JPWO2018100929A1 - Active energy ray-curable composition and film using the same - Google Patents

Abstract

The present invention is an active energy ray-curable composition containing an active energy ray-curable compound (A) and silica particles (B), wherein the wet energy tension of the cured coating film surface of the active energy ray-curable composition is Provided is an active energy ray-curable composition characterized by being in a range of 35 to 60 mN / m. It is preferable that the compounding quantity of the said silica particle (B) is the range of 1-60 mass parts with respect to 100 mass parts of active energy ray hardening compounds (A). The problem to be solved by the present invention is to provide an active energy ray-curable composition capable of providing a high anti-blocking property on the film surface and capable of forming a hard coat layer having high transparency and high adhesive adhesion to OCA and the like. It is to provide the film used.

Description

  The present invention provides an active energy ray-curable composition that can impart a high antiblocking property to a film surface by coating and curing the film surface, and can form a hard coat layer having high transparency and high adhesive adhesion. And a film using the same.

  Various resin films include scratch prevention films on the surface of flat panel displays (FPD) such as liquid crystal displays (LCD), organic EL displays (OLED), plasma displays (PDP), decorative films (sheets) for interior and exterior of automobiles, It is used for various applications such as low reflection film for windows and heat ray cut film. However, since the resin film surface is soft and has low scratch resistance, a hard coat layer comprising a UV curable composition or the like may be applied to the film surface and cured to provide a hard coat layer on the film surface in order to compensate for this. Generally done. The outline of the process of providing a hard coat layer is sent out from a film roll wound in a roll shape to a coating machine, a hard coat agent is applied, cured by ultraviolet irradiation to form a hard coat layer, and again It is wound up into a roll.

  Here, since the surface of the hard coat layer is smooth, the films stick to each other when the roll is wound again (blocking), and when the film is unwound from the roll during reprocessing, friction due to blocking occurs, and the film There was a problem of scratching the surface.

  As a method for preventing the blocking of the film (anti-blocking), a method is proposed in which fine particles such as silica particles are added to the hard coating agent to form irregularities on the hard coating surface of the hard coating agent (for example, , See Patent Documents 1 and 2.) In addition, a method in which silica particles having an average primary particle diameter of 5 to 80 nm and silica particles having an average primary particle diameter of 100 to 300 nm are used in combination has been proposed (see, for example, Patent Document 3).

  Here, the structure of the indium tin oxide (ITO) film used in the touch panel is such that a high refractive index hard coat layer is formed on one side of a polyethylene terephthalate (PET) base material, and the other side is blocked between the films. It is the mainstream to form an anti-booking property-imparting hard coat layer that prevents the above. On the high refractive index hard coat layer side, after a low refractive index layer is laminated thereon, ITO is sputtered and annealed.

  On the other hand, a heat-resistant protective PET film is applied to the anti-booking property imparting hard coat layer side until the annealing treatment is completed. Thereafter, the heat-resistant protective PET is peeled off, and a touch panel module is assembled using a highly transparent adhesive tape (OCA). However, the cured coating film of the hard coating agent that imparts the above antiblocking property does not sufficiently adhere to the OCA. There was a problem.

  Therefore, there has been a demand for an active energy ray-curable composition that can impart high antiblocking properties to the film surface and can form a hard coat layer having high transparency and high adhesion to OCA.

JP 2012-27401 A JP2011-98529A JP 2009-132880 A

  The problem to be solved by the present invention is to provide an active energy ray-curable composition capable of providing a high anti-blocking property on the film surface and capable of forming a hard coat layer having high transparency and high adhesive adhesion to OCA and the like. It is to provide the film used.

  As a result of intensive studies to solve the above problems, the inventors of the present invention have a high wetting tension on the surface of the cured coating film of the active energy ray-curable composition containing silica particles, which is high for OCA and the like. It discovered that it had adhesive adhesiveness, and completed this invention.

  That is, it is an active energy ray-curable composition containing the active energy ray-curable compound (A) and the silica particles (B), and the wetting tension of the cured coating film surface of the active energy ray-curable composition is 35 to 35. The present invention relates to an active energy ray-curable composition characterized by being in a range of 60 mN / m and a film using the same.

  The active energy ray-curable composition of the present invention is capable of imparting high antiblocking properties to the film surface by coating and curing on the resin film surface, and has high transparency and high adhesive adhesion to OCA and the like. A layer can be formed. Therefore, since the cured coating film of the active energy ray-curable composition of the present invention has scratch resistance, it is possible to prevent scratches on the surface of various resin films, and when winding up into a roll shape, when blocking from the roll, blocking occurs. Since the trouble which becomes the cause can also be avoided, the film excellent in subsequent handling can be provided. Moreover, the film which has a hard-coat layer which consists of a cured coating film of the active energy ray curable composition of this invention is flat panel displays, such as a liquid crystal display (LCD), an organic electroluminescent display (OLED), and a plasma display (PDP) ( It can be used for various applications such as a film for protecting scratches (FPD) on the surface (protective film), a touch panel, a decorative film (sheet) for automobile interior and exterior, a low reflection film for windows, and a heat ray cut film. In particular, it can be suitably used for touch panel applications that require high adhesive adhesion with OCA.

  The active energy ray-curable composition of the present invention is an active energy ray-curable composition containing an active energy ray-curable compound (A) and silica particles (B), The wetting tension on the surface of the cured coating film is in the range of 35-60 mN / m.

  Examples of the active energy ray-curable compound (A) include polyfunctional (meth) acrylate (A1) and urethane (meth) acrylate (A2). These can be used alone or in combination of two or more.

  In the present invention, “(meth) acrylate” refers to one or both of acrylate and methacrylate, and “(meth) acryloyl group” refers to one or both of acryloyl group and methacryloyl group.

  The polyfunctional (meth) acrylate (A1) is a compound having two or more (meth) acryloyl groups in one molecule. Specific examples of the polyfunctional (meth) acrylate (a1) include 1,4-butanediol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, and 1,6-hexanediol. Di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate , Tricyclodecane dimethanol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di ( (Meth) acrylate, etc. Di (meth) acrylate of dihydric alcohol, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, di (meth) acrylate of tris (2-hydroxyethyl) isocyanurate, 4 moles per mole of neopentyl glycol Di (meth) acrylate of diol obtained by adding ethylene oxide or propylene oxide as described above, di (meth) acrylate of diol obtained by adding 2 mol of ethylene oxide or propylene oxide to 1 mol of bisphenol A, trimethylolpropane Tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, ditri Tyrolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol Examples include tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. These polyfunctional (meth) acrylates (A1) can be used alone or in combination of two or more. Among these polyfunctional (meth) acrylates (A1), since the scratch resistance of the cured coating film of the active energy ray-curable composition of the present invention is improved, dipentaerythritol hexa (meth) acrylate, di Pentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, and pentaerythritol tri (meth) acrylate are preferred.

  The urethane (meth) acrylate (A2) is obtained by reacting a polyisocyanate (a2-1) with a (meth) acrylate (a2-2) having a hydroxyl group.

  Examples of the polyisocyanate (a2-1) include aliphatic polyisocyanates and aromatic polyisocyanates, but since the coloring of the cured coating film of the active energy ray-curable composition of the present invention can be reduced, aliphatic polyisocyanates. Isocyanates are preferred.

  The aliphatic polyisocyanate is a compound in which a portion excluding an isocyanate group is composed of an aliphatic hydrocarbon. Specific examples of the aliphatic polyisocyanate include aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, and lysine triisocyanate; norbornane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), 1,3-bis (isocyanato). And cycloaliphatic polyisocyanates such as methyl) cyclohexane, 2-methyl-1,3-diisocyanatocyclohexane and 2-methyl-1,5-diisocyanatocyclohexane. A trimerized product obtained by trimming the aliphatic polyisocyanate or the alicyclic polyisocyanate can also be used as the aliphatic polyisocyanate. These aliphatic polyisocyanates can be used alone or in combination of two or more.

  Among the aliphatic polyisocyanates, in order to improve the scratch resistance of the coating film, among the aliphatic polyisocyanates, hexamethylene diisocyanate, which is a linear aliphatic hydrocarbon diisocyanate, norbornane diisocyanate, which is an alicyclic diisocyanate, isophorone Diisocyanate is preferred.

  The (meth) acrylate (a2-2) is a compound having a hydroxyl group and a (meth) acryloyl group. Specific examples of the (meth) acrylate (a2-2) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth). Divalent compounds such as acrylate, 1,5-pentanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, and hydroxypivalate neopentyl glycol mono (meth) acrylate Mono (meth) acrylate of alcohol; trimethylolpropane di (meth) acrylate, ethylene oxide (EO) modified trimethylolpropane (meth) acrylate, propylene oxide (PO) modified trimethylolpropane di (meta) Mono- or di (meth) acrylate of a trivalent alcohol such as acrylate, glycerin di (meth) acrylate, bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate, or a part of these alcoholic hydroxyl groups Mono- and di (meth) acrylates having hydroxyl groups modified with ε-caprolactone; monofunctional hydroxyl groups such as pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and 3 A compound having a functional (meth) acryloyl group or a polyfunctional (meth) acrylate having a hydroxyl group obtained by further modifying the compound with ε-caprolactone; dipropylene glycol mono (meth) acrylate, diethylene group (Meth) acrylates having an oxyalkylene chain such as coal mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate; polyethylene glycol-polypropylene glycol mono (meth) acrylate, polyoxybutylene-poly (Meth) acrylate having an oxyalkylene chain having a block structure such as oxypropylene mono (meth) acrylate; poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate, poly (propylene glycol-tetramethylene glycol) mono (meth) And (meth) acrylate having an oxyalkylene chain having a random structure such as acrylate. These (meth) acrylates (a2-2) can be used alone or in combination of two or more.

  Among the urethane (meth) acrylate (A2), since it can improve the scratch resistance of the cured coating film of the active energy ray-curable composition of the present invention, it has four or more (meth) acryloyl groups in one molecule. Those are preferred. Since the urethane (meth) acrylate (A2) has four or more (meth) acryloyl groups in one molecule, the (meth) acrylate (a2-2) has 2 (meth) acryloyl groups. Those having at least two are preferred. Examples of such (meth) acrylate (a2-2) include trimethylolpropane di (meth) acrylate, ethylene oxide-modified trimethylolpropane di (meth) acrylate, propylene oxide-modified trimethylolpropane di (meth) acrylate, Glycerin di (meth) acrylate, bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. Can be mentioned. These (meth) acrylates (a2-2) can be used singly or in combination of two or more of the aliphatic polyisocyanate (a1). Among these (meth) acrylates (a2-2), pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate are preferable because they can improve scratch resistance.

  The reaction of the polyisocyanate (a2-1) and the (meth) acrylate (a2-2) can be carried out by a conventional urethanization reaction. Moreover, in order to accelerate | stimulate progress of a urethanation reaction, it is preferable to perform a urethanation reaction in presence of a urethanization catalyst. Examples of the urethanization catalyst include amine compounds such as pyridine, pyrrole, triethylamine, diethylamine and dibutylamine; phosphorus compounds such as triphenylphosphine and triethylphosphine; dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dibutyltin Examples thereof include organic tin compounds such as diacetate and tin octylate, and organic zinc compounds such as zinc octylate.

  Moreover, as needed, as active energy ray-curable compound (A) other than said polyfunctional (meth) acrylate (A1) and urethane (meth) acrylate (A2), epoxy (meth) acrylate, polyester (meth) An acrylate, a polyether (meth) acrylate, etc. can be used. Examples of the epoxy (meth) acrylate include those obtained by reacting (meth) acrylic acid with bisphenol-type epoxy resin, novolac-type epoxy resin, polyglycidyl methacrylate and the like and esterifying it. Moreover, as said polyester (meth) acrylate, (meth) acrylic acid is made to react and esterify with the polyester which the both terminal obtained by polycondensation of polyhydric carboxylic acid and polyhydric alcohol is a hydroxyl group, for example. Or a product obtained by reacting (meth) acrylic acid with ester obtained by adding an alkylene oxide to a polyvalent carboxylic acid. Furthermore, as said polyether (meth) acrylate, what was obtained by reacting (meth) acrylic acid with polyether polyol and esterifying is mentioned, for example.

  The primary average particle diameter of the silica particles (B) is usually preferably 1 nm or more, and is preferably 50 nm or less, more preferably 40 nm or less, and even more preferably 30 nm or less because transparency can be further improved. In addition, the primary average particle diameter of the said silica particle (B) is calculated | required from the result observed with the transmission electron microscope.

  Moreover, it is preferable to use what the silica particle which has said primary average particle diameter secondary aggregated as said silica particle (B). The particle size at D50 in the particle size distribution after the secondary aggregation of the silica particles (hereinafter simply abbreviated as “average particle size”) is preferably 50 nm or more because both high antiblocking properties and high transparency can be achieved. 100 nm or more is more preferable, and 120 nm or more is more preferable. For the same reason, the average particle size after secondary aggregation of the silica particles is preferably 500 nm or less, more preferably 400 nm or less, and even more preferably 300 nm or less. In addition, the particle diameter at D50 in the particle size distribution represents the particle diameter when the integrated amount occupies 50% in the integrated particle amount curve of the particle size distribution measurement result.

  As the silica particles (B), for example, those produced by a wet method can be used. Moreover, although the precipitation method and the gel method are known as a wet method, the silica particle manufactured by any method can be used. Further, in order to obtain silica particles having a primary average particle size and a secondary average particle size of the size used in the present invention, both the precipitation method and the gel method are mineral acids such as sodium silicate and sulfuric acid which are raw materials for silica particles. Can be achieved by adjusting the reaction conditions (pH, raw material concentration, reaction temperature, etc.). Alternatively, silica particles having a larger secondary average particle diameter can be produced once and then pulverized to obtain a desired secondary average particle diameter.

  The apparatus used for pulverizing the silica particles includes a ball mill, a bead mill, a rod mill, a SAG mill, a high-pressure pulverizing roll, a vertical axis impactor (VSI) mill, a colloid mill, a conical mill, a disk mill, an edge mill, a hammer mill, a mortar, and a jet mill. Etc.

  In addition, when pulverizing the silica particles, it is also preferable to add a silane coupling agent and modify the surface of the silica particles with an organic group simultaneously with the pulverization. Examples of the silane coupling agent include trifluoropropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, methyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane.

  Since the compounding quantity of the said silica particle (B) can improve antiblocking property more, the range of 1-60 mass parts is preferable with respect to 100 mass parts of said active energy ray hardening compounds (A), and 2-50 The range of parts by mass is more preferable, and the range of 5 to 40 parts by mass is more preferable.

  The wetting tension on the surface of the cured coating film of the active energy ray-curable composition of the present invention is in the range of 35 to 60 mN / m, but 40 mN / m or more is preferable because the adhesion with OCA can be further improved. A range of ˜55 mN / m is more preferable. The wetting tension is a value measured according to JIS test method K6768: 1999.

  In order to make the said wetting tension into a desired range, it can carry out by adjusting suitably the kind, surface treatment, compounding quantity, etc. of the said silica particle (B).

  Moreover, the active energy ray curable composition of this invention can be made into a cured coating film by irradiating an active energy ray after apply | coating to a base material. The active energy rays refer to ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When irradiating ultraviolet rays as active energy rays to form a cured coating film, it is preferable to improve the curability by adding a photopolymerization initiator (C) to the active energy ray-curable composition of the present invention. Further, if necessary, a photosensitizer (D) can be further added to improve curability. On the other hand, when ionizing radiation such as electron beam, α-ray, β-ray, γ-ray, etc. is used, it cures quickly without using a photopolymerization initiator (C) or photosensitizer (D). It is not necessary to add a photopolymerization initiator (C) or a photosensitizer (D).

  Examples of the photopolymerization initiator (C) include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, oligo {2-hydroxy-2-methyl-1- [4- ( 1-methylvinyl) phenyl] propanone}, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy -2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) -Acetophenone compounds such as butanone; benzoin, benzoin methyl ether, benzoy Benzoin compounds such as isopropyl ether; acylphosphine oxide compounds such as 2,4,6-trimethylbenzoin diphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; benzyl (dibenzoyl) and methylphenyl Benzylic compounds such as glyoxyester, oxyphenylacetic acid 2- (2-hydroxyethoxy) ethyl ester, oxyphenylacetic acid 2- (2-oxo-2-phenylacetoxyethoxy) ethyl ester; benzophenone, methyl o-benzoylbenzoate -4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, acrylated benzophenone, 3,3 ', , 4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone and other benzophenone compounds; 2-isopropylthioxanthone, Thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone and 2,4-dichlorothioxanthone; Aminobenzophenone compounds such as Michler's ketone and 4,4'-diethylaminobenzophenone; 10-butyl-2- Chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, 1- [4- (4-benzoylphenylsulfanyl) phenyl] -2-methyl-2- (4-methylphenylsal Fonyl) Propan-1-one etc. are mentioned. These photopolymerization initiators (C) can be used alone or in combination of two or more.

  Examples of the photosensitizer (D) include tertiary amine compounds such as diethanolamine, N-methyldiethanolamine, and tributylamine, urea compounds such as o-tolylthiourea, sodium diethyldithiophosphate, and s-benzylisothiuro. And sulfur compounds such as nitro-p-toluenesulfonate.

  The photopolymerization initiator (C) and the photosensitizer (D) are used in the active energy ray-curable compound (A) and the compound (B) in the active energy ray-curable composition of the present invention. Is preferably 0.05 to 20 parts by mass, and more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass in total.

  In addition to the active energy ray-curable compound (A) and the silica particles (B), the active energy ray-curable composition of the present invention includes an organic solvent, a polymerization inhibitor, a surface, depending on applications and required characteristics. Conditioner, antistatic agent, antifoaming agent, viscosity modifier, light stabilizer, weathering stabilizer, heat stabilizer, ultraviolet absorber, antioxidant, leveling agent, organic pigment, inorganic pigment, pigment dispersant, silica beads Additives such as organic beads; inorganic fillers such as silicon oxide, aluminum oxide, titanium oxide, zirconia, and antimony pentoxide can be blended. These other blends can be used alone or in combination of two or more.

  The organic solvent is useful in appropriately adjusting the solution viscosity of the active energy ray-curable composition of the present invention, and it is easy to adjust the film thickness particularly for performing thin film coating. Examples of the organic solvent that can be used here include alcohols such as methanol, ethanol, isopropanol, and t-butanol; ester compounds such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate; acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Ketone compounds of the following: aromatic hydrocarbons such as toluene and xylene. These organic solvents can be used alone or in combination of two or more.

  The base film used in the film of the present invention may be in the form of a film or a sheet, and the thickness is preferably in the range of 20 to 500 μm. The material of the base film is preferably a highly transparent resin, for example, a polyester resin such as polyethylene terephthalate, polybutylene terephthalate, or polyethylene naphthalate; a polyolefin resin such as polypropylene, polyethylene, or polymethylpentene-1. Resins; Cellulose acetates such as cellulose acetate (diacetyl cellulose, triacetyl cellulose, etc.), cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate propionate butyrate, cellulose acetate phthalate, cellulose nitrate, etc .; polymethyl methacrylate, etc. Acrylic resin; Vinyl chloride resin such as polyvinyl chloride and polyvinylidene chloride; Polyvinyl alcohol; Ethylene-vinyl acetate copolymer; Poly Polyethylene; Polysulfone; Polyethersulfone; Polyetheretherketone; Polyimide resin such as polyimide and polyetherimide; Norbornene resin (for example, “ZEONOR” manufactured by Nippon Zeon Co., Ltd.), modified norbornene resin (for example, (“Arton” manufactured by JSR Corporation), cyclic olefin copolymers (for example, “Appel” manufactured by Mitsui Chemicals, Inc.), etc. Further, two or more types of base materials made of these resins are bonded together. May be used.

  The thickness of the resin film is preferably in the range of 20 to 200 μm, more preferably in the range of 30 to 150 μm, and still more preferably in the range of 40 to 130 μm. By setting the thickness of the film substrate within the above range, curling can be easily suppressed even when a hard coat layer is provided on one side of the cyclic olefin resin film with the active energy ray-curable composition of the present invention.

  The film of the present invention is obtained by applying the active energy ray-curable composition of the present invention to at least one surface of the film and then irradiating the active energy ray to form a cured coating film. . Examples of the method for applying the active energy ray-curable composition of the present invention to a film include die coating, micro gravure coating, gravure coating, roll coating, comma coating, air knife coating, kiss coating, spray coating, transfer coating, and dip coating. Examples thereof include a coat, a spinner coat, a wheeler coat, a brush coat, a solid coat by silk screen, a wire bar coat, and a flow coat.

  In addition, when the active energy ray-curable composition of the present invention contains an organic solvent, after applying the active energy ray-curable composition to the substrate film, before irradiating the active energy ray, the organic solvent It is preferable to heat or dry at room temperature in order to volatilize the silica particles and segregate the silica particles (B) on the coating film surface. The conditions for heat drying are not particularly limited as long as the organic solvent volatilizes. Usually, the temperature is 50 to 100 ° C. and the time is 0.5 to 10 minutes. preferable.

  In addition, as a device for irradiating ultraviolet rays to cure the active energy ray-curable composition, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, an electrodeless lamp (fusion lamp), a chemical Lamp, black light lamp, mercury-xenon lamp, short arc lamp, helium / cadmium laser, argon laser, sunlight, LED lamp, and the like.

  The film having a cured coating film of the active energy ray-curable composition of the present invention is applicable to various applications because of its excellent anti-blocking property and excellent scratch resistance on its surface. ) And an optical film used for an image display unit of an image display device such as an organic EL display (OLED). In particular, since it has excellent scratch resistance even if it is thin, for example, electronic notebooks, mobile phones, smartphones, portable audio players, mobile personal computers, tablet terminals, etc. It can use suitably as an optical film of the image display part of this image display apparatus. Moreover, when using as an optical film, it can use as a protective film used for the outermost surface of the image display part of an image display apparatus, and a base material of a touch panel. Furthermore, when used as a protective film, for example, in an image display device having a configuration in which a transparent panel for protecting the image display module is provided on the upper part of an image display module such as an LCD module or an OLED module, the transparent panel By sticking to the front or back surface of the plate, it is effective for preventing damage and preventing scattering when the transparent panel is damaged.

  Hereinafter, the present invention will be described in more detail with reference to examples. The average particle size of the silica particles was measured using a particle size distribution meter ("Microtrack UPA" manufactured by Nikkiso Co., Ltd.).

(Preparation Example 1: Preparation of silica dispersion (1))
To 16 parts by mass of silica particles (“Nipples E-220A” manufactured by Tosoh Silica Co., Ltd., average particle size: 1.7 μm, surface untreated product), 42 parts by mass of methyl ethyl ketone and 42 parts by mass of propylene glycol monomethyl ether are added. After mixing by par mill, pulverize and disperse using a bead mill ("Dynomill ECM" manufactured by Willy et Bacofen); media: zirconium beads, bead diameter: 0.3 to 0.4 mm, bead filling rate: 60%) Thus, a silica dispersion liquid (1) having a silica particle content of 16% by mass was obtained. The average particle diameter of the silica particles in this silica dispersion (1) was 251 nm.

(Preparation Example 2: Preparation of silica dispersion (2))
The same procedure as in Preparation Example 1 was carried out except that silica particles (“Nipples BY-200” manufactured by Tosoh Silica Co., Ltd., average particle size: 1.7 μm, surface untreated product) were used, and the content of silica particles was 16 mass. % Silica dispersion (2) was obtained. The average particle diameter of the silica particles in this silica dispersion (2) was 455 nm.

(Preparation Example 3: Preparation of silica dispersion (3))
The same procedure as in Preparation Example 1 except that silica particles (“Aerosil 50” manufactured by Nippon Aerosil Co., Ltd., average particle size: 0.3 μm, surface untreated product) was used. A dispersion (3) was obtained. The average particle diameter of the silica particles in this silica dispersion (3) was 368 nm.

(Preparation Example 4: Preparation of silica dispersion (4))
To 16 parts by mass of silica particles (“Nipples E-220A” manufactured by Tosoh Silica Co., Ltd., average particle size: 1.7 μm, surface untreated product), 42 parts by mass of methyl ethyl ketone and 42 parts by mass of propylene glycol monomethyl ether are added. After mixing by permill, 0.5% by mass of trifluoropropyltrimethoxysilane (“KBM-7103” manufactured by Shin-Etsu Chemical Co., Ltd.) is added to the silica particles, and further mixed by a disper mill. The silica particles are pulverized and dispersed using a bead mill ("Dynomill ECM" manufactured by Willy et Bacofen; media: zirconium beads, bead diameter: 0.3 to 0.4 mm, bead filling rate: 60%). A silica dispersion (4) having a content of 16% by mass was obtained. The average particle diameter of the silica particles in this silica dispersion (4) was 214 nm.

(Preparation Example 5: Preparation of silica dispersion (5))
The same procedure as in Preparation Example 4 was conducted except that the trifluoropropyltrimethoxysilane used in Preparation Example 4 was changed to 3-acryloxypropyltrimethoxysilane (“KBM-5103” manufactured by Shin-Etsu Chemical Co., Ltd.). A silica dispersion (5) having a content of 16% by mass was obtained. The average particle diameter of the silica particles in this silica dispersion (5) was 237 nm.

(Preparation Example 6: Preparation of silica dispersion (6))
The same procedure as in Preparation Example 4 was conducted except that the trifluoropropyltrimethoxysilane used in Preparation Example 4 was changed to methyltrimethoxysilane (“KBM-13” manufactured by Shin-Etsu Chemical Co., Ltd.), and the silica particle content was 16 A mass dispersion of silica (6) was obtained. The average particle diameter of the silica particles in this silica dispersion (6) was 209 nm.

(Preparation Example 7: Preparation of silica dispersion (7))
The same procedure as in Preparation Example 4 was conducted except that the trifluoropropyltrimethoxysilane used in Preparation Example 4 was changed to 3-methacryloxypropyltrimethoxysilane (“KBM-503” manufactured by Shin-Etsu Chemical Co., Ltd.). A silica dispersion (7) having a content of 16% by mass was obtained. The average particle diameter of the silica particles in this silica dispersion (7) was 223 nm.

(Preparation Example 8: Preparation of silica dispersion (8))
The same procedure as in Preparation Example 4 was conducted except that the trifluoropropyltrimethoxysilane used in Preparation Example 4 was changed to vinyltrimethoxysilane (“KBM-1003” manufactured by Shin-Etsu Chemical Co., Ltd.), and the silica particle content was 16 A mass dispersion of silica (8) was obtained. The average particle diameter of the silica particles in this silica dispersion (8) was 225 nm.

(Preparation Example 9: Preparation of silica dispersion (9))
Silica particles were prepared in the same manner as in Preparation Example 4 except that trifluoropropyltrimethoxysilane used in Preparation Example 4 was changed to 3-glycidoxypropyltrimethoxysilane (“KBM-403” manufactured by Shin-Etsu Chemical Co., Ltd.). A silica dispersion liquid (9) having a content of 16% by mass was obtained. The average particle diameter of the silica particles in this silica dispersion (9) was 219 nm.

(Preparation Example 10: Preparation of silica dispersion (10))
To 16 parts by mass of silica particles (“Nipples BY-200” manufactured by Tosoh Silica Co., Ltd., average particle size: 1.7 μm, surface untreated product), 42 parts by mass of methyl ethyl ketone and 42 parts by mass of propylene glycol monomethyl ether are added. After mixing by permill, 0.5% by mass of trifluoropropyltrimethoxysilane (“KBM-7103” manufactured by Shin-Etsu Chemical Co., Ltd.) is added to the silica particles, and further mixed by a disper mill. The silica particles are pulverized and dispersed using a bead mill ("Dynomill ECM" manufactured by Willy et Bacofen; media: zirconium beads, bead diameter: 0.3 to 0.4 mm, bead filling rate: 60%). A silica dispersion liquid (10) having a content of 16% by mass was obtained. The average particle diameter of the silica particles in this silica dispersion (10) was 452 nm.

(Preparation Example 11: Preparation of silica dispersion (11))
The same procedure as in Preparation Example 10 was conducted except that the trifluoropropyltrimethoxysilane used in Preparation Example 10 was changed to 3-acryloxypropyltrimethoxysilane (“KBM-5103” manufactured by Shin-Etsu Chemical Co., Ltd.). A silica dispersion (9) having a content of 16% by mass was obtained. The average particle diameter of the silica particles in this silica dispersion (9) was 463 nm.

(Preparation Example 12: Preparation of silica dispersion (12))
The same procedure as in Preparation Example 10 was performed except that the trifluoropropyltrimethoxysilane used in Preparation Example 10 was changed to methyltrimethoxysilane (“KBM-13” manufactured by Shin-Etsu Chemical Co., Ltd.), and the silica particle content was 16 A mass dispersion of silica (9) was obtained. The average particle diameter of the silica particles in this silica dispersion (9) was 423 nm.

(Preparation Example 13: Preparation of silica dispersion (13))
0.5 part by mass of trifluoropropyltrimethoxysilane used in Preparation Example 10 was mixed with 0.5% by mass of 3-acryloxypropyltrimethoxysilane (“KBM-5103” manufactured by Shin-Etsu Chemical Co., Ltd.) based on silica particles, and The same procedure as in Preparation Example 10 was conducted except that methyltrimethoxysilane (“KBM-13” manufactured by Shin-Etsu Chemical Co., Ltd.) was changed to 0.5 mass% with respect to the silica particles, and the silica particle content was 16 mass%. A silica dispersion (10) was obtained. The average particle diameter of the silica particles in this silica dispersion (10) was 315 nm.

(Preparation Example 14: Preparation of silica dispersion (14))
To 8 parts by mass of silica particles (“Aerosil 50” manufactured by Nippon Aerosil Co., Ltd., average particle size: 0.3 μm, surface untreated product), 42 parts by mass of methyl ethyl ketone and 42 parts by mass of propylene glycol monomethyl ether are added and mixed by a disper mill. After that, 0.5% by mass of trifluoropropyltrimethoxysilane (“KBM-7103” manufactured by Shin-Etsu Chemical Co., Ltd.) is added to the silica particles, and further mixed by a disper mill. (Willie and Bacofen "Dynomill ECM"; media: zirconium beads, bead diameter: 0.3 to 0.4 mm, bead filling rate: 60%), pulverized and dispersed to contain silica particles A silica dispersion liquid (14) having a rate of 16% by mass was obtained. The average particle diameter of the silica particles in this silica dispersion (14) was 263 nm.

(Preparation Example 15: Preparation of silica dispersion (15))
The same procedure as in Preparation Example 14 was carried out except that the trifluoropropyltrimethoxysilane used in Preparation Example 14 was changed to 3-acryloxypropyltrimethoxysilane (“KBM-5103” manufactured by Shin-Etsu Chemical Co., Ltd.). A silica dispersion (15) having a content of 16% by mass was obtained. The average particle diameter of the silica particles in this silica dispersion (15) was 293 nm.

(Preparation Example 16: Preparation of silica dispersion (16))
The same procedure as in Preparation Example 14 was performed except that the trifluoropropyltrimethoxysilane used in Preparation Example 14 was changed to methyltrimethoxysilane (“KBM-13” manufactured by Shin-Etsu Chemical Co., Ltd.), and the silica particle content was 16 A mass dispersion of silica (16) was obtained. The average particle diameter of the silica particles in this silica dispersion (16) was 281 nm.

(Preparation Example 17: Preparation of silica dispersion (17))
To 8 parts by mass of silica particles (“Aerosil NAX50” manufactured by Nippon Aerosil Co., Ltd., average particle diameter: 27.2 μm, surface treatment product with hexamethyldisilazane), 46 parts by mass of methyl ethyl ketone and 46 parts by mass of propylene glycol monomethyl ether are added. After mixing by a disper mill, it is pulverized using a bead mill ("Dynomill ECM" manufactured by Willy et Bacofen); media: zirconium beads, bead diameter: 0.3 to 0.4 mm, bead filling rate: 60%), Dispersion gave a silica dispersion (17) having a silica particle content of 8% by mass. The average particle diameter of the silica particles in this silica dispersion (17) was 207 nm.

(Preparation Example 18: Preparation of silica dispersion (18))
Silica with a silica particle content of 8% by mass, except that silica particles (“Aerosil 200” manufactured by Nippon Aerosil Co., Ltd., average particle size: 42.2 μm, surface untreated product) were used. A dispersion (18) was obtained. The average particle diameter of the silica particles in this silica dispersion (18) was 259 nm.

(Preparation Example 19: Preparation of silica dispersion (19))
The same procedure as in Preparation Example 17 was conducted except that silica particles (“Aerosil R974” manufactured by Nippon Aerosil Co., Ltd., average particle size: 52.0 μm, surface-treated product with dimethyldichlorosilane) were used, and the silica particle content was 8 mass. % Silica dispersion (19) was obtained. The average particle diameter of the silica particles in this silica dispersion (19) was 149 nm.

(Preparation Example 20: Preparation of silica dispersion (20))
The same procedure as in Preparation Example 1 was performed except that “Nipples SS-50F” manufactured by Tosoh Silica Co., Ltd., average particle size: 1.2 μm, surface-treated product with dimethylpolysiloxane was used, and the silica particle content was 16 mass. % Silica dispersion (20) was obtained. The average particle diameter of the silica particles in this silica dispersion (20) was 97 nm.

(Preparation Example 21: Preparation of silica dispersion (21))
The same procedure as in Preparation Example 1 was performed except that “Nipples SBY-61” manufactured by Tosoh Silica Co., Ltd., average particle size: 1.5 μm, surface-treated product with dimethylpolysiloxane was used, and the content of silica particles was 16 mass. % Silica dispersion (21) was obtained. The average particle diameter of the silica particles in this silica dispersion (21) was 358 nm.

(Preparation Example 22: Preparation of silica dispersion (22))
The same procedure as in Preparation Example 17 was performed except that silica particles (“Aerosil NY50” manufactured by Nippon Aerosil Co., Ltd., average particle size: 29.4 μm, surface-treated product with dimethyldichlorosilane) were used, and the silica particle content was 8 mass. % Silica dispersion (22) was obtained. The average particle diameter of the silica particles in this silica dispersion (22) was 234 nm.

(Preparation Example 23: Preparation of silica dispersion (23))
The same procedure as in Preparation Example 17 was performed except that silica particles (“Aerosil RY200” manufactured by Nippon Aerosil Co., Ltd., average particle size: 59.4 μm, surface-treated product with dimethyldichlorosilane) were used, and the silica particle content was 8 mass. % Silica dispersion (23) was obtained. The average particle diameter of the silica particles in this silica dispersion (23) was 901 nm.

(Example 1)
10 parts by mass of dipentaerythritol hexaacrylate (“LumiCure DPA-620” manufactured by Toagosei Co., Ltd., partially containing dipentaerythritol pentaacrylate; hereinafter abbreviated as “DPHA”), pentaerythritol triacrylate (Toagosei Co., Ltd.) "Aronix M-450" manufactured by Co., Ltd., partially containing pentaerythritol triacrylate; hereinafter abbreviated as "PETA") 20 parts by mass, isocyanuric acid EO (ethylene oxide) modified triacrylate (manufactured by Toagosei Co., Ltd.) 30 parts by mass of “Aronix M-315”) and 40 parts by mass of urethane acrylate (“PU-610” manufactured by MIWON) were mixed uniformly.

  Next, the silica dispersion (1) obtained in Preparation Example 1 was diluted with a mixed solvent of methyl ethyl ketone and propylene glycol monomethyl ether (mass ratio = 50/50) so that the content of silica particles was 8% by mass. After adding 20 parts by mass of the product and 4 parts by mass of a photopolymerization initiator (a mixture of “Irgacure 184” and “Irgacure 2959” by BASF Japan Ltd. in a mass ratio of 1: 1), the non-volatile content is 30 with methyl isobutyl ketone. It diluted so that it might become mass%, and active energy ray hardening composition (1) was obtained.

(Examples 2 to 19)
Active energy ray curing is carried out in the same manner as in Example 1 except that the silica dispersion (1) used in Example 1 is changed to the silica dispersions (2) to (19) obtained in Preparation Examples 2 to 19. Sex compositions (2) to (19) were obtained.

(Comparative Examples 1-4)
Active energy ray curing is carried out in the same manner as in Example 1 except that the silica dispersion (1) used in Example 1 is changed to the silica dispersions (20) to (23) obtained in Preparation Examples 20 to 23. Sex compositions (R1) to (R4) were obtained.

[Production of evaluation film]
The active energy ray-curable compositions (1) to (19) and (R1) to (R4) obtained above were converted into polyethylene terephthalate (PET) films ("Lumirror UH-13" manufactured by Toray Industries, Inc., thickness: 50 μm) was coated using a wire bar and dried at 60 ° C. for 60 seconds. Next, UV irradiation is performed using an ultraviolet irradiation device (eye graphic “UV irradiation device”, high pressure mercury lamp: 120 W / cm, irradiation light amount: 1.5 kJ / m ² ) in an air atmosphere, and a cured coating having a film thickness of 2 μm. An evaluation film having a membrane was obtained.

[Measurement of wetting tension]
The wetting tension of the cured coating film surface of the evaluation film obtained above was measured according to JIS test method K6768: 1999.

[Measurement of haze value and evaluation of transparency]
About the film for evaluation obtained above, it measured with the haze meter (Nippon Denshoku Industries Co., Ltd. "NDH2000"). From the obtained haze value, transparency was evaluated according to the following criteria.
A: The haze value is less than 0.5.
B: The haze value is 0.5 or more and less than 2.0.
C: Haze value is 2.0 or more.

[Evaluation of anti-blocking properties]
The cured coating film surfaces of the evaluation film obtained above, or the cured coating film surface of the evaluation film and the substrate surface (the opposite surface of the cured coating film) are brought into contact with each other, and anti-blocking property ( Hereinafter, it is abbreviated as “AB property”).
A: Even if it rubs strongly, it does not catch.
B: Slightly caught when rubbed strongly.
C: It sticks.

[Evaluation of OCA adhesion]
OCA with a width of 25 mm and a film thickness of 25 μm (“Fine Tuck CT-6030” and “Fine Tack Curing Agent DN” manufactured by DIC Corporation) is 100/1 with respect to the cured coating film surface of the evaluation film obtained above. The mixture was mixed at a ratio, and a 180 ° peel test was conducted with a tensile tester to measure the peel strength. The adhesion was evaluated from the obtained peel strength value according to the following criteria.
A: Peel strength is 17N or more.
B: Peel strength is 12N or more and less than 17N.
C: Peel strength is less than 12N.

  Table 1 shows the silica species and the evaluation results used in the active energy ray-curable compositions prepared in Examples 1 to 19 and Comparative Examples 1 to 4.

  The cured coating film of the active energy ray-curable composition of the present invention (Examples 1 to 19) was confirmed to have high transparency, good AB property, and high adhesion to OCA.

  On the other hand, the active energy ray-curable compositions of Comparative Examples 1 to 4 are examples in which the wet tension of the cured coating film surface is less than 35 mN / m, but at least one of transparency and OCA adhesion is insufficient. I was able to confirm.

Claims (4)

  An active energy ray-curable composition containing an active energy ray-curable compound (A) and silica particles (B), wherein the wet tension of the cured coating film surface of the active energy ray-curable composition is 35 to 60 mN / An active energy ray-curable composition having a range of m.   The active energy ray-curable composition according to claim 1, wherein the amount of the silica particles (B) is in the range of 1 to 60 parts by mass with respect to 100 parts by mass of the active energy ray-curable compound (A).   A cured product of the active energy ray-curable composition according to claim 1 or 2.   A film comprising a cured coating film of the active energy ray-curable composition according to claim 1.