TW201412896A - Active energy ray-curable composition and film using the same - Google Patents

Abstract

The present invention provides an active energy ray-curable composition, which contains porous silicon dioxide particle (A) and a multifunctional (meth)acrylate ester (B) containing a hydroxyl group. The above-mentioned porous silicon dioxide particle (A) is obtained by adding a mixture solution (solution I) containing tetraalkoxysilane, alkyl amine, and alcohol into a mixture solution (solution II) containing ammonium, alcohol, and water, and removing the alkyl amine from the silicon dioxide particle after the hydrolysis and condensation reactions of the tetraalkoxysilane to obtain the silicon dioxide particle. Its surface contains tiny pores. Also, because the transparency can be maintained without reduction to endow the thin film with an excellent anti-sticky property by means of coating the active energy ray-curable composition onto the surface of the thin film to make the curable coated film, the present invention can provide various thin films such as a protective thin film and an optical thin film having high transparency and excellent anti-sticky property.

Description

Active energy ray-curable composition and film using the same

The present invention relates to an active energy ray-curable composition which imparts anti-blocking property to a film without lowering transparency, and a film using the same.

The surface of the flat panel display (FPD, Flat Panel Display), the anti-damage hard coating film, the exterior decorative sheet, the window low-reflection film or the infrared blocking film are coated to impart the desired functions. Active energy ray-curable composition. These films are sent from a roll which is wound into a roll shape to a coater, and the active energy ray-curable composition is applied and cured by an active energy ray, and then wound up into a roll shape. At this time, the film wound into a roll has the following problem: since the coated surface is finally smooth, the film adheres to each other, that is, the adhesion, and the film is caused by the adhesion when the film is continuously fed from the roll during the reworking. The friction causes the film to be damaged.

Therefore, as a method of suppressing the adhesion of the film as described above and imparting blocking resistance to the film, there is known a method of forming irregularities on the surface of the film, for example, inorganic particles known to be kneaded in the raw material resin of the film to form irregularities. A method of forming a film after the filming, a method of applying a coating agent containing inorganic particles or the like on the surface of the film, and the like.

For example, as the coating agent, an anti-blocking coating agent containing inorganic particles such as cerium oxide particles is proposed (for example, see Patent Document 1). However, although the coating agent can prevent adhesion to some extent, it is not necessarily sufficient. Moreover, in order to make the blocking resistance sufficient, it is necessary to mix inorganic particles and the like at a relatively high compounding ratio. Therefore, there is a problem in that the resin in the coating agent originally has properties such as hardness and flexibility.

Therefore, the industry has sought a coating agent which can impart a high anti-blocking property to a film with a small amount of compounding.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 5-132645

An object of the present invention is to provide an active energy ray-curable composition which imparts excellent blocking resistance to a film without lowering the transparency, and a film using the film.

The inventors of the present invention conducted intensive studies and found that an active energy ray-curable composition containing porous ceria particles produced by a specific method and a polyfunctional (meth) acrylate having a hydroxyl group is coated. In the film, a film having excellent blocking resistance can be obtained, thereby completing the present invention.

That is, the present invention relates to an active energy ray-curable composition and a film using the same, wherein the active energy ray-curable composition is characterized by containing porous cerium oxide particles (A) and a polyfunctional group having a hydroxyl group (A) The acrylate (B), the porous cerium oxide particle (A) is a mixture of a tetraalkoxy decane, an alkylamine and an alcohol (liquid I) added to a mixture containing ammonia, an alcohol and water. In the (II liquid), the cerium oxide particles are obtained by hydrolysis and condensation reaction of a tetraalkoxy decane, and then the alkylamine is removed from the cerium oxide particles, and the surface thereof has fine pores.

By applying the active energy ray-curable composition of the present invention to the surface of the film to form a cured coating film, it is possible to easily obtain a film having excellent blocking resistance and high transparency. Further, the obtained film can be used for protecting various films such as a film and an optical film.

The active energy ray-curable composition of the present invention contains porous cerium oxide particles (A) and a polyfunctional (meth) acrylate (B) having a hydroxyl group, and the porous cerium oxide particles (A) are contained. A mixture of tetraalkoxy decane, alkylamine and alcohol (liquid I) is added to a mixed solution (II liquid) containing ammonia, alcohol and water, and is obtained by hydrolysis and condensation reaction of tetraalkoxy decane. After the cerium oxide particles are obtained, the alkylamine is removed from the cerium oxide particles, and the surface has fine pores.

Examples of the tetraalkoxy decane which is a raw material of the porous ceria particles among the constituent components of the I liquid include tetramethoxy decane, tetraethoxy decane, and tetrapropoxy decane. Among these, tetramethoxydecane is preferred in terms of higher reactivity. In addition, these tetraalkoxy decane may be used alone or in combination of two or more.

The alkylamine which is a constituent component of the I liquid functions as a so-called template for forming pores on the surface of the ceria particles, and therefore the number, size or shape of the pores can be controlled by the type and amount of addition. Further, the alkylamine functions as a catalyst for hydrolysis and condensation reaction of the tetraalkoxydecane together with ammonia described later. The amine compound having an alkyl group having 6 to 18 carbon atoms as the alkylamine has good solubility in an alcohol which is a solvent of the liquid I or the liquid II, and is easy to obtain a porous cerium oxide having a particle diameter of, for example, 100 to 250 nm. Microparticles are therefore preferred. Specific examples of the amine compound having an alkyl group having 6 to 18 carbon atoms include octylamine, decylamine, laurylamine, tetradecylamine, and oleylamine. These alkylamines may be used alone or in combination of two or more.

Further, when the ratio of the tetraalkoxydecane to the alkylamine (tetraalkoxydecane/alkylamine) described later is reduced, the number of pores of the cerium oxide particles can be increased. Further, in order to increase the size of the pores of the cerium oxide particles, for example, an alkylamine having a large carbon number may be used.

The alcohol which is a constituent component of the I liquid functions as a solvent, and exhibits an effect of easily obtaining an I liquid which dissolves and uniformly mixes the alkylamine. As an alcohol, preferably mixed with water By. Further, from the viewpoint of preventing the reaction system from being complicated by the exchange reaction of the alkoxydecane with the alcohol, it is particularly preferred to have the same number of carbon atoms as the alkoxy moiety of the tetraalkoxydecane used. alcohol. Specific examples thereof include methanol, ethanol, and propanol.

The ratio of the tetraalkoxydecane to the alkylamine in the liquid I [tetraalkoxydecane/alkylamine] is preferably a molar ratio in order to obtain particles having pores on the surface and spherical particles in the primary particles. It is preferably in the range of 1/0.05 to 1/5, more preferably in the range of 1/0.1 to 1/3.0 in terms of molar ratio, and more preferably 1/0.1 to 1/2.0 in terms of molar ratio. Within the scope.

Further, the content of the tetraalkoxydecane in the liquid I is preferably from 10 to 60 parts by mass, more preferably from 25 to 45 parts by mass per 100 parts by mass of the liquid I can be produced in a large amount of production. Share.

The ammonia which is a constituent component of the II liquid functions as a catalyst for hydrolysis and condensation reaction of tetraalkoxy decane. The ammonia to be used may be added with ammonia water, or ammonia may be introduced into the reaction solution as a gas, but it is preferably used as ammonia water in terms of easy control of the amount of use.

As the alcohol which is a constituent component of the II liquid, for example, an alcohol used for the preparation of the above I liquid can be used. The alcohol to be used may be the same as those used in the preparation of the liquid I, or may be used differently. Further, only one type may be used, or two or more types may be used in combination.

Among the constituent components of the II liquid, water used as a solvent in the production method of the present invention is preferably pure water in order to avoid mixing impurities in the reaction system as much as possible.

The ratio of ammonia to water in the liquid II [ammonia/water] is preferably in the range of 1/1 to 1/20 in terms of molar ratio in order to obtain particles having pores on the surface and spherical particles in the primary particles. . Further, in terms of the ease of carrying out the reaction operation using ammonia water, it is more preferable that the molar ratio of ammonia to water is in the range of 1/2.5 to 1/20.

Further, as the mass of the water in the liquid of the second liquid, it is preferable to control the particle diameter of the porous ceria particles, preferably from 1 to 40 parts by mass, more preferably from 2 parts by mass to 100 parts by mass of the II liquid. 30 parts by mass.

The porous cerium oxide particles (A) used in the present invention are produced by the following steps. The step of adding the above liquid I to the second liquid, performing hydrolysis and condensation reaction of the tetraalkoxy decane to obtain cerium oxide particles (hereinafter referred to as "step 1"); and removing the alkyl group from the cerium oxide particles. The step of the amine (hereinafter referred to as "step 2").

The above steps will be described in detail below. Step 1 is a step of hydrolyzing and condensing the tetraalkoxydecane to form cerium oxide particles. When the liquid I is mixed with the liquid II, it is preferable to obtain the amount of ammonia which acts as a catalyst for the hydrolysis and condensation reaction of the tetraalkoxysilane. It is preferable to mix the I liquid and the II liquid so that the pH of the mixed liquid (reaction system) of the liquid I and the liquid II is in the range of 8 to 12, and more preferably, the pH is set to be in the range of 9 to 11. Mix the I and II solutions in the same amount.

When the liquid I is added to the liquid II, for example, it may be added by dropping the liquid I from the container in which the liquid is placed, or by placing the catheter nozzle in the container in which the liquid is placed. The nozzle flows out of the I liquid and the I liquid is added to the II liquid. Further, when the liquid I is added to the second liquid, the liquid I can be injected while stirring the liquid II.

The temperature at the time of mixing the I liquid and the II liquid is preferably in the range of 5 to 80 ° C in terms of the solubility of the reaction raw material in the reaction system and in order to obtain particles in which the primary particles are spherical.

The injection time of the I liquid to the II liquid is preferably in the range of 0 to 240 minutes, more preferably in the range of 30 to 150 minutes. Here, 0 minute means that the liquid I is once supplied to the liquid II. Further, it is preferred to further stir the reaction for 10 minutes or more in the temperature range of 5 to 80 ° C after the injection of the I solution. By this step 1, cerium oxide particles which are the basis of the porous cerium oxide particles can be obtained.

In the first step, by adding the liquid I to the liquid II, and further adding a mixed liquid (I' liquid) containing a tetraalkoxy decane and an alcohol, it is possible to suppress the other compound, such as a solvent or a resin, from being fined. Porous cerium oxide particles infiltrated. The I' solution can be added quickly after adding the liquid I to the liquid II, or the liquid I can be added to the second liquid, and then it is added after standing or stirring.

Step 2 removes the alkylamine from the cerium oxide particles obtained in the above step 1. As Examples of the method for removing the alkylamine include a method of washing the cerium oxide particles with an acid, a method of spraying the cerium oxide particles at a high temperature, and a method of baking the cerium oxide particles.

When the alkylamine is removed from the cerium oxide particles, the cerium oxide particles may be washed in advance. As a method of washing the cerium oxide particles, for example, first, the cerium oxide particles are centrifugally separated from the reaction solution obtained in the step 1, and the cerium oxide particles are extracted. An alcohol was added to the cerium oxide particles and stirred to prepare a suspension, and the suspension was again centrifuged, and cerium oxide particles were extracted. The cerium oxide particles are washed with alcohol by performing this step several times. The alcohol to be used at this time is preferably the same type as the alcohol used in the preparation of the above I liquid and II liquid. Further, the method of extracting the cerium oxide particles from the reaction solution and the alcohol suspension is not limited to centrifugal separation, and for example, ultrafiltration may also be used. Further, the washing step can be continuously performed using an ultrafiltration device.

Examples of the acid used in the method of washing the above-mentioned ceria particles by acid include hydrochloric acid, nitric acid, sulfuric acid, acetic acid, and the like. Among these acids, inorganic acids are preferred in terms of water-soluble salts.

When the above cerium oxide particles are washed with an acid, it is preferably carried out in the presence of an alcohol in addition to water. In this case, the alcohol to be used may be the same type as the alcohol used in the above-mentioned I liquid and II liquid. Further, the extraction of the alkylamine is preferably carried out by heating, and as the temperature range, it is preferably in the vicinity of the boiling point of the alcohol to be used in terms of high extraction efficiency.

In order to spray the cerium oxide particles at a high temperature, for example, a commercially available spray dryer capable of spraying the cerium oxide particles in an environment of about 270 to 800 ° C may be used. Here, when the cerium oxide particles are sprayed at a high temperature, the above-mentioned cerium oxide particles may be washed with an alcohol or washed with an acid.

In the method of calcining the above cerium oxide particles, the above-mentioned cerium oxide particles may be washed with an alcohol or washed with an acid.

The drying temperature for drying the cerium oxide particles after the above washing is preferably in the range of 60 to 150 ° C, more preferably in the range of 80 to 130 ° C.

The dried cerium oxide particles are calcined to remove all of the organic matter remaining in the cerium oxide particles. Thereby, the alkylamine used as a template can be removed. As a condition of the calcination step, the calcination temperature is preferably in the range of from 400 to 1,000 ° C, more preferably in the range of from 500 to 800 ° C. Further, the baking time is preferably 30 minutes or longer, more preferably 1 hour or longer. By performing the calcination step, all the organic substances remaining in the ceria particles can be removed, so that porous ceria having pores on the surface of the ceria particles can be produced.

After the calcination, it is preferred to carry out the pulverization in the case where the particles are agglomerated. Examples of the pulverizer used for pulverization include a ball mill, a colloid mill, a conical mill, a disc mill, an edge mill, a pulverizer, a hammer mill, a mortar, and granulation. A pellet mill, a jet mill, a vertical SHAS impactor (VSI), a Wiley mill, a roll mill, and the like.

Further, in order to prevent self-coagulation of the cerium oxide particles and to improve the dispersibility to the organic solvent or the resin, it is preferred to obtain the porous material by surface treatment after the above-mentioned baking step by a surface treatment agent. The hydroxyl group of the stanol group present on the surface of the cerium oxide particle is replaced with a hydrophobic group. The method of performing the surface treatment includes, for example, a method in which porous ceria is immersed in a solution obtained by dissolving a surface treatment agent in a solvent, and heating is carried out as needed. Examples of the solvent used for the surface treatment include methanol, ethanol, isopropanol, benzene, toluene, xylene, N,N-dimethylformamide, hexamethyldioxane, and the like. Further, examples of the surface treatment agent for surface modification include a decane compound or a decane compound such as methyltrimethoxydecane, dimethyldimethoxydecane, phenyltrimethoxydecane, and methyltriethyl. Oxy decane, dimethyl diethoxy decane, phenyl triethoxy decane, hexyl trimethoxy decane, hexyl triethoxy decane, decyl trimethoxy decane, trifluoropropyl trimethoxy decane, Hexamethyldioxane, trimethylmethoxydecane, ethyltrimethoxydecane, trimethylethoxydecane, dimethyldiethoxydecane, hexamethyldi "Dow Corning 2634 Coating" (manufactured by Dow Corning Co., Ltd.) as a perfluoropolyether having a methoxy decane terminal, and "Fluorolink S10" as a perfluoropolyether having an ethoxy decane terminal ( Solvay Solexis company) and so on. In particular, by surface treatment with the above-described decazane compound, porous cerium oxide particles surface-modified with a decazane compound can be obtained. Specifically, by performing the step of surface-modifying the obtained porous ceria particles by the above step 2 (the step of removing the alkylamine from the ceria particles), surface modification using the aziridine compound can be obtained. Porous ceria particles. As the decane compound used herein, hexamethyldioxane is preferred.

When the surface of the porous ceria particles is surface-modified by a decane compound, it is preferred to use a catalyst. Examples of the catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid; organic acids such as oxalic acid, acetic acid, formic acid, methanesulfonic acid, and toluenesulfonic acid; inorganic bases such as sodium hydroxide, potassium hydroxide, and ammonia; and triethylamine. And organic bases such as pyridine; metal alkoxides such as aluminum triisopropoxide and zirconium tetrabutoxide. In the above, an acid catalyst (inorganic acid or organic acid) can be used in terms of the production stability or storage stability of the dispersion of the porous ceria particles (A). Among the inorganic acids, hydrochloric acid, sulfuric acid and the like are preferred, and among the organic acids, methanesulfonic acid, oxalic acid, phthalic acid, malonic acid, acetic acid, and particularly preferably acetic acid are preferred.

The method of performing surface modification of the porous ceria particles is, for example, a method in which porous ceria is immersed in a solution obtained by dissolving a surface modifying agent in a solvent, and if necessary, heating. Examples of the solvent used for the surface modification include methanol, ethanol, isopropanol, benzene, toluene, xylene, N,N-dimethylformamide, acetone, methyl ethyl ketone, and methyl isobutylene. Ketone and the like.

In order to stabilize the primary particles without causing secondary aggregation of the porous ceria particles (A), the amount of the surface modifier used in the surface modification of the porous ceria particles is relative to the above porous ceria particles ( A) 100 parts by mass, preferably a surface modifier It is in the range of 0.3 to 60 parts by mass, more preferably in the range of 0.5 to 50 parts by mass.

Further, it is preferred to simultaneously pulverize the agglomerated particles of the porous ceria particles (A) when the surface modification is performed to obtain a dispersion in a primary particle state.

By passing through the above steps 1 and 2, porous ceria particles can be obtained. The particle shape, average particle diameter, average pore diameter and specific surface area of the obtained porous ceria particles can be measured by the following measurement methods.

[particle shape]

The particle shape can be confirmed by observation using a Field Emission Scanning Electron Microscope (FE-SEM) (for example, "JSM6700" manufactured by JEOL Ltd.).

[The average particle size]

The average particle diameter can be confirmed by observation using a field emission type scanning electron microscope (FE-SEM) (for example, "JSM6700" manufactured by JEOL Ltd.).

[Average pore size]

The average pore diameter can be measured using a pore size distribution measuring apparatus (for example, "ASAP2020" by Shimadzu Corporation).

[specific surface area]

The specific surface area can be measured by a BET (Brunauer-Emmett-Teller) method using a pore size distribution measuring apparatus (for example, "ASAP2020" manufactured by Shimadzu Corporation).

The particle shape, the average particle diameter, the average pore diameter, and the specific surface area of the obtained porous ceria particles (A) can be measured by the above measurement method. The porous cerium oxide particles used in the present invention are porous cerium oxide particles having a substantially spherical appearance, and the average particle diameter can be controlled by adjusting the amount of ammonia used as described above, preferably 50 to 300 nm. Within the range, it is better to be in the range of 100 to 250 nm. Further, the volume average particle diameter of the porous ceria particles (A) is preferably in the range of 80 to 150 nm, more preferably in the range of 90 to 120 nm. Further, the average pore diameter and specific surface area of the porous cerium oxide particles (A) can be controlled by the type and amount of the alkylamine, and the average pore diameter can be obtained in the range of 1 to 4 nm. , can be obtained within the range of 40 ~ 900m ² / g.

Moreover, since the active energy ray-curable composition containing the porous cerium oxide particles (A) is applied to a film to be described later, the cured coating film is preferably more uniform, and thus the porous cerium oxide particles (A) It is preferred that the particle size distribution is narrower. Therefore, the coefficient of variation (CV) indicating the index of the particle size distribution of the porous ceria particle (A) is preferably in the range of 0 to 40%, more preferably in the range of 0 to 35%. . Moreover, in consideration of ease of production of the porous ceria particles (A), the lower limit of the coefficient of variation is preferably 5%, more preferably 10%, still more preferably 15%, and still more preferably 20%. In addition, the coefficient of variation is calculated by the following formula (1), and the standard deviation in the following formula (1) is calculated by the following formula (2). Further, d84% in the following formula (2) represents an 84% particle diameter in the volume particle size distribution, and d16% represents a 16% particle diameter in the volume particle size distribution.

[Number 1] Coefficient of variation (%) = standard deviation (nm) / volume average particle diameter (nm) × 100 (1) Standard deviation (nm) = (d84% (nm) - d16% (nm)) / 2 ( 2)

The porous cerium oxide particles (A) having the volume average particle diameter and the coefficient of variation as described above can be included in the above step 2 by removing the alkylamine from the cerium oxide particles by the above-described production method. After the step), the step of surface-modifying the obtained cerium oxide particles with a surface modifying agent is obtained. The particle shape and specific surface area of the obtained porous cerium oxide particles (E) can be measured by the above method, and the peaks of the volume average particle diameter, the coefficient of variation, and the pore diameter distribution can be measured by the following measurement methods.

[Volume average particle size and coefficient of variation]

The volume average particle diameter can be measured by a particle size distribution meter using a laser Doppler method (for example, "Zeta potential. Particle size measuring system ELSZ-2" manufactured by Otsuka Electronics Co., Ltd.). Further, the coefficient of variation can be obtained by the above formula (1) based on the volume average particle diameter and the standard deviation measured by the apparatus.

[Crest of pore size distribution]

The peak of the pore size distribution can be measured by a pore size distribution measuring apparatus (for example, "ASAP2020" by Shimadzu Corporation, Ltd.), which is the peak of the pore diameter distribution obtained.

Next, the polyfunctional (meth) acrylate (B) having a hydroxyl group used in the active energy ray-curable composition of the present invention will be described. The polyfunctional (meth) acrylate (B) is a compound having a hydroxyl group and two or more (meth) acrylonitrile groups. Examples of such a polyfunctional (meth)acrylate (B) include trimethylolpropane di(meth)acrylate and ethylene oxide-modified trimethylolpropane di(meth)acrylate. Propylene oxide modified trimethylolpropane di(meth)acrylate, glycerol di(meth)acrylate, isocyanuric acid bis(2-(methyl)propenyloxyethyl)hydroxyethyl ester, etc. a mono(meth)acrylate or di(meth)acrylate of a triol, or a mono(meth)acrylic acid having a hydroxyl group modified by ε-caprolactone as a part of a hydroxyl group of the compounds Ester and di(meth)acrylate; pentaerythritol tri(meth)acrylate, di(trimethylolpropane)tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, etc. having one hydroxyl group and A polyfunctional (meth) acrylate having a hydroxyl group, or a compound having three or more (meth) acrylonitrile groups, or a part of a hydroxyl group of the compounds, which is partially modified with ε-caprolactone. Among these polyfunctional (meth) acrylates (B), pentaerythritol tri(meth) acrylate is preferable in that the blocking resistance of the film is further improved and the physical properties of the cured coating film are also good. Dipentaerythritol penta (meth) acrylate. Further, these polyfunctional (meth) acrylates (B) may be used singly or in combination of two or more.

In the present invention, the term "(meth)acrylate" means either or both of methacrylate and acrylate, and "(meth)acryloyl" means methacryl fluorenyl and propylene. One of the bases or both.

Further, in addition to the above polyfunctionality, the active energy ray-curable composition of the present invention In addition to the (meth) acrylate (B), a polyfunctional (meth) acrylate (C) having no hydroxyl group, an active energy ray-curable monomer (D), and an active energy ray-curable resin (E) may be blended. )Wait.

Examples of the polyfunctional (meth) acrylate (C) having no hydroxyl group include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and triethylene glycol di( Methyl) acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol having a number average molecular weight of 150 to 1000 Di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,3-butanediol II having a number average molecular weight in the range of 150 to 1000 Methyl) acrylate, 1,4-butanediol di(meth) acrylate, 1,6-hexanediol di(meth) acrylate, hydroxypivalate neopentyl glycol di(methyl) Acrylate, bisphenol A di(meth)acrylate, trimethylolpropane tri(meth)acrylate, bis(trimethylolpropane)tetra(meth)acrylate, pentaerythritol tetra(meth)acrylic acid Ester, dipentaerythritol hexa(meth) acrylate, dicyclopentenyl di(meth)acrylate, and the like. Among these, in particular, in terms of excellent hardness of the cured coating film, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(methyl) is preferred. a trifunctional or higher polyfunctional (meth) acrylate such as an acrylate. These polyfunctional (meth) acrylates (C) having no hydroxyl group may be used singly or in combination of two or more kinds.

The above porous cerium oxide particles (A) may be locally present on the surface of the coating film of the active energy ray-curable composition of the present invention, and the above-mentioned polyfunctional group having a hydroxyl group may be further improved in terms of blocking resistance ( The mass ratio [(B)/(C)] of the methyl acrylate (B) to the above polyfunctional (meth) acrylate (C) having no hydroxyl group is preferably in the range of 10/90 to 90/10. More preferably, it is in the range of 20/80 to 80/20, and further preferably in the range of 30/70 to 70/30.

Examples of the active energy ray-curable monomer (D) include methyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and tert-butyl (meth)acrylate. 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, (meth)acrylic acid (meth)acrylic acid alkyl esters such as stearyl ester and isostearyl (meth)acrylate, glyceryl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (meth)acrylic acid 3 -Chloro-2-hydroxypropyl ester, glycidyl (meth)acrylate, allyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, 2-(2-ethyl) Amino)ethyl ester, 2-(dimethylamino)ethyl (meth)acrylate, γ-(meth)acryloxypropyltrimethoxydecane, 2-methoxyethyl (meth)acrylate Ester, methoxydiethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, nonyl phenoxy polyethylene glycol (meth) acrylate, decyl phenoxy poly Propylene glycol (meth) acrylate, (meth) acrylate Oxyethyl ester, phenoxy dipropylene glycol (meth) acrylate, phenoxy polypropylene glycol (meth) acrylate, polybutadiene (meth) acrylate, polyethylene glycol-polypropylene glycol (methyl Acrylate, polyethylene glycol-polybutylene glycol (meth) acrylate, polystyryl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, ( Dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, (meth)acrylic acid Ester, methoxylated cyclodecene triene (meth) acrylate, phenyl (meth) acrylate; maleimide, N-methyl maleimide, N-ethyl cis Butylene diimide, N-propyl maleimide, N-butyl maleimide, N-hexyl maleimide, N-octyl maleimide, N-dodecylmethyleneimine, N-stearyl norimide, N-phenyl maleimide, N-cyclohexyl maleimide , 2-m-butylene iminoethyl-ethyl carbonate, 2-m-butylene iminoethyl propyl carbonate, N-ethyl-(2-butene) Diterpene imidoethyl)ester, N,N-hexamethylenebis-synylene diimide, polypropylene glycol-bis(3-maleoximeiminopropyl)ether, carbonic acid double ( 2-m-butylene iminoethyl), maleimide such as 1,4-dimethyleneimine-based cyclohexane, and the like. These active energy ray-curable monomers (D) may be used singly or in combination of two or more.

Examples of the active energy ray-curable resin (E) include (meth)acrylic acid urethane resin, unsaturated polyester resin, epoxy (meth) acrylate resin, and polyester (meth) acrylate. Ester resin, acryl(meth)acrylate Resin, resin having a maleimide group, and the like.

The (meth)acrylic acid urethane resin used herein may be a urethane obtained by reacting an aliphatic polyisocyanate compound or an aromatic polyisocyanate compound with a (meth) acrylate compound having a hydroxyl group. A bond and a (meth)acrylonitrile-based resin.

Examples of the aliphatic polyisocyanate compound include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, and methylene group. Diisocyanate, 2-methyl-1,5-pentane diisocyanate, 3-methyl-1,5-pentane diisocyanate, dodecamethylene diisocyanate, 2-methylpentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, lower Alkyl diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated toluene diisocyanate, hydrogenated dimethyl diisocyanate, hydrogenated tetramethyl dimethyl diisocyanate, cyclohexyl diisocyanate, and the like. Further, examples of the aromatic polyisocyanate compound include toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, benzodimethyl diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, and benzene. Diisocyanate and the like.

On the other hand, examples of the acrylate compound having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate. 4-hydroxybutyl acrylate, 1,5-pentanediol mono(meth)acrylate, 1,6-hexanediol mono(meth)acrylate, neopentyl glycol mono(meth)acrylate Mono(meth)acrylate of diol such as hydroxypivalic acid neopentyl glycol mono(meth)acrylate; trimethylolpropane di(meth)acrylate, ethylene oxide modified trishydroxyl Methyl propane di(meth)acrylate, propylene oxide modified trimethylolpropane di(meth)acrylate, glycerol di(meth)acrylate, isocyanuric acid bis(2-(methyl) a mono (meth) acrylate or a di(meth) acrylate of a trihydric alcohol such as propylene methoxyethyl) hydroxyethyl ester, or a part of a hydroxyl group of the compounds modified by ε-caprolactone Mono(meth)acrylate and di(meth)acrylate having a hydroxyl group; pentaerythritol tri(meth)acrylate, di(trimethylolpropane) three a compound having one hydroxyl group and three or more (meth) acrylonitrile groups such as (meth) acrylate or dipentaerythritol penta (meth) acrylate, or a part of a hydroxyl group of the compounds is ε-hexyl a polyfunctional (meth) acrylate having a hydroxyl group modified by a lactone; dipropylene glycol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate a (meth) acrylate compound having an alkylene chain such as polyethylene glycol mono(meth)acrylate; polyethylene glycol-polypropylene glycol mono(meth)acrylate, polyoxybutylene-polyoxygen (meth) acrylate compound having a block structure of an alkylene chain such as propylene mono(meth)acrylate; poly(ethylene glycol-1,4-butanediol) mono(meth)acrylate, A (meth) acrylate compound having a random structure of an alkylene chain such as a poly(propylene glycol-1,4-butanediol) mono(meth)acrylate.

The reaction of the above aliphatic polyisocyanate compound or aromatic polyisocyanate compound with a (meth) acrylate compound having a hydroxyl group can be carried out by a usual method in the presence of a urethane catalyst. Specific examples of the urethane-based catalyst which can be used herein include amines such as pyridine, pyrrole, triethylamine, diethylamine and dibutylamine, and phosphines such as triphenylphosphine and triethylphosphine. Organotin compounds such as dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dibutyltin diacetate, tin octoate, and organometallic compounds such as zinc octoate.

The urethane (meth) acrylate resin is particularly preferred in terms of transparency, excellent sensitivity to active energy ray, and excellent curability. The isocyanate compound is obtained by reacting with a (meth) acrylate compound having a hydroxyl group. Further, as the (meth) acrylate compound having a hydroxyl group, a polyfunctional (meth) acrylate compound having a plurality of (meth) acrylonitrile groups is preferred in terms of excellent hardness of the cured coating film. .

The unsaturated polyester resin is a curable resin obtained by polycondensation of an α,β-unsaturated dibasic acid or an anhydride thereof, an aromatic saturated dibasic acid or an anhydride thereof, and a diol, as α, β. - an unsaturated dibasic acid or an anhydride thereof, and examples thereof include maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chloro-maleic acid, and the like. Wait. As Fang Examples of the aromatic saturated dibasic acid or its anhydride include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, tetrahydrophthalic anhydride, and endia Methyltetrahydrophthalic anhydride, halogenated phthalic anhydride, and the like. Examples of the aliphatic or alicyclic saturated dibasic acid include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, sebacic acid, glutaric acid, hexahydrophthalic anhydride, and the like. Ester and the like. Examples of the diols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butylene glycol, 1,4-butanediol, and 2-methylpropane-1,3-diol. Neopentyl glycol, triethylene glycol, tetraethylene glycol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, ethylene glycol carbonate, 2,2- In addition to the above, an oxide such as ethylene oxide or propylene oxide can be used in the same manner as in the case of di-(4-hydroxypropoxydiphenyl)propane.

Examples of the epoxy (meth) acrylate resin include epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, and cresol novolac type epoxy resin. A resin obtained by reacting an epoxy group with (meth)acrylic acid.

The polyester (meth) acrylate resin may, for example, be a resin obtained by reacting a hydroxyl group of a polyester polyol with (meth)acrylic acid.

The acryl-based (meth) acrylate resin, for example, is obtained by polymerizing glycidyl methacrylate and, if necessary, another (meth) acrylate monomer to obtain an epoxy resin having an epoxy group. A resin obtained by reacting the epoxy group with (meth)acrylic acid.

Examples of the resin having a maleimide group include a difunctional cis-butyl group obtained by subjecting N-hydroxyethyl maleimide and an isophorone diisocyanate to ureidolation. An enediminoimine urethane compound, a difunctional maleimide ester compound obtained by esterifying maleimide and acetic acid with poly(1,4-butanediol), a tetrafunctional maleimide ester compound obtained by esterifying maleic acid imide hexanoic acid with pentaerythritol tetraethylene oxide adduct, and maleimide acetic acid and plural A polyfunctional maleimide ester compound obtained by esterification of an alcohol compound. Such alive The performance amount curable resin (E) may be used singly or in combination of two or more.

In the active energy ray-curable composition of the present invention, the anti-blocking property of the film of the present invention to be described later is improved, and the amount of the porous cerium oxide particles (A) is adjusted as described above. The total amount of the components (B) to (E) is 100 parts by mass, preferably in the range of 1 to 50 parts by mass, more preferably in the range of 1 to 20 parts by mass, still more preferably in the range of 1 to 10 parts by mass. Inside.

The film of the present invention has a base material as a film and has a cured coating film formed by applying the active energy ray-curable composition of the present invention on at least one side thereof. Here, a method of producing the film of the present invention will be described. First, after applying the active energy ray-curable composition of the present invention to a base film, the active energy ray is irradiated to cure the active energy ray-curable composition to form a cured coating film. Examples of the active energy ray include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When a cured coating film is formed by irradiating ultraviolet rays as an active energy ray, it is preferred to add a photopolymerization initiator (F) to the active energy ray-curable composition to improve the curability. Further, a photosensitizer (G) may be further added as needed to improve the hardenability. On the other hand, when ionizing radiation such as electron beam, alpha ray, beta ray, or gamma ray is used, it is rapidly hardened without using a photopolymerization initiator or a photosensitizer, so that it is not necessary to add a photopolymerization initiator or Photosensitizer.

Examples of the photopolymerization initiator (F) include an intramolecular cleavage type photopolymerization initiator and a hydrogen abstraction type photopolymerization initiator. Examples of the intramolecular cleavage type photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and benzoin dimethyl 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- Phytyl (4-thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4- Acetophenone-based compound such as phenylphenyl)-butanone, 2-[2-oxy-2-phenylethoxyethoxyethoxy]ethyl ester, 2-(2-hydroxyethoxy)ethyl ester Benzoin, benzoin methyl ether, benzoin and other benzoin; 2,4,6-trimethylbenzoin diphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene)-phenyl a fluorenylphosphine oxide compound such as phosphine oxide; benzoin or methylphenylglyoxylate.

On the other hand, examples of the hydrogen abstraction type photopolymerization initiator include benzophenone, methyl phthalic acid methyl ester-4-phenylbenzophenone, and 4,4'-dichlorodiphenyl. Ketone, hydroxybenzophenone, 4-benzylidene-4'-methyl-diphenyl sulfide, acrylated benzophenone, 3,3',4,4'-tetra (t-butyl a benzophenone compound such as benzoyl peroxide, benzophenone or 3,3'-dimethyl-4-methoxybenzophenone; 2-isopropyl 9-oxosulfur 2,4-dimethyl 9-oxosulfur 2,4-diethyl 9-oxosulfur 2,4-dichloro 9-oxosulfur 9-oxosulfur a compound; an aminobenzophenone-based compound such as rice ketone or 4,4'-diethylaminobenzophenone; 10-butyl-2-chloroacridone, 2-ethyl hydrazine, 9,10-Phosphorus, camphor and so on.

Further, examples of the photosensitizer (G) include amines such as aliphatic amines and aromatic amines, ureas such as o-tolylthiourea, sodium diethyldithiophosphate and S-benzylisothiourea. A sulfur compound such as toluenesulfonate or the like.

The amount of the photopolymerization initiator (F) and the photosensitizer (G) to be used is preferably 0.01 to 20 parts by mass, more preferably 0.01 to 20 parts by mass, per 100 parts by mass of the non-volatile component in the active energy ray-curable composition. 0.1 to 15% by mass, and more preferably 0.3 to 7 parts by mass.

Further, in the active energy ray-curable composition of the present invention, adjustment of viscosity or refractive index, adjustment of color tone of a coating film, or the like may be performed within a range that does not impair the effects of the present invention for purposes such as use and characteristics. Various adjustment materials such as various organic solvents, acrylic resins, phenol resins, polyester resins, polystyrene resins, polyurethane resins, urea resins, melamine resins, etc., are formulated for the purpose of adjusting the properties of the coating or the properties of the coating film. Various resins such as alkyd resin, epoxy resin, polyamide resin, polycarbonate resin, petroleum resin, fluororesin, PTFE (polytetrafluoroethylene), polyethylene, polypropylene, carbon, titanium oxide, aluminum oxide Various organic or inorganic particles such as copper, cerium oxide microparticles, polymerization initiators, polymerization inhibitors, antistatic agents, defoamers, viscosity modifiers, light stabilizers, weathering stabilizers, heat stabilizers, antioxidants, Rust inhibitor, slip agent, wax, gloss adjuster, mold release agent, compatibilizer, conductive adjuster, color Materials, dyes, dispersants, dispersion stabilizers, anthrones, hydrocarbon surfactants, and the like.

Among the above-mentioned respective components, the organic solvent is useful for appropriately adjusting the solution viscosity of the active energy ray-curable composition of the present invention, and in particular, it is easy to adjust the film thickness to perform film coating. Examples of the organic solvent which can be used herein include aromatic hydrocarbons such as toluene and xylene; alcohol compounds such as methanol, ethanol, isopropanol and tert-butanol; and esters such as ethyl acetate and propylene glycol monomethyl ether acetate. a compound; a ketone compound such as methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone. These solvents may be used singly or in combination of two or more.

Here, the amount of the organic solvent used varies depending on the film thickness and viscosity of the application or the target, and is preferably in the range of 0.5 to 10 times by mass based on the total mass of the hardened component.

The active energy ray-curable composition of the present invention can be obtained by mixing the above components, and it is preferred to prevent the coating film defects caused by the incorporation of impurities generated during the production of the coating film, and the obtained film is obtained as needed. The composition was filtered. In this case, the pore diameter of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and still more preferably 1 μm or less.

As the active energy ray for curing the active energy ray-curable composition of the present invention, as described above, it is an ionizing radiation such as an ultraviolet ray, an electron beam, an α ray, a β ray or a γ ray, and is a specific energy source or curing device, for example. Examples thereof include a germicidal lamp, an ultraviolet fluorescent lamp, a carbon arc lamp, a xenon lamp, a high pressure mercury lamp for photocopying, a medium or high pressure mercury lamp, an ultrahigh pressure mercury lamp, an electrodeless lamp, a metal halide lamp, and an LED (Light Emitting Diode). Ultraviolet light, such as a polar body, natural light, or the like, or an electron beam generated by a scanning type or a curtain type electron beam accelerator. In terms of the simplicity of the device, it is preferred to use a device that generates ultraviolet rays.

The base 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. Moreover, as a material of the base film, a resin having high transparency is preferable, and examples thereof include polytrimethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. Ester resin; polyolefin resin such as polypropylene, polyethylene, polymethyl 1-pentene; cellulose acetate (diacetyl cellulose, triethyl cellulose, etc.), cellulose acetate propionate, Cellulose resin such as cellulose acetate butyrate, cellulose acetate propionate butyrate, cellulose acetate phthalate or nitrocellulose; acrylic resin such as polymethyl methacrylate; polyvinyl chloride, Vinyl chloride resin such as polyvinylidene chloride; polyvinyl alcohol; ethylene-vinyl acetate copolymer; polystyrene; polyamine; polycarbonate; polyfluorene; polyether oxime; polyether ether ketone; A polyamidene resin such as an amine or a polyether quinone imide; Ethylene resin (for example, "ZEONOR" manufactured by Japan ZEON Co., Ltd.), modified drop An olefin resin (for example, "ARTON" manufactured by JSR Co., Ltd.), a cyclic olefin copolymer (for example, "APEL" manufactured by Mitsui Chemicals, Inc.), and the like. Further, it is also possible to use two or more types of substrates in which the resins are contained.

Examples of the method for applying the active energy ray-curable composition of the present invention to a substrate include a gravure coater, a roll coater, a comma coater, a knife coater, and an air knife coat. Cloth machine, curtain coater, contact coater, coater, wheel coater (Wheeler Coater), spin coater, dip coater, screen printing, sprayer, applicator, bar coating Coating method of machine.

Further, when the active energy ray-curable composition of the present invention contains an organic solvent, the active energy ray-curable composition is applied to the base film, and then the organic solvent is volatilized before the irradiation of the active energy ray. Further, in order to segregate the porous ceria (A) on the surface of the coating film, it is preferred to carry out heating or room temperature drying. The conditions for the heat drying are not particularly limited as long as the organic solvent is volatilized, and it is usually preferred to carry out heat drying in a range of from 50 to 100 ° C for a period of from 1 to 10 minutes.

The film of the present invention is obtained by operating in the manner described above.

[Examples]

Hereinafter, the present invention will be described in detail by way of examples and comparative examples. Again, borrow The characteristic values of the synthesized porous ceria particles were measured by the following methods.

[particle shape]

The particle shape was confirmed by observation using a field emission type scanning electron microscope (FE-SEM) ("JSM6700" manufactured by JEOL Ltd.) at 50,000 times.

[Volume average particle size and coefficient of variation]

The volume average particle diameter is measured by a particle size distribution meter using a laser Doppler method ("Zeta potential. Particle size measuring system ELSZ-2" manufactured by Otsuka Electronics Co., Ltd.). Further, the coefficient of variation is obtained by the following formula (1) based on the volume average particle diameter and the standard deviation measured by the apparatus. Further, the standard deviation in the following formula (1) is obtained by the following formula (2). Further, d84% in the following formula (2) represents an 84% particle diameter in a volume particle size distribution, and d16% represents a 16% particle diameter in a volume particle size distribution.

[Number 2] Coefficient of variation (%) = standard deviation (nm) / volume average particle diameter (nm) × 100 (1) Standard deviation (nm) = (d84% (nm) - d16% (nm)) / 2 ( 2)

[Crest of pore size distribution]

The peak of the pore size distribution is the peak of the pore distribution obtained by measurement using a pore distribution measuring apparatus ("ASAP2020" manufactured by Shimadzu Corporation).

[specific surface area]

The specific surface area was measured by a BET method using a pore distribution measuring apparatus ("ASAP2020" of Shimadzu Corporation).

(Synthesis Example 1: Synthesis of Porous Ceria Particles (1))

To a 500-mL four-necked flask equipped with a thermometer and a stirring blade, 213.2 g of methanol, 61.3 g of pure water, and 27.4 g of 28% by mass aqueous ammonia were added, and the mixture was uniformly mixed by stirring (II liquid), and the internal temperature was maintained at 20 °C. Further, 34.3 g of tetramethoxynonane, 45.1 g of methanol, and 9.3 g of laurylamine were uniformly mixed in another container (Liquid I). While maintaining the inside of the flask at 20 ° C, the solution I was poured into the liquid II for 120 minutes. After the injection of the liquid I is completed, the reaction is continued at 20 ° C. 60 minutes. After completion of the reaction, the reaction solution was centrifuged at 10,000 rpm for 10 minutes, and then the supernatant was discarded to extract a precipitate.

200 g of methanol was added to the precipitate obtained above and mixed to obtain a suspension. The suspension was centrifuged at 10,000 rpm for 10 minutes, the supernatant was discarded, and the precipitate was washed with methanol. This methanol washing was repeated twice more. The precipitate obtained in the above manner was dried at 120 ° C for 6 hours to obtain a white powder. The obtained white powder was placed in an electric furnace, heated from 25 ° C to 600 ° C at a temperature elevation rate of 2 ° C / min in an air atmosphere, and calcined at 600 ° C for 3 hours. The calcined powder was cooled, and then pulverized by a mortar to obtain 12 g of white porous ceria particles. The obtained porous ceria particles were observed by a field emission type scanning electron microscope (FE-SEM), and as a result, the particle shape was spherical. Further, the obtained pore size distribution of the porous ceria particles (1) was 1.8 nm, and the specific surface area measured by the BET method was 216 m ² /g.

5 g of the above-mentioned porous ceria particles and 44.5 g of isopropyl alcohol were mixed, and an ultrasonic homogenizer ("US-600T" manufactured by Nippon Seiki Co., Ltd.) was used, and after dispersing for 5 minutes at an output of 300 W, 0.5 g of acetic acid and 0.5 g of hexamethyldioxane were added to the dispersion, and dispersed by a wet jet mill ("NANO JET PAL JN-10" manufactured by Changguang Co., Ltd.) at a treatment pressure of 130 MPa for 30 minutes. . The obtained dispersion liquid was placed in a 200 mL four-necked flask equipped with a thermometer and a stirring blade, and heated under reflux for 60 minutes. After the reaction solution was centrifuged at 10,000 rpm for 10 minutes, the supernatant was discarded to obtain a precipitate. 50 g of isopropyl alcohol was added to the precipitate, and an ultrasonic homogenizer ("US-600T" manufactured by Nippon Seiki Co., Ltd.) was used, and the output was dispersed at 300 W for 5 minutes, and then No. 5C filter paper and Tongshan funnel (Tongshan) were used. The dispersion was filtered to obtain a dispersion of porous cerium oxide particles (1) having a solid content of 7.9% by mass.

The porous ceria particles (1) in the dispersion of the porous ceria particles (1) obtained had a volume average particle diameter of 139 nm and a coefficient of variation of 22%.

(Example 1)

227.8 parts by mass of the dispersion of the porous ceria particles (1) obtained in Synthesis Example 1 (containing 18 parts by mass of the porous ceria particles (1)), a mixture of polyfunctional acrylates (dipentaerythritol pentaacrylate) (hereinafter referred to as "DPPA (dipentaerythritol pentaacrylate)"), a mixture of 55 mass% and dipentaerythritol hexaacrylate (hereinafter abbreviated as "DPHA (dipentaerythritol hexaacrylate)), 45 mass%; hereinafter referred to as "polyfunctional acrylate (1) 364 parts by mass of a photopolymerization initiator ("IRGACURE 184" manufactured by BASF JAPAN Co., Ltd., 1-hydroxycyclohexyl phenyl ketone; hereinafter referred to as "Irg. 184") 18 parts by mass and isopropanol 390.2 The parts by mass are uniformly mixed to obtain an active energy ray-curable composition (1).

(Example 2)

Instead of the polyfunctional acrylate used in Example 1, 364 parts by mass of a mixture of a polyfunctional acrylate (a mixture of 35 mass% DPPA and 65 mass% DPHA; hereinafter abbreviated as "polyfunctional acrylate (2)") was used. In the same manner as in Example 1, except that the active energy ray-curable composition (2) was obtained.

(Example 3)

A mixture of a polyfunctional acrylate (n-pentaerythritol triacrylate (hereinafter referred to as "PE3A") 70% by mass and pentaerythritol tetraacrylate (hereinafter abbreviated as "E4A") 30% by mass; hereinafter, simply referred to as "multifunctional acrylic acid" An active energy ray-curable composition (3) was obtained in the same manner as in Example 1 except that 364 parts by mass of the ester (3)") was used instead of the polyfunctional acrylate (1) used in Example 1.

(Example 4)

364 parts by mass of a mixture of a polyfunctional acrylate (a mixture of 60% by mass of PE3A and 40% by mass of PE4A; hereinafter abbreviated as "polyfunctional acrylate (4)")) was used instead of the polyfunctional acrylate used in Example 1. 1) The operation was carried out in the same manner as in Example 1 to obtain an active energy ray-curable composition (4).

(Example 5)

364 parts by mass of a mixture of a polyfunctional acrylate (a mixture of 30% by mass of PE3A and 70% by mass of PE4A; hereinafter abbreviated as "polyfunctional acrylate (5)")) was used instead of the polyfunctional acrylate used in Example 1. 1) The operation was carried out in the same manner as in Example 1 to obtain an active energy ray-curable composition (5).

(Comparative Example 1)

Instead of the porous cerium oxide particles used in Example 1, 18 parts by mass of solid cerium oxide ("SEAHOSTAR KE-P10" manufactured by Nippon Shokubai Co., Ltd., particle size: 100 to 200 nm, surface untreated) was used. In the same manner as in Example 1, except that the amount of the isopropyl alcohol was changed from 390.2 parts by mass to 600 parts by mass, the active energy ray-curable composition (R1) was obtained.

(Comparative Example 2)

Instead of the porous cerium oxide particles used in Example 1, 18 parts by mass of solid cerium oxide ("SEAHOSTAR KE-P100" manufactured by Nippon Shokubai Co., Ltd., particle size 900 to 1,300 nm, surface untreated) was used. 1) The active energy ray-curable composition (R2) was obtained in the same manner as in Example 1 except that the amount of the isopropyl alcohol was changed from 390.2 parts by mass to 600 parts by mass.

(Comparative Example 3)

Ethylene oxide modified trimethylolpropane triacrylate (triacrylate added to trimethylolpropane to 3 moles of ethylene oxide; hereinafter referred to as "EO-TMPTA (ethylene oxide-trimethylolpropane) In the same manner as in Example 1, except that the polyfunctional acrylate (1) used in Example 1 was replaced by 364 parts by mass, an active energy ray-curable composition (R3) was obtained.

(Comparative Example 4)

364 parts by mass of bis(trimethylolpropane) tetraacrylate (hereinafter, abbreviated as "DTMPTA (di-trimethylolpropane triacrylate)") was used instead of the one used in Example 1. An active energy ray-curable composition (R4) was obtained in the same manner as in Example 1 except that the functional acrylate (1) was used.

The compositions of the active energy ray-curable compositions obtained in the above Examples 1 to 5 and Comparative Examples 1 to 4 are shown in Table 1.

(Example 6) [Production of film for evaluation]

The active energy ray-curable composition (1) obtained in the above Example 1 was applied onto a polyethylene terephthalate (PET) film substrate having a thickness of 100 μm using a bar coater #24. After drying at 25 ° C for 10 seconds, it was dried by a dryer at 80 ° C for 1 minute. Then, using an ultraviolet curing device (a molten lamp (H vacuum tube, ultraviolet irradiation amount: 300 J/m ² ), it was hardened in a nitrogen atmosphere to prepare a film for evaluation.

[Evaluation of anti-adhesion]

The surface of the cured coating film of the film for evaluation obtained above or the surface of the cured coating film of the film for evaluation was brought into contact with the surface of the substrate (opposite surface of the cured coating film), and the anti-adhesion was evaluated based on the following five grades. Sex.

5: Not stuck.

4: If it rubs strongly, it will stick slightly.

3: If it is weakly rubbed, it will stick slightly.

2: Adhesion.

1: Fit.

[Measurement of haze value and evaluation of transparency]

The film for evaluation obtained above was measured by a haze meter ("NDH2000" manufactured by Nippon Denshoku Industries Co., Ltd.), and transparency was evaluated based on the obtained haze value based on the following five levels.

5: The haze value is less than 0.5.

4: The haze value is 0.5 or more and less than 1.0.

3: The haze value is 1.0 or more and less than 5.0.

2: The haze value is 5.0 or more and less than 10.0.

1: Haze value is 10.0 or more.

(Examples 7 to 10 and Comparative Examples 5 to 8)

Using the active energy ray-curable compositions (2) to (5) and (R1) to (R4) obtained in the above Examples 2 to 5 and Comparative Examples 1 to 4, the same procedure as in Example 6 was carried out to prepare and evaluate. After the film was used, the evaluation of blocking resistance and transparency was carried out.

The evaluation results of the above blocking resistance and transparency are shown in Table 2.

[Table 2]

From the above results, it is understood that the films of the hardened coating films of the active energy ray-curable compositions (1) to (5) of the present invention having high blocking resistance and high transparency are obtained. Sex.

On the other hand, Comparative Example 1 is an example in which solid cerium oxide particles having a small particle diameter and having no pores on the surface of the cerium oxide particles are used, and although the transparency is high, the surface of the coating film is adhered and anti-adhesion is adhered. Sex is not sufficient.

In Comparative Example 2, a solid cerium oxide particle having a large particle diameter and having no pores on the surface of the cerium oxide particle was used. Although the blocking resistance was good, the haze value was 7.5%, and the transparency was insufficient. .

In Comparative Examples 3 and 4, a polyfunctional acrylate having a hydroxyl group was not used, and only a polyfunctional acrylate having no hydroxyl group was used. Although the transparency was high, the coating film surface was adhered and the blocking resistance was insufficient.

Claims (6)

An active energy ray-curable composition comprising porous cerium oxide particles (A) and a polyfunctional (meth) acrylate (B) having a hydroxyl group, and the porous cerium oxide particles (A) Adding a mixed liquid (I liquid) containing tetraalkoxy decane, alkylamine and alcohol to a mixed liquid (II liquid) containing ammonia, alcohol and water by hydrolysis and condensation reaction of tetraalkoxy decane After obtaining the cerium oxide particles, the alkylamine is removed from the cerium oxide particles, and the surface has fine pores. The active energy ray-curable composition according to claim 1, wherein the porous cerium oxide particles (A) are surface-modified with hexamethyldioxane. The active energy ray-curable composition according to claim 1 or 2, wherein the polyfunctional (meth) acrylate (B) is pentaerythritol tri(meth) acrylate and/or dipentaerythritol penta (meth) acrylate. The active energy ray-curable composition according to any one of claims 1 to 3, which further comprises a polyfunctional (meth) acrylate (C) having no hydroxyl group, and the above polyfunctional (meth) acrylate having a hydroxyl group The mass ratio [(B)/(C)] of the ester (B) to the polyfunctional (meth) acrylate (C) having no hydroxyl group is in the range of 10/90 to 90/10. A cured product obtained by hardening an active energy ray-curable composition according to any one of claims 1 to 4. A film comprising a cured coating film of an active energy ray-curable composition according to any one of claims 1 to 4 on at least one side of a substrate film.