalkylene glycol dialkyl ether, polyalkylene glycol mono(meth)acrylate, polyalkylene glycol di(meth)acrylate, and alkoxy polyalkylene glycol (meth)acrylate.

Description

Technical Field

[0001] The present invention relates to an active energy ray-curable composition and a laminate having a cured film thereof.

Background Art

[0002] From the aspects of ensuring the performance and safety measures of information and communication equipment, etc., it has been conventionally practiced to protect the surface of information and communication equipment with a cured film having scratch resistance and antistatic properties. In addition, since the occurrence of cracks or the like in the cured film leads to problems that the reliability of information and communication equipment is impaired, flexural strength enough not to cause cracks or the like is also required. The development of information and communication equipment has been remarkable in recent years, and the actual situation is that further performance improvement of these cured films is required.

[0003] As a method for imparting scratch resistance, it is well known to form a cured film of a polyfunctional (meth) acrylate. Further, as a method for imparting antistatic properties, methods such as incorporating various surfactants such as cationic, anionic, and nonionic surfactants, and salts such as alkali metal salts, alkaline earth metal salts, and ammonium salts into the above-mentioned cured film are known. However, in order to obtain sufficient antistatic properties, it was necessary to add a large amount of surfactants or salts (Patent Document 1). However, the addition of a large amount of surfactants or salts tends to cause deterioration of scratch resistance, and there are problems such as poor antistatic performance in a low-humidity environment. In addition, there was a concern that surfactants or salts would bleed on the surface of the cured film over time, or that the antistatic performance would decrease under high humidity.

[0004] Other methods for imparting antistatic properties include adding conductive particles such as tin oxide (TO), antimony-doped tin oxide (ATO), phosphorus-doped tin oxide (PTO), tin-doped indium oxide (ITO), and antimony pentoxide (Sb2O5) to the cured film. However, in this method, in order to improve transparency, it is necessary to disperse the secondary aggregated fine particles down to the primary particle level, which often increases the surface resistance and worsens the antistatic performance. This is because the more the secondary aggregates of conductive particles in the film dissolve, the less likely electrical conduction is to occur due to contact or proximity of individual primary particles.

[0005] Patent Document 2 discloses an antistatic curable composition containing conductive inorganic fine particles with an average primary particle diameter of 5 to 100 nm, silicon dioxide with an average primary particle diameter of 5 to 100 nm, a functional group formed by reacting an ethylenically unsaturated double bond with a primary or secondary amine, and an amino group-containing photocurable compound having an unreacted ethylenically unsaturated double bond. However, this invention contains a large amount of conductive inorganic fine particles, raising concerns that transparency and flexibility may be impaired.

[0006] Patent Document 3 discloses an antistatic hard coat coating material comprising an active energy ray curable resin composition containing 50% by weight or more of a compound having three or more (meth)acryloyl groups in its molecule, a photopolymerization initiator, and conductive metal oxide fine particles whose particle surface is treated with a hydrolyzable organosilicon compound as essential components. However, it is unclear whether or not it has flexibility. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Publication No. 2000-281736 [Patent Document 2] Japanese Patent Publication No. 2008-019414 [Patent Document 3] Japanese Patent Publication No. 2012-236921 [Overview of the project] [Problems that the invention aims to solve]

[0008] The problem that the present invention aims to solve is to provide an active energy ray curable composition that can form a cured film that contains conductive particles while possessing excellent properties in terms of transparency, antistatic properties, scratch resistance, and flexibility, and a laminate having the cured film. [Means for solving the problem]

[0009] The inventors of this invention have diligently conducted research to solve the above problems and have completed the following inventions [1] to [7].

[0010] [1] An active energy ray curable composition comprising: a polyfunctional (meth)acrylate (A) having three or more (meth)acryloyl groups in the molecule; conductive particles (B); and a compound (C) having at least one polyoxyalkylene chain selected from the group consisting of polyalkylene glycol, polyalkylene glycol monoalkyl ether, polyalkylene glycol dialkyl ether, polyalkylene glycol mono(meth)acrylate, polyalkylene glycol di(meth)acrylate, and alkoxy polyalkylene glycol (meth)acrylate.

[0011] [2] The active energy ray curable composition wherein the conductive particle (B) is antimony pentoxide.

[0012] [3] The above-mentioned active energy ray curable composition wherein the compound (C) having the polyoxyalkylene chain is polyalkylene glycol.

[0013] [4] The above-mentioned active energy ray curable composition wherein the polyalkylene glycol is polyethylene glycol.

[0014] [5] The active energy ray curable composition wherein the content of the conductive particles (B) is 7 to 65% by mass of the nonvolatile content of the active energy ray curable composition.

[0015] [6] The active energy ray curable composition wherein the content of the compound (C) having a polyoxyalkylene chain is 15% by mass or less in the nonvolatile content of the active energy ray curable composition.

[0016] [7] A laminate comprising a cured film formed from the above-mentioned active energy ray curable composition arranged on a substrate. [Effects of the Invention]

[0017] The present invention provides an active energy ray curable composition that can form a cured film possessing excellent properties in terms of transparency, antistatic properties, scratch resistance, and flexibility, as well as a laminate having the cured film. [Modes for carrying out the invention]

[0018] Embodiments of the present invention will be described in detail below, but it goes without saying that other embodiments are also included in the scope of the present invention as long as they are consistent with the spirit of the present invention. In this specification, numerical ranges specified using "~" include the numbers before and after "~" as the lower and upper limits. The notation "E+n" (where n is an integer) between numbers means "×10 n This means (10 to the power of n). In the following explanation, when "(meth)acryloyl group" and "(meth)acrylate" are used, they refer to "acryloyl group or methacryloyl group" and "acrylate or methacrylate," respectively, unless otherwise specified. "Polyfunctional (meth)acrylate (A) having three or more (meth)acryloyl groups in the molecule" is sometimes abbreviated as "polyfunctional (meth)acrylate (A)". The "compound (C) having at least one polyoxyalkylene chain selected from the group consisting of polyalkylene glycol, polyalkylene glycol monoalkyl ether, polyalkylene glycol dialkyl ether, polyalkylene glycol mono(meth)acrylate, polyalkylene glycol di(meth)acrylate, and alkoxypolyalkylene glycol (meth)acrylate" may be abbreviated as the "compound (C) having a polyoxyalkylene chain" or simply the "compound (C)". Unless otherwise noted, each component in the present specification may be used independently alone or in admixture of two or more thereof.

[0019] <Active energy ray-curable composition> Hereinafter, each element constituting the present invention will be described. The active energy ray curable composition of the present invention uses a combination of a polyfunctional (meth)acrylate (A) having three or more (meth)acryloyl groups in its molecule, conductive particles (B), and a compound (C) having polyoxyalkylene chains. By including the polyfunctional (meth)acrylate (A) as a curing component, a cross-linked structure is formed between the polymer chains after curing, resulting in a cured film with high scratch resistance. Furthermore, because the cured film is an acrylic resin, excellent light transmittance is also obtained. The conductive particles (B) are used to lower the surface resistance, but as mentioned above, in order to achieve both high transparency and high antistatic function, a considerable amount of conductive particles (B) must be added. The compound (C) having polyoxyalkylene chains has very weak conductivity on its own and, when used alone, contributes almost nothing to the reduction of the surface resistance of the cured film. However, it has been found that when combined with conductive particles (B), the compound (C) having polyoxyalkylene chains acts as a conductive additive between the conductive particles on the surface, significantly reducing the surface resistance. Therefore, the amount of conductive particles (B) and compound (C) having polyoxyalkylene chains required to obtain antistatic performance can be far less than when each is used individually. Consequently, the reduction in haze due to the addition of conductive particles (B) and the reduction in scratch resistance due to the addition of compound (C) having polyoxyalkylene chains with a flexible structure can be minimized. Furthermore, by adding an appropriate amount of compound (C) having polyoxyalkylene chains, flexibility is imparted and bendability is improved. As a result, it is possible to provide an active energy ray curable composition and a laminate using the composition that are excellent in transparency, antistatic properties, scratch resistance, and bend resistance.

[0020] The active energy ray-curable composition refers to a composition containing a resin component that cures through a crosslinking reaction or the like upon irradiation with active energy rays such as ultraviolet rays or electron beams. After the application of the active energy ray-curable composition, a cured film is formed by irradiating it with active energy rays such as ultraviolet rays or electron beams. Representative examples of such resins include ultraviolet-curable resins and electron beam-curable resins. However, a resin that cures upon ultraviolet irradiation is preferred because it has excellent mechanical film strength (scratch resistance, pencil hardness). Examples of such resins include resins having a plurality of (meth)acryloyl groups, polyfunctional (meth)acrylate monomers, and the like.

[0021] <Polyfunctional (meth)acrylate (A) having three or more (meth)acryloyl groups in the molecule> As the polyfunctional (meth)acrylate (A), it can be selected regardless of the molecular weight, such as low molecular weight compounds, high molecular weight compounds, etc. Also, two or more of these can be used in combination.

[0022] Examples of the polyfunctional (meth)acrylate (A) include trifunctional (meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate; tetrafunctional (meth)acrylate compounds such as pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate; pentafunctional (meth)acrylate compounds such as dipentaerythritol penta(meth)acrylate; hexafunctional (meth)acrylate compounds such as dipentaerythritol hexa(meth)acrylate, and the like.

[0023] Commercially available polyfunctional (meth)acrylates (A) include trimethylolpropane tri(meth)acrylate (Miwon Specialty Chemical, Miramer M300, etc.), glycerin tri(meth)acrylate (Toagosei Co., Ltd., Arronix M-930, etc.), pentaerythritol tri(meth)acrylate (Miwon Specialty Chemical, Miramer M340, etc.), pentaerythritol tetra(meth)acrylate (Kyoeisha Chemical Co., Ltd., Light Acrylate PE-4A, etc.), ditrimethylolpropane tetra(meth)acrylate (Toagosei Co., Ltd., Arronix M-408, etc.), dipentaerythritol penta(meth)acrylate (Arkema (Sartomer) Inc., SR399, etc.), and dipentaerythritol hexa(meth)acrylate (Miwon Specialty Chemical, Miramer Examples include the M600, etc.

[0024] Other examples of polyfunctional (meth)acrylates (A) not mentioned above include polyfunctional urethane acrylates having three or more (meth)acryloyl groups in the molecule, polyfunctional polyester acrylates having three or more (meth)acryloyl groups in the molecule, and polyfunctional epoxy acrylates having three or more (meth)acryloyl groups in the molecule.

[0025] The content of polyfunctional (meth)acrylate (A) is preferably 13% by mass or more in the nonvolatile content of the active energy ray curable composition from the viewpoint of improving scratch resistance and flexural resistance and maintaining high transparency without increasing haze, and preferably 83% by mass or less from the viewpoint of lowering the surface resistance. The active energy ray curable composition of the present invention may also contain polyfunctional (meth)acrylate having two or fewer (meth)acryloyl groups in the molecule.

[0026] <Conductive particles (B)> The conductive particles (B) preferably contain at least one element selected from the group consisting of antimony, indium, tin, zinc, aluminum, titanium, gallium, phosphorus, and fluorine. In particular, those containing any one of antimony, indium, tin, and zinc are more preferable because they also exhibit good conductivity. Furthermore, the form in which the elements are contained is preferably a metal oxide, specifically, antimony pentoxide, antimony-doped tin oxide (ATO), tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), phosphorus-doped tin oxide (PTO), aluminum-doped zinc oxide (AZO), indium-doped zinc oxide (IZO), tin oxide, ATO-coated titanium oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, etc. Among these, antimony pentoxide and ATO are preferred as the conductive particles (B) of the present invention due to their significant effect in reducing the surface resistance when combined with the compound (C) having a polyoxyalkylene chain, and antimony pentoxide is more preferred. These conductive particles (B) may be used in combination of two or more types.

[0027] Commercially available conductive particles (B) include Nissan Chemical's "Sun Epoch EFR-6N (Antimony Pentoxide)" and "Sun Epoch EFR-6NP (Antimony Pentoxide)", Ishihara Sangyo's "SN-100P (ATO)", "FS-10P (ATO)", "SN-102P (ATO)", "FS-12P (ATO)", and "ET-300W (ATO-coated Titanium Oxide)", and Mitsubishi Materials' "T-1 (ITO)", "S-1200 (Tin Oxide)", "S-2000 (Tin Oxide)", "EP T-1-5L (ATO)", and "EP Examples include SP-2 (PTO), Pastran (ITO, ATO) from Mitsui Mining & Smelting Co., Ltd., Nanotech ITO and Nanotech SnO2 from Takiron CI Co., Ltd., TL-20 (ATO), TL-30 (ATO), TL-30S (PTO), TL-120 (ITO), and TL-130 (ITO) from JGC Catalysts & Chemicals Co., Ltd., PazetCK (aluminum-doped zinc oxide) and PazetGK (gallium-doped zinc oxide) from Hakusui Tech Co., Ltd., and SC-18 (aluminum-doped zinc oxide) from Sakai Chemical Industry Co., Ltd.

[0028] Furthermore, commercially available conductive particle (B) dispersions in which conductive particles (B) are dispersed in a solvent or water include Ishihara Sangyo Co., Ltd.'s "SNS-10M(ATO)", "SNS-10T(ATO)", "FSS-10M(ATO)", and "FSS-10T(ATO)", and Nissan Chemical Corporation's "Celnax CX-Z603M-F2(AZO)", "Celnax CX-Z610M-F2(AZO)", "Celnax CX-Z210IP-F(AZO)", and Examples include Lunax CX-Z210IP-F2 (AZO), Celnax CX-Z410M-F (AZO), Celnax CX-Z401M-F (AZO), HX-305M5 (methanol dispersion of tin oxide, zirconium oxide, antimony pentoxide, and silicon dioxide composite), and HIT-301M1 (methanol dispersion of tin oxide, titanium oxide, zirconium oxide, and antimony pentoxide composite), as well as JGC Catalysts & Chemicals' "ELCOM P-30 (ATO)", "ELCOM P-32 (ATO)", "ELCOM P-35 (PTO)", "ELCOM P-45 (antimony pentoxide)", "ELCOM V-4564 (antimony pentoxide)", "ELCOM P-120 (ITO)", and "ELCOM P-130 (ITO)".

[0029] The conductive particles (B) contained in the active energy ray curable composition of the present invention may contain insulating metal oxides or be surface-treated with hydrolyzable organometallic compounds. Examples of insulating metal oxides include silicon oxide, aluminum oxide, and zirconium oxide. Examples of hydrolyzable organometallic compounds include metal alkoxides and metal ketonates.

[0030] In the present invention, the content of conductive particles (B) in the nonvolatile content of the active energy ray curable composition is preferably 7% by mass or more, and more preferably 10% by mass or more, from the viewpoint of obtaining a sufficient surface resistance value. From the viewpoint of sufficient scratch resistance and flexibility, and from the viewpoint of sufficiently wetting the surface of the conductive fine particles (B) with resin to prevent haze, it is preferably 65% ​​by mass or less, and more preferably 60% by mass or less.

[0031] <Compounds containing polyoxyalkylene chains (C)> As used herein, a compound (C) having a polyoxyalkylene chain means at least one selected from the group consisting of polyalkylene glycol, polyalkylene glycol monoalkyl ether, polyalkylene glycol dialkyl ether, polyalkylene glycol mono(meth)acrylate, polyalkylene glycol di(meth)acrylate, and alkoxy polyalkylene glycol (meth)acrylate.

[0032] As for the compound (C) having a polyoxyalkylene chain, from the viewpoint of its effect in lowering the surface resistance value as a conductive additive for conductive particles (B), "polyalkylene glycols" having hydrophilic hydroxyl groups at both ends of the main chain in the molecule, such as polyethylene glycol and polypropylene glycol, are highly effective and preferred. Similarly, from the viewpoint of using it as a conductive additive for conductive particles (B), it is also possible to use "polyalkylene glycols" having hydroxyl groups at both ends, with one or both ends of the hydroxyl groups substituted with alkyl, or esterified with (meth)acrylic acid, which are included in the compound (C) having a polyoxyalkylene chain of the present invention. Examples of these compounds (C) include "polyalkylene glycol monoalkyl ether," "polyalkylene glycol dialkyl ether," "polyalkylene glycol mono(meth)acrylate," "polyalkylene glycol di(meth)acrylate," and "alkoxy polyalkylene glycol (meth)acrylate."

[0033] <Polyalkylene glycol> Preferred polyalkylene glycols are those having hydroxyl groups at both ends of the main chain in the molecule, such as polyethylene glycol and polypropylene glycol. Commercially available products include "PEG-200", "PEG-300", "PEG-400", "PEG-600", "PEG-1000", "PEG-2000", "PEG-10000", and "PEG-20000" from Sanyo Chemical Industries, Ltd., and "PEG#200", "PEG#300", "PEG#400", "PEG#600", "PEG#1000", "PEG#2000", "PEG#4000", "PEG#6000", "PEG#11000", "PEG#20000", "Uniol D-200", "Uniol D-250", "Uniol D-700", "Uniol D-1000", "Uniol D-1200", "Uniol D-2000", and "Uniol D-4000" from NOF Corporation.

[0034] <Polyalkylene glycol monoalkyl ether> Examples of polyalkylene glycol monoalkyl ethers include polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether, polypropylene glycol monomethyl ether, polypropylene glycol monoethyl ether, and polypropylene glycol monophenyl ether. Commercially available products include NOF Corporation's "Uniox M-400," "Uniox M-550," "Uniox M-1000," "Uniox M-2000," and "Uniox M-4000."

[0035] <Polyalkylene glycol dialkyl ether> Examples of polyalkylene glycol dialkyl ethers include polyethylene glycol dimethyl ether. A commercially available example is "Uniox MM-400" manufactured by NOF Corporation.

[0036] <Polyalkylene glycol mono(meth)acrylate> Examples of polyalkylene glycol mono(meth)acrylates of the present invention include polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, polyethylene glycol-polypropylene glycol-monomethacrylate, etc. Commercially available products include NOF Corporation's "Bremmer AE-200," "Bremmer AE-400," "Bremmer AP-200," "Bremmer AP-400," "Bremmer AP-550," and "Bremmer AP-800."

[0037] <Polyalkylene glycol di(meth)acrylate> Examples of polyalkylene glycol di(meth)acrylates include polyethylene glycol-diacrylate, polypropylene glycol-diacrylate, polyethylene glycol-dimethacrylate, and polypropylene glycol-dimethacrylate. Commercially available products include NOF Corporation's "Bremmer ADE-200," "Bremmer ADE-300," "Bremmer ADE-400A," "Bremmer ADP-400," "Bremmer PDE-100," "Bremmer PDE-150," "Bremmer PDE-200," "Bremmer PDE-400," "Bremmer PDE-600," and "Bremmer PDP-400N."

[0038] <Alkoxypolyalkylene glycol (meth)acrylate> Examples of alkoxy polyalkylene glycol (meth)acrylates include methoxypolyethylene glycol acrylate, nonylphenoxypolypropylene glycol acrylate, methoxypolyethylene glycol methacrylate, lauroxypolyethylene glycol methacrylate, and stearoxypolyethylene glycol methacrylate. Commercially available products include NOF Corporation's "Bremmer AME-400," "Bremmer ANP-300," "Bremmer PME-100," "Bremmer PME-200," "Bremmer PME-400," "Bremmer PME-1000," "Bremmer PME-4000," "Bremmer PLE-200," and "Bremmer PSE-1300."

[0039] Among the compounds (C) having polyoxyalkylene chains, polyethylene glycol is particularly preferred because it has high hydrophilicity and can more effectively reduce surface resistance with a small amount.

[0040] In the present invention, the content of the compound (C) having a polyoxyalkylene chain in the nonvolatile components of the active energy ray curable composition is preferably 0.5% by mass or more from the viewpoint of raising a sufficient surface resistance value in coexistence with conductive fine particles (B), and preferably 15% by mass or less from the viewpoint of obtaining sufficient hardness and scratch resistance.

[0041] The number-average molecular weight (hereinafter sometimes abbreviated as Mn) of these polyoxyalkylene chain compounds is not particularly limited in its lower limit, but is preferably 200 or higher, and is preferably 8100 or lower from the viewpoint of suppressing the increase in surface resistance, transparency, and compatibility. As the molecular weight of a polyoxyalkylene chain compound increases, its solubility in organic solvents and compatibility with other components tend to decrease. Therefore, if Mn exceeds 8100, it may precipitate in the cured film, potentially causing problems such as an increase in surface resistance and a decrease in transparency.

[0042] In this specification, Mn refers to the number-average molecular weight of polystyrene as the standard substance, measured by gel permeation chromatography (GPC) under the following conditions.

[0043] [GPC measurement conditions] Model: TOSOH HLC-8420GPC Column: TSKGEL SuperHZM-N Developing solvent: Tetrahydrofuran (THF) Flow rate: 0.35mL / min Column temperature: 40℃ Detector: Differential refractive index detector (RI) Molecular weight standard: Polystyrene equivalent Sample concentration: Dilute with THF to 0.5% to 1%.

[0044] <Photopolymerization initiator> Examples of photopolymerization initiators that can be included in the active energy ray curable composition of the present invention include monocarbonyl photopolymerization initiators, dicarbonyl photopolymerization initiators, acetophenone photopolymerization initiators, benzoin ether photopolymerization initiators, acylphosphine oxide photopolymerization initiators, and aminocarbonyl photopolymerization initiators. The photopolymerization initiator may be used in combination with a sensitizer.

[0045] Commercially available photopolymerization initiators include, but are not limited to, IGM Resins BV's "Omnirad 184," "Omnirad 651," "Omnirad 500," "Omnirad 907," "Omnirad 127," "Omnirad 369," "Omnirad 784," "Omnirad 2959," and "ESACURE ONE," and BASF's "Lucilin TPO." Mixtures of two or more of these can also be used. In particular, "Omnirad 184" and "ESACURE ONE" are preferred from the viewpoint of resistance to yellowing after active energy ray curing.

[0046] The content of the photopolymerization initiator is not limited as long as it contains enough to cure the active energy ray curable composition to the desired physical properties by ultraviolet light. However, from the viewpoint of curing speed and the hardness and scratch resistance of the active energy ray curable composition, it is preferable that the initiator contains 1 to 15% by mass, and more preferably 3 to 10% by mass, of 100% by mass of the nonvolatile content of the active energy ray curable composition.

[0047] <Other ingredients> The active energy ray curable composition of the present invention may optionally contain other components such as organic solvents and additives. Examples of additives include thermosetting resins, polymerization inhibitors, leveling agents, slip agents, defoaming agents, surfactants, antibacterial agents, antiblocking agents, plasticizers, ultraviolet absorbers, infrared absorbers, antioxidants, silane coupling agents, conductive agents, inorganic fillers, pigments, dyes, and the like.

[0048] <Leveling agent> The active energy ray curable composition of the present invention may contain a leveling agent depending on the performance to be imparted to the cured film formed. The leveling agent is not particularly limited as long as it provides the desired leveling effect, i.e., an effect of suppressing coating defects such as repelling during coating, or an effect of smoothing the surface of the formed coating layer. Examples of such leveling agents include silicone-based leveling agents, fluorine-based leveling agents, acrylic-based leveling agents, siloxane-modified acrylic-based leveling agents, vinyl-based leveling agents, etc. For example, as a fluorine-based leveling agent, a copolymer of polyoxyalkylene and fluorocarbon can be used, and commercially available products include the Megafac series from DIC and the FC series from 3M.

[0049] <Organic solvents> The active energy ray-curable composition of the present invention may contain an organic solvent. As the organic solvent, known organic solvents such as aromatic organic solvents like toluene and xylene, ketone-based organic solvents like methyl ethyl ketone and methyl isobutyl ketone, ester-based organic solvents like ethyl acetate, n-propyl acetate, isopropyl acetate, and isobutyl acetate, and alcohol-based organic solvents like methanol, ethanol, propanol, 2-propanol, and butanol can be used. When an organic solvent is included, the content of the organic solvent is preferably in the range of 1 to 60% by mass, from the viewpoint of coating properties and film-forming properties, such that the non-volatile content of the active energy ray-curable composition of the present invention is 1 to 60% by mass.

[0050] <Manufacturing of activated energy ray-curable compositions> The active energy ray curable composition of the present invention can be manufactured by uniformly stirring and mixing or dispersing its components using a stirrer, homogenizer, three-roll mill, sand mill, gamma mill, or the like.

[0051] <Manufacturing of hardened films and their laminates> Next, a method for producing a cured film obtained by curing an active energy ray-curable composition will be described. The method for producing a cured film includes, for example, the steps of applying an active energy ray-curable composition to a substrate and curing the active energy ray-curable composition on the substrate by irradiating it with active energy rays. More specifically, the active energy ray-curable composition can be applied to a substrate so that the film thickness after drying is preferably 0.1 to 30 μm, more preferably 1 to 10 μm, and then cured.

[0052] Examples of substrates include metals, ceramics, glass, plastics, wood, and slate, and are not particularly limited. Examples of plastic materials include polyester, polyolefin, polycarbonate, polystyrene, polymethyl methacrylate, triacetylcellulose resin, ABS resin, AS resin, polyamide, epoxy resin, and melamine resin. Examples of substrate shapes include film (sheet), panel, lens shape, disc shape, and fiber shape, but are not particularly limited.

[0053] The cured film may be formed (laminated) by direct coating onto the substrate, or one or more underlying layers may be present between the cured film and the substrate. Known methods can be used for coating, such as methods using rods or wire bars, or various coating methods such as microgravure, gravure, die, curtain, lip, slot, or spin.

[0054] The curing of active energy ray-curable compositions can be performed by irradiation with active energy rays such as ultraviolet light, visible light, or electron beams. For visible light, a wavelength of 400-500 nm is preferred. Suitable sources (light sources) for ultraviolet and visible light include high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, gallium lamps, xenon lamps, carbon arc lamps, etc. Suitable electron sources include thermionic emission guns, electrolytic emission guns, etc.

[0055] The energy dose to be irradiated is 5-2000 mJ / cm². 2 It is preferable that the range be 50-1000 mJ / cm², and furthermore, from the standpoint of ease of control during the process, it is preferable to have a range of 50-1000 mJ / cm². 2 It is more preferable that the irradiation is within this range. When irradiating with these active energy rays, heat treatment using infrared rays, far-infrared rays, hot air, high-frequency heating, etc., can be used in combination.

[0056] The cured film of the present invention may be formed by coating a substrate with a curable composition, allowing it to dry naturally or by forced drying, and then performing a curing treatment, or by coating and performing a curing treatment, followed by natural or forced drying. However, it is more preferable to perform the curing treatment after natural or forced drying.

[0057] In particular, when curing with an electron beam, it is preferable to perform the curing treatment after natural or forced drying to prevent curing inhibition by water or a decrease in the strength of the coating film due to residual organic solvents.

[0058] Furthermore, the curing process can be performed simultaneously with the coating or afterward.

[0059] The resulting cured film exhibits excellent antistatic properties, scratch resistance, transparency, and flexibility, making it suitable for use as an optical material. Therefore, the cured film of the present invention can be used as a laminate for the front panel of various display devices such as cathode ray tubes and flat display panels (liquid crystal displays, plasma displays, electrochromic displays, light-emitting diode displays, etc.) or as an input device for these devices. In addition, this cured film can be widely used in optical lenses, eyeglass lenses, optical recording discs (compact discs, DVD discs, Blu-ray discs, etc.), light cases, and the like.

[0060] The surface resistance of the cured film of the present invention is preferably less than 1.0E+12 (Ω / □). If the surface resistance is less than 1.0E+12 (Ω / □), sufficient antistatic performance can be achieved.

[0061] The laminate of the present invention comprises the cured film of the present invention and a substrate. Any of the above-executed materials can be used as the substrate, and a plastic substrate is particularly preferred. The shape of the substrate is preferably a film shape, a lens shape, or a disc shape. Furthermore, in addition to these, the laminate preferably includes one or more layers such as a film with a different refractive index, an adhesive layer, or an information recording layer.

[0062] An example of the laminate of the present invention is shown below. The laminate, which includes at least one film and layer (M) selected from films with different refractive indices and an information recording layer, can have a layer configuration such as (I) to (IX) below.

[0063] (I) Base material / (M) / cured film (II) Base material / cured film / (M) (III) Base material / (M) / cured film / (M) (IV) (M) / Substrate / Cured film (V) (M) / Substrate / (M) / Cured film (VI) (M) / Substrate / Cured film / (M) (VII) (M) / Substrate / (M) / Cured film / (M) (VIII) (M) / cured film / base material / cured film (IX) Cured film / (M) / Substrate / cured film

[0064] A film or information recording layer with a different refractive index has functions other than those of the cured product of the present invention. The method of formation is not particularly limited and can be formed by known methods. For example, dry coating methods such as vapor deposition and sputtering, methods using rods and wire bars, and wet coating methods such as microgravure, gravure, die, curtain, lip, slot, and spin can be used. The material used is also not limited, and any material can be used that can impart one or more functions to the laminate, such as information recording function, anti-glare function, Newton's ring prevention function, adhesive function, specific wavelength blocking, improved adhesion, and color correction, as needed.

[0065] The information recording layer can be any material that records information by causing some kind of chemical change using laser light or the like. For example, organic materials include polymethine dyes, naphthalocyanine-based, phthalocyanine-based, squarylium-based, anthraquinone-based, xanthene-based, and triphenylmethane-based metal complex compounds. One or more of these dyes can be used. Inorganic recording layers can use one or more of the following metals and metalloids: Te, Ge, Se, In, Sb, Sn, Zn, Au, Al, Cu, Pt, etc. The information recording layer may be a laminate, and the photochemical change can be phase change, bubble, or hole-punching. Furthermore, it may be a magneto-optical recording layer mainly composed of Fe, Tb, and Co, or a spiropyran or flukide-based photochromic material.

[0066] From the viewpoint of anti-reflection, a high refractive index cured film can also be used as a laminate to which a low refractive index coating cured film is provided on the surface to impart an anti-reflection function. That is, it is preferable to use a laminate obtained by forming a cured film on a substrate such as a film, and more preferably forming a coating cured film, as an anti-reflection film. In laminates where reflection interference fringes are a problem, it is preferable to adjust the amount of metal oxide blended in the curable composition of the present invention so that the difference in refractive index between the cured film and the substrate, or, if any layer exists between the cured film and the substrate, the difference in refractive index between the cured film and the underlying layer in contact with the cured film, is within ±0.02. [Examples]

[0067] The present invention will be described in more detail below with reference to examples and comparative examples, but the following examples do not limit the technical scope of the present invention in any way. In the examples, "parts" means "parts by mass," and "%" means "percentage by mass." The amounts of each component listed in Table 1 represent parts by mass of the non-volatile content after excluding the solvent from each component. Blank spaces in the table indicate that the component was not included. The apparatus and conditions used for composition preparation, creation of substrates with cured films, and evaluation of physical properties in the examples and comparative examples are as follows.

[0068] [Example 1] <Preparation of Active Energy Ray Curable Composition> The following ingredients are used: 28.2 parts of polyfunctional (meth)acrylate (A) having three or more (meth)acryloyl groups in the molecule (product name "KAYARAD PET-30", manufactured by Nippon Kayaku Co., Ltd., a mixture of pentaerythritol triacrylate (number of acryloyl groups: 3) and pentaerythritol tetraacrylate (number of acryloyl groups: 4)); 20 parts of conductive particles B1 (product name "ELCOM V-4564", manufactured by JGC Catalysts & Chemicals Co., Ltd., a dispersion of propylene glycol monomethyl ether containing 40% by mass of antimony pentoxide) as conductive particles (B) (8 parts as conductive particles (B)); 2 parts of compound C1 (product name "PEG-1000", manufactured by Sanyo Chemical Industries, Ltd., polyethylene glycol, Mn: 1010) as a compound having a polyoxyalkylene chain (C); and as a photopolymerization initiator (product name "ESACURE ONE", IGM Resins) A composition curable by active energy rays was obtained by thoroughly mixing 1.4 parts of (manufactured by BV) and 1 part of a leveling agent (product name "Megafac RS-76-E", manufactured by DIC, containing 40% by mass of a fluorine-based surfactant and containing methyl ethyl ketone, ethyl acetate, etc. as solvents) (0.4 parts of the fluorine-based surfactant), and adjusting the amount of propylene glycol monomethyl ether as an organic solvent to 40% by mass of non-volatile content.

[0069] <Preparation of a substrate (coated material) with a cured film> The activated energy ray-curable composition obtained above was coated onto a 50 μm thick polyethylene terephthalate (PET) film (product name "Lumirror U403", manufactured by Toray Industries, Inc.) using a bar coater to achieve a dry film thickness of 4 μm. After drying in a 100°C hot air dryer for 2 minutes, it was cured with a high-pressure mercury lamp at 400 mJ / cm². 2 A substrate having a cured film was prepared by irradiating it with ultraviolet light (corresponding to the "laminated body" of the present invention, and referred to as "coated material" in the following description).

[0070] [Examples 2-23, Comparative Examples 1-4] Except for changing the composition and blending amounts (mass %) of each component based on the non-volatile content excluding the solvent) as shown in Table 1, active energy ray curable compositions with a non-volatile content of 40% by mass were obtained in the same manner as in Example 1. Coated materials were also prepared in the same manner as in Example 1. The surface resistance, scratch resistance, transparency (Haze value), and flexural resistance of the obtained coated materials were evaluated using the evaluation method shown below. The results are shown in Table 2.

[0071] The breakdown of the symbols in the table is as follows: <Polyfunctional (meth)acrylate (A)> A1: Product name "KAYARAD PET-30", manufactured by Nippon Kayaku Co., Ltd., a mixture of pentaerythritol triacrylate (acryloyl group count: 3) and pentaerythritol tetraacrylate (acryloyl group count: 4). A2: Product name "Miramer M500", manufactured by Miwon Specialty Chemical, a mixture of dipentaerythritol pentaacrylate (5 acryloyl groups) / dipentaerythritol hexaacrylate (6 acryloyl groups) = 50 / 50 (mass ratio). A3: Product name "Shiko UV-1700B", manufactured by Mitsubishi Chemical Corporation, urethane acrylate, acryloyl group count: 10 <Polyfunctional (meth)acrylate having two or fewer (meth)acryloyl groups in the molecule> A4: Product name "Miramer PU2100", manufactured by Miwon Specialty Chemical, urethane acrylate, number of acryloyl groups: 2

[0072] <Conductive particles (B)> B1: Antimony pentoxide (product name "ELCOM V-4564", manufactured by JGC Catalysts & Chemicals, a propylene glycol monomethyl ether dispersion containing 40% by mass of antimony pentoxide) B2: Antimond-doped tin oxide (ATO) (product name "DLAT-002-30ND1", manufactured by Daiken Chemical Industry Co., Ltd., methyl ethyl ketone dispersion containing 30% by mass of ATO particles)

[0073] <Compounds containing polyoxyalkylene chains (C)> C1: Product name "PEG-1000", manufactured by Sanyo Chemical Industries, Ltd., polyethylene glycol, Mn: 1010 C2: Product name "Uniox M-1000", manufactured by NOF Corporation, polyethylene glycol monomethyl ether, Mn: 1080 C3: Product name "Uniox MM-400", manufactured by NOF Corporation, polyethylene glycol dimethyl ether, Mn: 470 C4: Product name "Bremmer AE-400", manufactured by NOF Corporation, polyethylene glycol monoacrylate, Mn: 750 C5: Product name "Bremmer ADE-400A", manufactured by NOF Corporation, polyethylene glycol diacrylate, Mn: 580 C6: Product name "Bremmer AME-400", manufactured by NOF Corporation, polyethylene glycol monomethyl ether acrylate, Mn: 510 C7: Product name "PEG-200", manufactured by Sanyo Chemical Industries, Ltd., polyethylene glycol, Mn: 200 C8: Product name "PEG-400", manufactured by Sanyo Chemical Industries, Ltd., polyethylene glycol, Mn: 420 C9: Product name "PEG-2000", manufactured by Sanyo Chemical Industries, Ltd., polyethylene glycol, Mn: 2040 C10: Product name "PEG#4000", manufactured by NOF Corporation, polyethylene glycol, Mn: 3410 C11: Product name "PEG#6000", manufactured by NOF Corporation, polyethylene glycol, Mn: 8100 C12: Product name "Uniol D-1000", manufactured by NOF Corporation, polypropylene glycol, Mn: 1340

[0074] <Photopolymerization initiator> ESACURE ONE (product name "ESACURE ONE", manufactured by IGM Resins BV) <Leveling agent> RS-76-E (product name "Megafac RS-76-E", manufactured by DIC Corporation, contains 40% by mass of fluorinated surfactant, and contains methyl ethyl ketone, ethyl acetate, etc. as solvents)

[0075] <Evaluation Method> (1) Surface resistance The surface resistance (Ω / □) of the cured film of the coated material was measured using a super-insulation meter (HIOKI SM-8220) after applying a voltage of 100V for 1 minute. The upper limit of what can be measured with this super-insulation meter is 9.4E+15 (Ω / □), and anything exceeding this value will display "OVER". A lower surface resistance value indicates better antistatic properties. The evaluation criteria are judged on the following five-point scale, with higher values ​​indicating better surface resistance. A value of less than 1.0E+12 (Ω / □) is considered to be at a level that does not pose practical problems. [Evaluation Criteria] 5: Less than 1.0E+10(Ω / □) 4: 1.0E+10 (Ω / □) or greater, less than 1.0E+11 (Ω / □) 3: 1.0E+11 (Ω / □) or greater, less than 1.0E+12 (Ω / □) 2:1.0E+12(Ω / □) or more and 9.4E+15(Ω / □) or less 1: Greater than 9.4E+15(Ω / □)

[0076] (2) Scratch resistance The abrasion resistance of the fabricated coated material was evaluated using a Japan Society for the Promotion of Science (JSPS) type friction fastness tester (manufactured by Tester Sangyo Co., Ltd.). A friction element with a load of 500g attached (surface area 1cm²) was used. 2 Steel wool #0000 was attached to the tool, and the surface of the hardened film (1cm x 13cm) was moved back and forth 10 times. The degree of scratching of the removed coated object was judged visually on the following four scales. A higher number indicates better scratch resistance. A score of 3 or higher is considered to be at a level that does not pose a practical problem. [Evaluation Criteria] 4: The hardened film is completely free of scratches. 3: A few fine scratches are observed on the hardened film, but there are no deep scratches. 2: The hardened film has deep scratches, but the substrate is not exposed. 1: The hardened film has deep scratches, and in some areas the hardened film has peeled off, exposing the substrate.

[0077] (3) Transparency (Haze value [%]) The turbidity (Haze value [%]) of the coated material was measured using a spectroscopic haze meter (SH 7000, manufactured by Nippon Denshoku Industries Co., Ltd.). A smaller value indicates better transparency. "〇" and "△" represent levels that are acceptable for practical use. [Evaluation Criteria] ○: Less than 1.0% (Good) △: 1.0% or more, less than 2.0% (usable) ×: 2.0% or more (Not practical)

[0078] (4) Flexibility The fabricated coated materials were measured using a coating film bending tester (Tester Sangyo Co., Ltd., PI-801) in accordance with JIS K 5600-5-1:1999, employing the cylindrical mandrel method. The coated material was wrapped around a mandrel with the cured film facing outwards, and the presence or absence of cracks in the cured film was visually confirmed. The evaluation was performed by decreasing the diameter of the mandrel as shown below, and the minimum diameter of the mandrel that did not cause cracks in the cured film was determined. A smaller minimum diameter indicates superior bending resistance. The evaluation was performed according to the following criteria. Note that "〇" and "△" are at a level that poses no practical problems. Mandrel diameters: 2mm, 3mm, 4mm, 5mm, 6mm, 8mm, 10mm [Evaluation Criteria] 〇: Minimum diameter is 3mm or less (good) △: Minimum diameter is 4mm (usable) ×: Minimum diameter 5mm or more (not practical)

[0079] [Table 1]

[0080] [Table 2]

[0081] The results in Table 2 show that the active energy ray curable composition of the example is capable of forming a cured film that has high transparency, low surface resistance, excellent antistatic performance, excellent scratch resistance of the cured film, and excellent flexibility resistance. On the other hand, the curable composition of the comparative example could not achieve both transparency, antistatic performance, scratch resistance of the cured film, and flexibility resistance.

Claims

1. An active energy ray curable composition comprising: a polyfunctional (meth)acrylate (A) having three or more (meth)acryloyl groups in the molecule; conductive particles (B); and a compound (C) having at least one polyoxyalkylene chain selected from the group consisting of polyalkylene glycol, polyalkylene glycol monoalkyl ether, polyalkylene glycol dialkyl ether, polyalkylene glycol mono(meth)acrylate, polyalkylene glycol di(meth)acrylate, and alkoxy polyalkylene glycol (meth)acrylate.

2. The active energy ray curable composition according to claim 1, wherein the conductive particle (B) is antimony pentoxide.

3. The active energy ray curable composition according to claim 1, wherein the compound (C) having the polyoxyalkylene chain is a polyalkylene glycol.

4. The active energy ray curable composition according to claim 3, wherein the polyalkylene glycol is polyethylene glycol.

5. The active energy ray curable composition according to claim 1, wherein the content of the conductive particles (B) is 7 to 65% by mass of the nonvolatile content of the active energy ray curable composition.

6. The active energy ray curable composition according to claim 1, wherein the content of the compound (C) having the polyoxyalkylene chain is 15% by mass or less in the nonvolatile content of the active energy ray curable composition.

7. A laminate comprising a substrate on which a cured film formed from an active energy ray curable composition according to any one of claims 1 to 6 is disposed.

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