TWI746685B - Manufacturing method of active energy ray curable composition and manufacturing method of thin film using the same - Google Patents

Abstract

The present invention provides an active energy ray curable composition, which is an active energy ray curable composition containing an active energy ray curable compound (A) and silica particles (B), and is characterized in that the active energy ray curable property The wetting tension of the hardened coating film surface of the composition is in the range of 35-60 mN/m. The blending amount of the aforementioned silica particles (B) is preferably in the range of 1 to 60 parts by mass relative to 100 parts by mass of the active energy ray curable compound (A). The problem to be solved by the present invention is to provide an active energy ray curable composition that can impart high anti-blocking properties to the film surface, and can form a hard coat with high transparency and high adhesion to OCA, etc., and Use its film.

Description

Manufacturing method of active energy ray curable composition and manufacturing method of thin film using the same

The present invention relates to a curable active energy ray composition and a film using the same. The curable active energy ray composition is coated on the surface of the film and hardened to impart high anti-blocking properties to the surface of the film , Can form a hard coat with high transparency and high adhesion.

Various resin films are used for damage prevention films on the surface of flat panel displays (FPD) such as liquid crystal displays (LCD), organic EL displays (OLED), and plasma displays (PDP), decorative films (sheets) for interior and exterior decoration of automobiles, Various applications such as low-reflection film for windows or heat-ray isolation film. However, the surface of the resin film is soft and the scratch resistance is low. Therefore, in order to compensate for this, it is generally performed to coat and harden a hard coat agent made of a UV curable composition on the surface of the film. A hard coating is provided on the surface. Outline the steps of setting up the hard coat layer, which is to send the film raw material wound into a roll to the coating machine, apply the hard coat agent, and harden by ultraviolet radiation to form the hard coat, and then roll it into a roll again .

Here, since the surface of the hard coat layer is smooth, the films will stick to each other (adhesion) when they are re-wound into a roll shape. When the film is sent out from the roll during reprocessing, the film will stick to each other. There is a problem of damaging the surface of the film.

As a method of preventing the adhesion of the above-mentioned film (anti-blocking), a method of adding fine particles such as silica particles to the hard coating agent to form irregularities on the surface of the hard coating film of the hard coating agent has been proposed (for example, refer to Patent Literature 1 and 2). In addition, there is also a method of combining silica particles with an average primary particle size of 5 to 80 nm and silica particles with an average primary particle size of 100 to 300 nm (for example, refer to Patent Document 3).

Here, the main composition of the indium tin oxide (ITO) film used in the touch panel is: a high refractive index hard coating is formed on one side of the polyethylene terephthalate (PET) substrate, and the other On one side, a hard coating with anti-blocking properties is formed to prevent the adhesion of the films to each other. After the high-refractive-index hard coat layer is laminated with a low-refractive index layer, ITO is sputtered and annealed.

On the other hand, the hard coat side with anti-blocking properties is bonded with a heat-resistant protective PET film before the above-mentioned annealing treatment is completed. Then, peel off the heat-resistant protective PET, use high-transparency adhesive tape (OCA) to assemble the touch panel module, but the hard coating film that can impart the anti-blocking properties mentioned above is not sufficiently dense for OCA. The problem.

Therefore, there is a demand for an active energy ray curable composition that can impart high anti-blocking properties to the film surface and can form a hard coat layer with high transparency and high adhesion to OCA.

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2012-27401 A

[Patent Document 2] JP 2011-98529 A

[Patent Document 3] JP 2009-132880 A

The problem to be solved by the present invention is to provide an active energy ray curable composition and a film using the same. The active energy ray curable composition can impart high anti-blocking properties to the surface of the film, and can be formed with high transparency and For OCA and other hard coatings with high adhesion.

In order to solve the above-mentioned problems, the inventors have intensively studied and found that the wetting tension of the surface of the cured coating film of the active energy ray curable composition containing silica particles is within a certain range, which has the advantages of OCA, etc. High adhesiveness and complete the present invention.

That is, regarding the active energy ray curable composition and the film using the same, the active energy ray curable composition is an active energy ray curable composition containing an active energy ray curable compound (A) and silica particles (B) It is characterized in that the wetting tension of the surface of the cured coating film of the active energy ray curable composition is in the range of 35-60 mN/m.

The active energy ray curable composition system of the present invention can be coated on the surface of a resin film and cured to impart high anti-blocking properties to the surface of the film, forming high transparency and high adhesion to OCA. Adhesive hard coating. Therefore, the cured coating film of the active energy ray curable composition of the present invention has scratch resistance and can prevent damage to the surface of various resin films. It can avoid the problem of blocking as a cause, so it can provide a film with excellent subsequent handling properties. In addition, a film having a hard coat layer formed from a hardened coating film of the active energy ray curable composition of the present invention can be used for liquid crystal displays (LCD), organic EL displays (OLED), plasma displays (PDP), etc. Various applications such as anti-damage films (protective films) on the surface of flat panel displays (FPD) or touch panels, decorative films (sheets) for interior and exterior decoration of automobiles, low-reflection films for windows, or heat-shielding films. It is especially suitable for touch panel applications that require high adhesion to OCA.

[The form of implementing the invention]

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), and the surface of the hardened coating film of the active energy ray curable composition The wetting tension is in the range of 35~60mN/m.

Examples of the active energy ray-curable compound (A) include polyfunctional (meth)acrylate (A1), urethane (meth)acrylate (A2), and the like. These systems may be used singly, or two or more of them may be used in combination.

Furthermore, in the present invention, the so-called "(meth)acrylate" refers to one or both of acrylate and methacrylate, and the so-called "(meth)acryloyl" refers to propylene One or both of an acyl group and a methacrylic group.

The aforementioned polyfunctional (meth)acrylate (A1) is a compound having two or more (meth)acryloyl groups in one molecule. As specific examples of this polyfunctional (meth)acrylate (a1), 1,4-butanediol di(meth)acrylate, 3-methyl-1,5-pentanediol bis(meth) Base) acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylic acid Ester, 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 and other dihydric alcohols (Meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, tris(2-hydroxyethyl) isocyanurate di(meth)acrylic acid Ester, bis(meth)acrylate of the diol obtained by adding 4 mol of ethylene oxide or propylene oxide to 1 mol of neopentyl glycol, and adding 1 mol of bisphenol A 2 moles of ethylene oxide or propylene oxide diol bis(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide modified trimethylolpropane Tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, two trimethylolpropane tri(meth)acrylate, two trimethylolpropane tetra(methyl) ) Acrylate, tris(2-(meth)acryloyloxyethyl) isocyanurate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth) ) Acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. These polyfunctional (meth)acrylate (A1) systems may be used alone, or two or more of them may be used in combination. In addition, among these polyfunctional (meth)acrylates (A1), dipentaerythritol 6 is preferred from the viewpoint of improved scratch resistance of the cured coating film of the active energy ray curable composition of the present invention (Meth)acrylate, dipentaerythritol penta(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate.

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

As the aforementioned polyisocyanate (a2-1), aliphatic polyisocyanate and aromatic polyisocyanate can be exemplified, but from the viewpoint of reducing the color of the cured coating film of the active energy ray curable composition of the present invention, aliphatic is preferred Group polyisocyanate.

烯二異氰酸酯、異佛爾酮二異氰酸酯、亞甲基雙(4-環己基異氰酸酯)、1,3-雙(異氰酸基甲基)環己烷、2-甲基-1,3-二異氰酸基環己烷、2-甲基-1,5-二異氰酸基環己烷等之脂環式聚異氰酸酯等。又，前述脂肪族聚異氰酸酯或脂環式聚異氰酸酯經三聚化的三聚化物亦可作為前述脂肪族聚異氰酸酯使用。還有，此等的脂肪族聚異氰酸酯係可單獨使用，也可併用2種以上。 The aforementioned aliphatic polyisocyanate is a compound in which parts other than isocyanate groups are composed of aliphatic hydrocarbons. Specific examples of this aliphatic polyisocyanate include aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, and lysine triisocyanate; and

Diisocyanate, isophorone diisocyanate, methylene bis(4-cyclohexyl isocyanate), 1,3-bis(isocyanatomethyl)cyclohexane, 2-methyl-1,3-di Alicyclic polyisocyanates such as isocyanatocyclohexane, 2-methyl-1,5-diisocyanatocyclohexane, etc. In addition, a trimerized product of the aforementioned aliphatic polyisocyanate or alicyclic polyisocyanate can also be used as the aforementioned aliphatic polyisocyanate. In addition, these aliphatic polyisocyanate systems may be used alone or in combination of two or more kinds.

烯二異氰酸酯、異佛爾酮二異氰酸酯。 Among the aforementioned aliphatic polyisocyanates, in order to improve the scratch resistance of the coating film, among the aliphatic polyisocyanates, hexamethylene diisocyanate, which is a diisocyanate of a straight-bonded aliphatic hydrocarbon, is preferably an alicyclic diisocyanate. Diisocyanate drop

Diisocyanate, isophorone diisocyanate.

The aforementioned (meth)acrylate (a2-2) is a compound having a hydroxyl group and a (meth)acryloyl group. Specific examples of this (meth)acrylate (a2-2) include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate Butyl ester, 4-hydroxybutyl (meth)acrylate, 1,5-pentanediol mono(meth)acrylate, 1,6-hexanediol mono(meth)acrylate, neopentyl glycol mono( Mono(meth)acrylates of diols such as meth)acrylate, neopentyl glycol mono(meth)acrylate, etc.; trimethylolpropane di(meth)acrylate, ring Ethylene oxide (EO) modified trimethylolpropane (meth)acrylate, propylene oxide (PO) modified trimethylolpropane di(meth)acrylate, glycerol di(meth)acrylate, Mono- or di-(meth)acrylates of triols such as bis(2-(meth)acryloyloxyethyl)hydroxyethyl isocyanurate, or a part of these alcoholic hydroxyl groups Mono and di(meth)acrylates with hydroxyl groups modified by ε-caprolactone; pentaerythritol tri(meth)acrylate, two trimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate (Meth)acrylic acid esters and other compounds having monofunctional hydroxyl groups and trifunctional or higher (meth)acrylic acid groups, or polyfunctional (meth)acrylic acid compounds having hydroxyl groups modified by ε-caprolactone Esters; dipropylene glycol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, etc. with alkylene oxide Chain (meth)acrylate; polyethylene glycol-polypropylene glycol mono(meth)acrylate, polyoxybutylene-polyoxypropylene mono(meth)acrylate, etc. which have block structure of alkylene oxide chain (Meth) acrylate; poly(ethylene glycol-tetramethylene glycol) mono(meth)acrylate, poly(propylene glycol-tetramethylene glycol) mono(meth)acrylate, etc. Structure of (meth)acrylates of alkylene oxide chains, etc. These (meth)acrylate (a2-2) systems may be used singly, or two or more of them may be used in combination.

Among the aforementioned urethane (meth)acrylates (A2), in order to improve the scratch resistance of the cured coating film of the active energy ray curable composition of the present invention, it is preferable to have 4 in one molecule The above (meth)acrylic acid base. Since the aforementioned urethane (meth)acrylate (A2) has 4 or more (meth)acrylic groups in one molecule, it is regarded as the aforementioned (meth)acrylate (a2-2) , Preferably having two or more (meth)acrylic groups. Examples of such (meth)acrylates (a2-2) include trimethylolpropane di(meth)acrylate and ethylene oxide modified trimethylolpropane di(meth)acrylate , Propylene oxide modified trimethylolpropane di(meth)acrylate, glycerol di(meth)acrylate, bis(2-(meth)acryloxyethyl) hydroxyethyl isocyanurate Acid ester, pentaerythritol tri(meth)acrylate, two trimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, etc. With respect to one type of the aforementioned aliphatic polyisocyanate (a1), one type of these (meth)acrylate (a2-2) systems may be used, or two or more types may be used in combination. In addition, 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 aforementioned polyisocyanate (a2-1) and the aforementioned (meth)acrylate (a2-2) can be carried out by a urethane reaction of a common method. Furthermore, in order to promote the urethane reaction, it is preferable to perform the urethane reaction in the presence of a urethane catalyst. Examples of the aforementioned carbamate catalyst include amine compounds such as pyridine, pyrrole, triethylamine, diethylamine, and dibutylamine; phosphorus compounds such as triphenylphosphine and triethylphosphine; Dibutyltin laurate, octyl tin trilaurate, octyl tin diacetate, dibutyl tin diacetate, tin octoate and other organic tin compounds, zinc octoate and other organic zinc compounds, etc.

In addition, as necessary, as the active energy ray curable compound (A) other than the above-mentioned polyfunctional (meth)acrylate (A1) and urethane (meth)acrylate (A2), epoxy can be used (Meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, etc. Examples of the epoxy (meth)acrylate include reacting (meth)acrylic acid with bisphenol type epoxy resin, novolak type epoxy resin, polyglycidyl methacrylate, etc., Those derived from esterification. In addition, as the aforementioned polyester (meth)acrylate, for example, a polyester obtained by polycondensing a polyhydric carboxylic acid and a polyhydric alcohol having hydroxyl groups at both ends, reacting (meth)acrylic acid, and ester Or obtained by reacting and esterifying (meth)acrylic acid with alkylene oxide added to polycarboxylic acid. In addition, as the aforementioned polyether (meth)acrylate, for example, one obtained by reacting and esterifying (meth)acrylic acid with a polyether polyol can be mentioned.

The primary average particle size of the aforementioned silica particles (B) is generally preferably 1 nm or more, and from the viewpoint of further improving transparency, it is preferably 50 nm or less, more preferably 40 nm or less, and particularly preferably 30 nm or less. In addition, the primary average particle size of the aforementioned silica particles (B) is determined from the result of observation with a transmission electron microscope.

In addition, it is preferable that the aforementioned silica particles (B) are those that are secondarily aggregated using silica particles having the above-mentioned primary average particle diameter. The particle size of D50 in the particle size distribution after the secondary agglomeration of silica particles (hereinafter referred to as "average particle size") is preferably 50nm or more from the viewpoint of achieving both high anti-blocking properties and high transparency. , More preferably 100nm or more, particularly preferably 120nm or more. In addition, for the same reason, the average particle size of the silica particles after secondary aggregation is preferably 500 nm or less, more preferably 400 nm or less, and particularly preferably 300 nm or less. Furthermore, the so-called D50 particle size in the particle size distribution is the particle size at which the cumulative amount occupies 50% in the cumulative particle amount curve of the particle size distribution measurement result.

The aforementioned silica particles (B) can be produced by a wet method, for example. In addition, in the wet method, the sedimentation method and the gel method are known, but silica particles produced by either method can be used. Furthermore, in order to become silica particles with the primary average particle diameter and the secondary average particle diameter of the size used in the present invention, both the sedimentation method and the gel method can be adjusted by adjusting the sodium silicate and sulfuric acid used as the raw material of the silica particles. The reaction conditions (pH, raw material concentration, reaction temperature, etc.) of the same mineral acid are achieved. Furthermore, once silica particles having a slightly larger secondary average particle size are produced, they can be pulverized to obtain the desired secondary average particle size.

As the above-mentioned equipment used for the pulverization of silica particles, ball mills, bead mills, rod mills, SAG mills, high-pressure crushing rolls, vertical axis impact (VSI) mills, colloidal mills, and cone mills can be mentioned. , Disc mill, wheel mill, hammer mill, mortar, jet mill, etc.

In addition, when pulverizing the silica particles, it is also preferable to add a silane coupling agent to modify the surface of the silica particles with an organic group at the same time as the pulverization. As the aforementioned silane coupling agent, for example, trifluoropropyltrimethoxysilane, 3-propenoxypropyltrimethoxysilane, methyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane can be used. Base silane and so on.

The compounding amount of the aforementioned silica particles (B) is preferably in the range of 1-60 parts by mass relative to 100 parts by mass of the active energy ray-curable compound (A) from the viewpoint of further improving anti-blocking properties. It is preferably in the range of 2-50 parts by mass, particularly preferably in the range of 5-40 parts by mass.

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 35-60 mN/m, but from the viewpoint of further improving the adhesion to OCA, it is preferably 40 mN/m or more, and more Preferably, it is in the range of 40~55mN/m. In addition, the wetting tension is a value measured in accordance with JIS test method K6768:1999.

In order to bring the aforementioned wetting tension into a desired range, it can be performed by appropriately adjusting the type, surface treatment, blending amount, etc. of the aforementioned silica particles (B).

In addition, the active energy ray curable composition of the present invention can be irradiated with active energy rays to form a cured coating film after being coated on a substrate. The so-called active energy rays refer to ionizing radiation such as ultraviolet rays, electron rays, α rays, β rays, and γ rays. When irradiating ultraviolet rays as an active energy ray to form a cured coating film, it is preferable to add a photopolymerization initiator (C) to the active energy ray curable composition of the present invention to improve the curability. In addition, if necessary, a photosensitizer (D) may be further added to improve the curability. On the other hand, when using ionizing radiation such as electron rays, α rays, β rays, and γ rays, it hardens quickly even without using photopolymerization initiator (C) or photosensitizer (D), so there is no In particular, it is necessary to add a photopolymerization initiator (C) or a photosensitizer (D).

啉基(4-硫甲基苯基)丙烷-1-酮、2-苄基-2-二甲基胺基-1-(4-

啉基苯基)-丁酮等之苯乙酮系化合物；苯偶姻、苯偶姻甲基醚、苯偶姻異丙基醚等之苯偶姻系化合物；2,4,6-三甲基苯偶姻二苯基氧化膦、雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦等之醯基氧化膦系化合物；二苯乙二酮(二苯甲醯)、甲基苯基乙醛酸酯、羥基苯基乙酸2-(2-羥基乙氧基)乙酯、羥基苯基乙酸2-(2-側氧基-2-苯基乙醯氧基乙氧基)乙酯等之二苯乙二酮系化合物；二苯基酮、鄰苯甲醯基苯甲酸甲基-4-苯基二苯基酮、4,4’-二氯二苯基酮、羥基二苯基酮、4-苯甲醯基-4’-甲基-二苯基硫化物、丙烯酸化二苯基酮、3,3’,4,4’-四(第三丁基過氧羰基)二苯基酮、3,3’-二甲基-4-甲氧基二苯基酮、2,4,6-三甲基二苯基酮、4-甲基二苯基酮等之二苯基酮系化合物；2-異丙基噻噸酮、2,4-二甲基噻噸酮、2,4-二乙基噻噸酮、2,4-二氯噻噸酮等之噻噸酮系化合物；米其勒酮、4,4’-二乙基胺基二苯基酮等之胺基二苯基酮系化合物；10-丁基-2-氯吖啶酮、2-乙基蒽醌、9,10-菲醌、樟腦醌、1-[4-(4-苯甲醯基苯基巰基)苯基]-2-甲基-2-(4-甲基苯基磺醯基)丙烷-1-酮等。此等之光聚合起始劑(C)係可單獨使用，也可併用2種以上。 As the aforementioned photopolymerization initiator (C), for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and oligo {2-hydroxy-2 -Methyl-1-[4-(1-methylvinyl)phenyl]acetone}, benzyl dimethyl ketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl Propane-1-one, 4-(2-hydroxyethoxy) phenyl-(2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-

Linyl (4-thiomethylphenyl) propane-1-one, 2-benzyl-2-dimethylamino-1-(4-

Acetophenone compounds such as linylphenyl)-butanone; benzoin compounds such as benzoin, benzoin methyl ether, and benzoin isopropyl ether; 2,4,6-trimethyl Benzoin diphenyl phosphine oxide, bis(2,4,6-trimethylbenzyl)-phenyl phosphine oxide and other phenyl phosphine oxide compounds; ), methyl phenyl glyoxylate, 2-(2-hydroxyethoxy) ethyl hydroxyphenylacetate, 2-(2-side oxy-2-phenylacetoxyethyl) hydroxyphenylacetate (Oxy) ethyl ester and other diacetophenone compounds; diphenyl ketone, phthalic acid methyl-4-phenyl diphenyl ketone, 4,4'-dichloro diphenyl ketone , Hydroxy diphenyl ketone, 4-benzyl-4'-methyl-diphenyl sulfide, acrylated diphenyl ketone, 3,3',4,4'-tetra(tertiary butyl per Oxycarbonyl) benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone, etc. Of diphenyl ketone compounds; 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, etc. Thioxanthone compounds; Aminobenzophenone compounds such as Michelone, 4,4'-diethylaminobenzophenone, etc.; 10-Butyl-2-chloroacridone, 2- Ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, 1-[4-(4-benzylphenylmercapto)phenyl]-2-methyl-2-(4-methylphenylsulfonate (Alkyl) propan-1-one and the like. These photopolymerization initiators (C) may be used alone or in combination of two or more kinds.

In addition, as the aforementioned photosensitizer (D), for example, tertiary amine compounds such as diethanolamine, N-methyldiethanolamine, and tributylamine, urea compounds such as o-tolylthiourea, and diethyldiethanolamine Sulfur compounds such as sodium thiophosphate, s-benzylisothiouronium p-toluenesulfonate, etc.

The usage amounts of the above-mentioned photopolymerization initiator (C) and photosensitizer (D) are relative to the active energy ray-curable compound (A) and the aforementioned compound ( The total of 100 parts by mass of B) is preferably 0.05 to 20 parts by mass, and more preferably 0.5 to 10 parts by mass.

In the active energy ray curable composition of the present invention, in addition to the above-mentioned active energy ray curable compound (A) and silica particles (B), etc., organic solvents and polymerization inhibitors may be blended according to the application and required characteristics. , Surface modifiers, antistatic agents, defoamers, viscosity modifiers, light stabilizers, weather stabilizers, heat stabilizers, ultraviolet absorbers, antioxidants, leveling agents, organic pigments, inorganic pigments, pigment dispersants, Additives for silica beads and organic beads; inorganic fillers for silica, alumina, titania, zirconia, antimony pentoxide, etc. These other blend systems may be used alone, or two or more of them may be used in combination.

The aforementioned organic solvents are useful for suitably adjusting the solution viscosity of the active energy ray curable composition of the present invention, especially for thin film coating, which can easily adjust the film thickness. Examples of organic solvents that can be used here include alcohols such as methanol, ethanol, isopropanol, and tert-butanol; ester compounds such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate; Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and other ketone compounds; toluene, xylene and other aromatic hydrocarbons. These organic solvents may be used alone or in combination of two or more kinds.

烯系樹脂(例如，日本ZEON股份有限公司製「Zeonor」)、改性降

烯系樹脂(例如，(JSR股份有限公司製「Arton」)、環狀烯烴共聚物(例如，三井化學股份有限公司製「Apel」)等。再者，亦可使用貼合有2種以上的由此等之樹脂所構成的基材者。 The aforementioned substrate film used in the film of the present invention may be in the form of a film or a sheet, and its thickness is preferably in the range of 20 to 500 μm. In addition, as the material of the aforementioned base film, a resin with high transparency is preferable, for example, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc. Polyester resins; Polyolefin resins such as polypropylene, polyethylene, polymethylpentene-1, etc.; Cellulose acetate (diacetyl cellulose, triacetyl cellulose, etc.), cellulose acetate propionate Cellulose resins such as esters, cellulose acetate butyrate, cellulose acetate propionate butyrate, cellulose acetate phthalate, and nitrocellulose; acrylic resins such as polymethyl methacrylate; Vinyl chloride resins such as polyvinyl chloride and polyvinylidene chloride; polyvinyl alcohol; ethylene-vinyl acetate copolymer; polystyrene; polyamide; polycarbonate; Ketones; Polyimine resins such as polyimine and polyetherimine; down

Olefin resin (for example, "Zeonor" manufactured by ZEON Co., Ltd.), modified and reduced

Olefin resins (for example, ("Arton" manufactured by JSR Co., Ltd.)), cyclic olefin copolymers (for example, "Apel" manufactured by Mitsui Chemicals Co., Ltd.), etc. In addition, two or more types bonded together can also be used Those made of such a resin as a base material.

In addition, the thickness of the aforementioned resin film is preferably in the range of 20 to 200 μm, more preferably in the range of 30 to 150 μm, and particularly preferably in the range of 40 to 130 μm. Since the thickness of the film substrate is within this range, 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, curling is easily suppressed.

The film of the present invention is obtained by coating the active energy ray curable composition of the present invention on at least one side of the film, and then irradiating the active energy ray to form a cured coating film. As a method of coating the active energy ray curable composition of the present invention on a film, for example, die coating, micro-gravure coating, gravure coating, roll coating, chipped wheel coating, air knife coating, kiss coating, spray coating, and frame coating can be mentioned. Hang coating, dip coating, spin coating, wheel coating, brush coating, full coating by screen, wire rod coating, flow coating, etc.

Furthermore, when an organic solvent is included in the active energy ray curable composition of the present invention, after the active energy ray curable composition is applied to the base film, before the active energy ray is irradiated, in order to volatilize the organic solvent, or in order to The aforementioned silica particles (B) are segregated on the surface of the coating film and are preferably heated or dried at room temperature. The heating and drying conditions are not particularly limited as long as the organic solvent volatilizes, but it is generally preferable to perform heating and drying at a temperature in the range of 50-100°C and a time in the range of 0.5-10 minutes.

In addition, as a device for curing the active energy ray curable composition and irradiating ultraviolet rays, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, an electrodeless lamp (fusion lamp), and a chemical lamp , Black light lamp, mercury-xenon lamp, short arc lamp, helium-cadmium laser, argon laser, sunlight, LED lamp, etc.

The film of the cured coating film with the active energy ray curable composition of the present invention can be used in various applications due to its high anti-blocking properties and excellent scratch resistance on the surface, but it is particularly suitable as a liquid crystal display ( Optical film used in the image display part of image display devices such as LCD) and organic EL display (OLED). Especially because it has excellent scratch resistance even if it is thin, it can be used as an electronic notebook, mobile phone, smart phone, portable audio player, portable computer, tablet terminal, etc. for miniaturization or thinning requirements, for example Optical film for the image display part of the image display device of the Gaozhi portable electronic terminal. In addition, when used as an optical film, it can be used as a protective film for the outermost surface of the image display part of an image display device, and a base material for a touch panel. Furthermore, when used as a protective film, for example, in an image display device with a transparent panel that can protect the image display module on top of an image display module such as an LCD module or an OLED module, by attaching Use on the front or back of the transparent panel is effective in preventing damage or scattering when the transparent panel is broken.

[Example]

Hereinafter, the present invention will be explained in more detail with examples. In addition, the average particle size of silica particles was measured using a particle size distribution meter ("Microtrac UPA" manufactured by Nikkiso Co., Ltd.).

(Preparation example 1: Preparation of silica dispersion liquid (1))

To 16 parts by mass of silica particles ("Nipsil E-220A" manufactured by Tosoh Silica Co., Ltd., average particle size: 1.7 μm, untreated surface), 42 parts by mass of methyl ethyl ketone and 42 parts by mass were added Propylene glycol monomethyl ether, after mixing with a dispersion mill, use a bead mill ("Dyno-Mill ECM" manufactured by Willy A. Bachofen; medium: zirconia beads, bead diameter: 0.3~0.4mm, bead filling rate : 60%), pulverize and disperse to obtain a silica dispersion (1) with a silica particle content of 16% by mass. The average particle diameter of the silica particles in this silica dispersion (1) is 251 nm.

(Preparation example 2: Preparation of silica dispersion liquid (2))

Except that silica particles ("Nipsil BY-200" manufactured by Tosoh Silica Co., Ltd., "Nipsil BY-200", average particle size: 1.7 μm, surface untreated product) were used, the same procedure as in Preparation Example 1 was carried out to obtain a silica particle content rate of 16 Mass% silica dispersion (2). The silica particles in this silica dispersion (2) have an average particle size of 455 nm.

(Preparation example 3: Preparation of silica dispersion liquid (3))

Except that silica particles ("Aerosil 50" manufactured by AEROSIL Co., Ltd., Japan, average particle size: 0.3μm, untreated surface) were used, the same procedure was carried out as in Preparation Example 1, and the content of silica particles was 16% by mass. The silica dispersion liquid (3). The average particle size of the silica particles in the silica dispersion liquid (3) is 368 nm.

(Preparation example 4: Preparation of silica dispersion liquid (4))

To 16 parts by mass of silica particles ("Nipsil E-220A" manufactured by Tosoh Silica Co., Ltd., average particle size: 1.7 μm, untreated surface), 42 parts by mass of methyl ethyl ketone and 42 parts by mass were added The propylene glycol monomethyl ether is mixed with a dispersing mill, and 0.5% by mass of trifluoropropyltrimethoxysilane (produced by Shin-Etsu Chemical Co., Ltd. "KBM-7103") is added to the silica particles. , Further mixing by a dispersion mill, using a bead mill ("Dyno-Mill ECM" manufactured by Willy A. Bachofen; medium: zirconia beads, bead diameter: 0.3~0.4mm, bead filling rate: 60%), and crush , Disperse the resulting mixture to obtain a silica dispersion (4) with a silica particle content of 16% by mass. The silica particles in this silica dispersion (4) have an average particle size of 214 nm.

(Preparation example 5: Preparation of silica dispersion liquid (5))

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

(Preparation example 6: Preparation of silica dispersion liquid (6))

Except that the trifluoropropyltrimethoxysilane used in Preparation Example 4 was changed to methyltrimethoxysilane ("KBM-13" manufactured by Shin-Etsu Chemical Co., Ltd.), the same procedure as in Preparation Example 4 was carried out to obtain silica A silica dispersion liquid (6) with a particle content of 16% by mass. The average particle size of the silica particles in this silica dispersion (6) is 209 nm.

(Preparation example 7: Preparation of silica dispersion liquid (7))

Except that the trifluoropropyltrimethoxysilane used in Preparation Example 4 was changed to 3-methacryloxypropyltrimethoxysilane ("KBM-503" manufactured by Shin-Etsu Chemical Co., Ltd.), the same as Preparation Example 4 In the same manner, a silica dispersion liquid (7) having a silica particle content of 16% by mass was obtained. The average particle diameter of the silica particles in this silica dispersion liquid (7) is 223 nm.

(Preparation example 8: Preparation of silica dispersion liquid (8))

Except that the trifluoropropyltrimethoxysilane used in Preparation Example 4 was changed to vinyltrimethoxysilane ("KBM-1003" manufactured by Shin-Etsu Chemical Co., Ltd.), the same procedure as in Preparation Example 4 was carried out to obtain silica A silica dispersion liquid (8) with a particle content rate of 16% by mass. The average particle size of silica particles in this silica dispersion (8) is 225 nm.

(Preparation example 9: Preparation of silica dispersion liquid (9))

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

(Preparation example 10: Preparation of silica dispersion liquid (10))

To 16 parts by mass of silica particles ("Nipsil BY-200" manufactured by Tosoh Silica Co., Ltd., average particle size: 1.7 μm, untreated surface), 42 parts by mass of methyl ethyl ketone and 42 parts by mass were added The propylene glycol monomethyl ether is mixed with a dispersing mill, and 0.5% by mass of trifluoropropyltrimethoxysilane (produced by Shin-Etsu Chemical Co., Ltd. "KBM-7103") is added to the silica particles. , Further mixing by a dispersion mill, using a bead mill ("Dyno-Mill ECM" manufactured by Willy A. Bachofen; medium: zirconia beads, bead diameter: 0.3~0.4mm, bead filling rate: 60%), and crush , Disperse the resulting mixture to obtain a silica dispersion (10) with a silica particle content of 16% by mass. The average particle size of the silica particles in the silica dispersion (10) is 452 nm.

(Preparation example 11: Preparation of silica dispersion liquid (11))

The same as Preparation Example 10 except that the trifluoropropyltrimethoxysilane used in Preparation Example 10 was changed to 3-propenoxypropyltrimethoxysilane ("KBM-5103" manufactured by Shin-Etsu Chemical Co., Ltd.) It was carried out to obtain a silica dispersion liquid (9) with a silica particle content of 16% by mass. The silica particles in this silica dispersion (9) have an average particle size of 463 nm.

(Preparation example 12: Preparation of silica dispersion liquid (12))

Except that the trifluoropropyltrimethoxysilane used in Preparation Example 10 was changed to methyltrimethoxysilane ("KBM-13" manufactured by Shin-Etsu Chemical Co., Ltd.), the same procedure as in Preparation Example 10 was carried out to obtain silica A silica dispersion liquid (9) with a particle content rate of 16% by mass. The average particle diameter of the silica particles in this silica dispersion (9) is 423 nm.

(Preparation example 13: Preparation of silica dispersion liquid (13))

Except that the 0.5 parts by mass of trifluoropropyltrimethoxysilane used in Preparation Example 10 was changed to 0.5% by mass of 3-propenoxypropyltrimethoxysilane with respect to silica particles (Shin-Etsu Chemical Co., Ltd. Co., Ltd. "KBM-5103") and 0.5% by mass of methyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd. "KBM-13") with respect to silica particles, the same as Preparation Example 10 Proceeding to obtain a silica dispersion liquid (10) having a silica particle content rate of 16% by mass. The average particle size of the silica particles in the silica dispersion (10) is 315 nm.

(Preparation example 14: Preparation of silica dispersion liquid (14))

To 8 parts by mass of silica particles ("Aerosil 50" manufactured by AEROSIL Co., Ltd., average particle size: 0.3μm, untreated surface), 42 parts by mass of methyl ethyl ketone and 42 parts by mass of propylene glycol are added Monomethyl ether is mixed with a dispersion mill, and 0.5% by mass of trifluoropropyltrimethoxysilane (“KBM-7103” manufactured by Shin-Etsu Chemical Co., Ltd.) is added to the silica particles. Further mixing by a dispersing mill, using a bead mill ("Dyno-Mill ECM" manufactured by Willy A. Bachofen; medium: zirconia beads, bead diameter: 0.3~0.4mm, bead filling rate: 60%), pulverizing and dispersing From the obtained mixed liquid, a silica dispersion liquid (14) having a silica particle content of 16% by mass was obtained. The silica particles in this silica dispersion (14) have an average particle size of 263 nm.

(Preparation Example 15: Preparation of Silica Dispersion Liquid (15))

The same as Preparation Example 14 except that the trifluoropropyltrimethoxysilane used in Preparation Example 14 was changed to 3-propenoxypropyltrimethoxysilane ("KBM-5103" manufactured by Shin-Etsu Chemical Co., Ltd.) It was carried out to obtain a silica dispersion liquid (15) with a silica particle content of 16% by mass. The average particle diameter of the silica particles in this silica dispersion (15) is 293 nm.

(Preparation example 16: Preparation of silica dispersion (16))

Except that the trifluoropropyltrimethoxysilane used in Preparation Example 14 was changed to methyltrimethoxysilane ("KBM-13" manufactured by Shin-Etsu Chemical Co., Ltd.), the same procedure as in Preparation Example 14 was carried out to obtain silica A silica dispersion liquid (16) with a particle content of 16% by mass. The average particle size of the silica particles in this silica dispersion (16) was 281 nm.

(Preparation example 17: Preparation of silica dispersion liquid (17))

To 8 parts by mass of silica particles ("Aerosil NAX50" manufactured by AEROSIL Co., Ltd., average particle size: 27.2μm, surface-treated product with hexamethyldisilazane), 46 parts by mass of methyl are added Ethyl ketone and 46 parts by mass of propylene glycol monomethyl ether were mixed by a dispersion mill, and then a bead mill ("Dyno-Mill ECM" manufactured by Willy A. Bachofen Co., Ltd.; medium: zirconia beads, bead diameter: 0.3 ~0.4mm, bead filling rate: 60%), pulverize and disperse to obtain a silica dispersion (17) with a silica particle content of 8% by mass. The average particle diameter of the silica particles in this silica dispersion (17) is 207 nm.

(Preparation example 18: Preparation of silica dispersion liquid (18))

Except that silica particles ("Aerosil 200" manufactured by AEROSIL Co., Ltd., Japan, average particle size: 42.2μm, untreated surface) were used, the same procedure as in Preparation Example 17 was carried out to obtain a silica particle content rate of 8% by mass. The silica dispersion (18). The silica particles in this silica dispersion (18) have an average particle size of 259 nm.

(Preparation Example 19: Preparation of Silica Dispersion Liquid (19))

Except that silica particles ("Aerosil R974" manufactured by AEROSIL Co., Ltd., Japan, average particle size: 52.0μm, surface-treated with dimethyldichlorosilane) were used, the same procedure as in Preparation Example 17 was carried out to obtain silica A silica dispersion liquid (19) with a particle content of 8% by mass. The silica particles in this silica dispersion (19) have an average particle size of 149 nm.

(Preparation example 20: Preparation of silica dispersion (20))

Except for using "Nipsil SS-50F" manufactured by Tosoh Silica Co., Ltd., average particle size: 1.2μm, surface-treated product with dimethylpolysiloxane), the same procedure as in Preparation Example 1 was carried out to obtain silica particles The silica dispersion liquid (20) with a content rate of 16% by mass. The average particle diameter of the silica particles in the silica dispersion (20) is 97 nm.

(Preparation example 21: Preparation of silica dispersion liquid (21))

Except for using "Nipsil SBY-61" manufactured by Tosoh Silica Co., Ltd., average particle size: 1.5μm, surface-treated product with dimethylpolysiloxane), the same procedure as in Preparation Example 1 was carried out to obtain silica particles The silica dispersion liquid (21) with a content rate of 16% by mass. The average particle diameter of the silica particles in this silica dispersion (21) is 358nm.

(Preparation example 22: Preparation of silica dispersion liquid (22))

Except that silica particles ("Aerosil NY50" manufactured by AEROSIL Co., Ltd., Japan, average particle size: 29.4μm, surface treated with dimethyldichlorosilane) were used, the same procedure as in Preparation Example 17 was carried out to obtain silica A silica dispersion liquid (22) with a particle content of 8% by mass. The average particle size of the silica particles in this silica dispersion (22) is 234 nm.

(Preparation example 23: Preparation of silica dispersion liquid (23))

Except that silica particles ("Aerosil RY200" manufactured by AEROSIL Co., Ltd., Japan, average particle size: 59.4μm, surface-treated with dimethyldichlorosilane) were used, the same procedure as in Preparation Example 17 was carried out to obtain silica A silica dispersion liquid (23) with a particle content of 8% by mass. The average particle size of the silica particles in this silica dispersion (23) is 901 nm.

(Example 1)

Uniformly mix 10 parts by mass of dipentaerythritol hexaacrylate (“Lumicure DPA-620” manufactured by Toagosei Co., Ltd., part of which contains dipentaerythritol pentaacrylate; hereinafter referred to as “DPHA”), and 20 parts by mass of pentaerythritol triacrylate (Toya "Aronix M-450" manufactured by Synthetic Co., Ltd., partly containing pentaerythritol triacrylate; hereinafter referred to as "PETA"), 30 parts by mass of isocyanuric acid EO (ethylene oxide) modified triacrylate (Toya Gosei "Aronix M-315" manufactured by Co., Ltd.) and 40 parts by mass of urethane acrylate ("PU-610" manufactured by MIWON).

Next, 20 parts by mass of the silica particles were added to the mixture and 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 became 8% by mass. The silica dispersion liquid (1) and 4 parts by mass of the photopolymerization initiator (a mixture of "Irgacure 184" and "Irgacure 2959" made by BASF Japan Co., Ltd. with a mass ratio of 1:1), then methyl The isobutyl ketone was diluted to a non-volatile content of 30% by mass, and an active energy ray curable composition (1) was obtained.

(Examples 2-19)

Except that the silica dispersion (1) used in Example 1 was changed to the silica dispersions (2) to (19) obtained in Preparation Examples 2 to 19, the same procedure as in Example 1 was carried out to obtain active energy ray curability Compositions (2)~(19).

(Comparative Examples 1~4)

Except that the silica dispersion (1) used in Example 1 was changed to the silica dispersions (20) to (23) obtained in Preparation Examples 20 to 23, the same procedure as in Example 1 was carried out to obtain active energy ray curability Composition (R1)~(R4).

[Production of evaluation film]

Using a wire rod, apply the curable active energy ray composition (1)~(19) and (R1)~(R4) obtained above on a polyethylene terephthalate (PET) film (Toray Co., Ltd. "Lumirror UH-13", thickness: 50μm), dried at 60°C for 60 seconds. Next, use an ultraviolet irradiation device (Eye Graphics "UV irradiation device", high-pressure mercury lamp: 120W/cm, irradiation light quantity: 1.5kJ/m ² ) in an air environment, and irradiate ultraviolet rays to obtain a cured coating film with a thickness of 2μm. Use film.

[Measurement of wetting tension]

With respect to the surface of the cured coating film of the evaluation film obtained above, the wetting tension was measured in accordance with JIS test method K6768: 1999.

[Determination of Haze Value and Evaluation of Transparency]

The evaluation film obtained above was measured with a haze meter ("NDH2000" manufactured by Nippon Denshoku Kogyo Co., Ltd.). From the obtained haze value, the 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: The haze value is 2.0 or more.

[Evaluation of anti-blocking property]

The surface of the cured coating film of the evaluation film obtained above or the surface of the cured coating film of the evaluation film and the substrate surface (the opposite side of the cured coating film) were brought into contact with each other, and the anti-blocking properties were evaluated according to the following criteria (hereinafter, Referred to as "AB sex").

A: Even strong friction is not involved.

B: Slightly involved in strong friction.

C: It will stick.

[Evaluation of OCA Adhesion]

On the hardened coating surface of the evaluation film obtained above, an OCA (Finetac CT-6030 made by DIC Co., Ltd. and "Finetac hardener DN" with a width of 25mm and a film thickness of 25μm at a blending ratio of 100/1 Mixer), perform a 180° peel test with a tensile testing machine to measure the peel strength. From the obtained value of the peel strength, the adhesion was evaluated in accordance with the following criteria.

A: The peel strength is 17N or more.

B: The peel strength is 12N or more and less than 17N.

C: The peel strength is less than 12N.

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

It can be confirmed that the cured coating film of the active energy ray curable composition (Examples 1 to 19) of the present invention has high transparency, good AB properties, and high adhesion to OCA.

On the other hand, although the active energy ray curable composition of Comparative Examples 1 to 4 is an example in which the wetting tension of the cured coating film surface is less than 35mN/m, it can be confirmed that at least one of transparency and OCA adhesion is insufficient.

Claims (3)

A method for manufacturing an active energy ray curable composition, which is a method for manufacturing an active energy ray curable composition containing an active energy ray curable compound (A) and silica particles (B), characterized in that: the silica Particles (B) are those with untreated surface, manufactured by a wet method, and pulverized by secondary agglomeration of silica particles with a primary average particle size, relative to 100 parts by mass of active energy Linear curable compound (A), the mixing amount of the silica particles (B) is in the range of 1 to 60 parts by mass, and the wetting tension of the cured coating film surface of the active energy ray curable composition is 35 to 60 mN/m The scope. A method for manufacturing a hardened product, which is a hardened product of the active energy ray hardenable composition of claim 1. A method of manufacturing a thin film, which is characterized by having a cured coating film of the active energy ray curable composition as claimed in claim 1.