KR20140011948A - Active energy ray-curable composition and film using the same - Google Patents

Abstract

The present invention provides an active energy ray-curable composition containing porous silica particles (A) having micropores on the surface thereof and multifunctional (meth)acrylate (B) having a hydroxyl group which is obtained by adding mixture liquid (I liquid) containing tetraalkoxysilane, alkyl amines and alcohol to mixture liquid (II liquid) containing ammonia, alcohol and water; obtaining silica particles via the hydrolysis and condensation reaction of tetraalkoxysilane; and removing alkyl amines from the silica particles. Also the present invention can grant an excellent anti-blocking property to a film without degrading transparency thereof by applying the active energy ray-curable composition to the surface of the film, thereby constituting a cured film. Accordingly the present invention can provide various films such as a protective film and an optical film having excellent transparency and an excellent anti-blocking property.

Description

ACTIVE ENERGY RAY-CURABLE COMPOSITION AND FILM USING THE SAME}

This invention relates to the active energy ray curable composition which can provide anti blocking property to a film, without reducing transparency, and the film using the same.

Active which can give a desired function to the surface of the absorption prevention hard coating film of a flat panel display (FPD), the decorative sheet for exterior decoration of a car, the low reflection film for windows, and the hot wire cut film, respectively. An energy ray curable composition is coated. These films are sent out from the original fabric wound in roll shape to a coating machine, and an active energy ray curable composition is coated, and after hardening by an active energy ray, it is wound up in roll shape again. At this time, the film wound in roll shape has a smooth finish on the coated surface, so that blocking occurs when the films stick together, and when the film is unrolled from the roll during reworking, friction due to blocking occurs to damage the film. There was a problem.

Therefore, a method of forming irregularities on the surface of the film is known as a method of suppressing the blocking of the film as described above and imparting anti-blocking property to the film. For example, inorganic particles for forming irregularities in the raw material resin of the film After joining, etc., the method of shape | molding a film, the method of coating the film surface with the coating agent containing an inorganic particle etc. in the film surface, etc. are known.

For example, as said coating agent, the antiblocking coating agent containing inorganic particle, such as a silica particle, is proposed (for example, refer patent document 1). However, although this coating agent can prevent blocking to some extent, it was not necessarily enough. Moreover, in order to make anti blocking property sufficient, it is necessary to mix | blend an inorganic particle etc. at a considerably high compounding ratio, and for this reason, there also existed a problem which sacrifices performance, such as hardness, flexibility, etc. which resin in a coating agent originally has.

Therefore, there has been a demand for a coating agent capable of imparting higher anti-blocking properties to a film with a smaller compounding amount.

Japanese Patent Application Laid-Open No. 5-132645

It is an object of the present invention to provide an active energy ray-curable composition and a film using the same, which can impart excellent anti-blocking properties to a film without degrading its transparency.

MEANS TO SOLVE THE PROBLEM As a result of earnest research, the present inventors have excellent anti blocking property by coating the film with the active energy ray curable composition containing the porous silica particle manufactured by the specific method, and the polyfunctional (meth) acrylate which has a hydroxyl group. The film was found and the present invention was completed.

That is, in the present invention, a mixed solution (liquid I) containing tetraalkoxysilane, alkylamine and alcohol is added to a mixed solution (liquid II) containing ammonia, alcohol and water, and subjected to hydrolysis and condensation reaction of tetraalkoxysilane. After obtaining silica particle, the porous silica particle (A) which has a pore on the surface obtained by removing an alkylamine from the said silica particle, and the polyfunctional (meth) acrylate (B) which has a hydroxyl group are contained. The present invention relates to an active energy ray curable composition and a film using the same.

By coating the active energy ray curable composition of this invention on a film surface, and making it into a cured coating film, the film which has the outstanding anti blocking property and high transparency is obtained simply. Moreover, the obtained film can be used for various films, such as a protective film and an optical film.

In the active energy ray-curable composition of the present invention, a mixed solution (liquid I) containing tetraalkoxysilane, alkylamine and alcohol is added to a mixed solution (liquid II) containing ammonia, alcohol, and water to hydrolyze tetraalkoxysilane. And after obtaining a silica particle by a condensation reaction, the porous silica particle (A) which has a pore in the surface obtained by removing an alkylamine from the said silica particle, and the polyfunctional (meth) acrylate (B) which has a hydroxyl group are contained. will be.

As tetraalkoxysilane which becomes a raw material of porous silica particle in the component of the said I liquid, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, etc. are mentioned, for example. Among these, tetramethoxysilane is preferable because of its high reactivity. In addition, these tetraalkoxysilanes may be used by only one type or may be used together 2 or more types.

Since alkylamine which is a component of liquid I acts as a so-called mold for making pores on the surface of silica particles, it is possible to control the number, size and shape of the pores in accordance with the type and the amount of addition thereof. The alkylamine also acts as a catalyst for the hydrolysis and condensation reaction of the tetraalkoxysilane with ammonia described later. As the alkylamine, the amine compound having an alkyl group having 6 to 18 carbon atoms has good solubility in an alcohol which is a solvent of I liquid or II liquid, and porous silica fine particles having a particle size of, for example, 100 to 250 nm are easy to obtain. Therefore, it is preferable. As an example of the amine compound which has a C6-C18 alkyl group, octylamine, decylamine, laurylamine, tetradecylamine, oleylamine, etc. are mentioned, for example. These alkylamines may be used by only one type or may be used together 2 or more types.

Moreover, if the ratio [tetraalkoxysilane / alkylamine] of the tetraalkoxysilane and alkylamine mentioned later is reduced, the number of the pore of a silica particle can be increased. In order to increase the size of the pores of the silica particles, for example, alkylamines having a large number of carbon atoms may be used.

The alcohol which is a constituent of the I liquid acts as a solvent, and dissolves the alkylamine and exhibits the effect of easily obtaining a uniformly mixed I liquid. As alcohol, it is preferable to mix with water. Moreover, it is especially preferable to have the same number of carbon atoms as the alkoxy site | part of the tetraalkoxysilane to be used from a viewpoint of preventing the reaction system from becoming complicated by the exchange reaction of an alkoxysilane and alcohol. Specific examples thereof include methanol, ethanol, propanol and the like.

As a ratio [tetraalkoxysilane / alkylamine] of the tetraalkoxysilane and alkylamine in I liquid, the thing of the range of 1 / 0.05-1/5 by molar ratio has pores on the surface, and primary particles are spherical. It is preferable in order to obtain the particle | grains which are), The range of 1 / 0.1-1 / 3.0 is more preferable by molar ratio, The range of 1 / 0.1-1 / 2.0 is still more preferable by molar ratio.

Moreover, as content of the tetraalkoxysilane in I liquid, since 10-60 mass parts can manufacture many quantities in 100 mass parts of I liquids, it is preferable, and 25-45 mass parts is more preferable.

Ammonia, which is a constituent of the liquid II, acts as a catalyst for the hydrolysis and condensation reaction of the tetraalkoxysilane. Although ammonia to be used may be added as ammonia water or ammonia may be introduced into the reaction solution as a gas, the amount of ammonia to be used is easy to control, so it is preferable to use ammonia water.

As an alcohol which is a component of liquid II, the alcohol used for preparation of the said liquid I can be used, for example. The alcohol to be used may be the same as the alcohol used for the preparation of the I liquid, or may use another. In addition, only one type may be used and two or more types may be used together.

In the component of the liquid II, as water used as a solvent in the production method of the present invention, pure water is preferably used in order to avoid the incorporation of impurities into the reaction system.

The ratio [ammonia / water] of ammonia and water in the II liquid is preferably in the range of 1/1 to 1/20 in molar ratio in order to obtain particles having pores on the surface and spherical primary particles. In addition, since the reaction operation can be facilitated by using ammonia water, the molar ratio of ammonia and water is more preferably in the range of 1 / 2.5 to 1/220.

Moreover, as a mass of the water in II liquid, since the particle diameter of porous silica microparticles | fine-particles is easy to control, 1-40 mass parts is preferable with respect to 100 mass parts of II liquids, and 2-30 mass parts is more preferable.

The porous silica particle (A) used by this invention adds the said I liquid to II liquid, performs hydrolysis and condensation reaction of tetraalkoxysilane, and obtains a silica particle (it abbreviates as "step 1" hereafter). And a step of removing the alkylamine from the silica particles (hereinafter abbreviated as "step 2").

The above process is explained in full detail below. Step 1 is a step of hydrolyzing and condensing tetraalkoxysilane to form silica particles. When mixing I liquid and II liquid, the amount of ammonia acting as a catalyst for the hydrolysis and condensation reaction of tetraalkoxysilane is such that the pH of the mixed liquid (reaction system) of I liquid and II liquid is in the range of 8 to 12. It is preferable to mix I liquid and II liquid so that it may be easy to obtain the particle | grains whose spherical particle is spherical, and it is more preferable to mix I liquid and II liquid so that it may become an amount which becomes pH in the range of 9-11.

In order to add I liquid to II liquid, you may add it by dropping I liquid from the container containing II liquid, for example, by putting a conduit nozzle in the container containing II liquid, and draining I liquid from a conduit nozzle. You may add liquid I to liquid II. In addition, when adding I liquid to II liquid, you may inject I liquid, stirring II liquid.

As temperature at the time of mixing of said I liquid and II liquid, the range of 5-80 degreeC is preferable in order to obtain the solubility to the reaction system of a reaction raw material, and the particle whose primary particle is spherical.

As injection time of I liquid to said II liquid, the range of 0-240 minutes is preferable, and the range of 30-150 minutes is more preferable. 0 minutes here means adding I liquid to II liquid collectively. Moreover, it is preferable to further carry out stirring reaction for 10 minutes or more in the temperature range of 5-80 degreeC after injecting I liquid. By this step 1, silica particles serving as a source of the porous silica particles are obtained.

In step 1, after adding I liquid to II liquid, the mixed liquid (I 'liquid) containing tetraalkoxysilane and alcohol is further added, and invasion into the pore of another compound, for example, a solvent and resin is carried out. A porous silica particle which can be suppressed is obtained. I 'liquid may be added promptly after adding I liquid to II liquid, and I liquid may be added to II liquid, and may be added after standing still or stirring after that.

Step 2 is to remove the alkylamine from the silica particles obtained in step 1 described above. As a method of removing an alkylamine, the method of washing the said silica particle with an acid, the method of spraying the said silica particle in high temperature, the method of baking the said silica particle, etc. are mentioned, for example.

When removing an alkylamine from a silica particle, you may wash | clean a silica particle beforehand. As a method of washing a silica particle, first, for example, a silica particle is centrifuged from the reaction solution obtained at the process 1, and a silica particle is taken out. Alcohol is added to the silica particles, the mixture is stirred to form a suspension, and the suspension is centrifuged again to remove the silica particles. By performing this step several times, the silica particles are washed with alcohol. It is preferable that the alcohol used at this time is the same kind as the alcohol used for preparation of the said I liquid and II liquid. Moreover, as a method of taking out silica particle from a reaction solution and an alcohol suspension, it is not limited to centrifugation, For example, you may use ultrafiltration. In addition, you may perform a washing | cleaning process continuously using an ultrafiltration apparatus.

As an acid used by the method of wash | cleaning the said silica particle with acid, hydrochloric acid, nitric acid, sulfuric acid, acetic acid etc. are mentioned, for example. Among these acids, since the neutralized salt is water-soluble, an inorganic acid is preferable.

When wash | cleaning the said silica particle with acid, it is preferable to carry out in presence of alcohol other than water. In this case, the alcohol used may be the same kind as the alcohol used in the above-mentioned I liquid and II liquid. Moreover, it is preferable to heat-extract alkylamine, and since the extraction efficiency is high as the temperature range, it is preferable that it is near the boiling point of the alcohol to be used.

In order to spray the said silica particle in high temperature, you may use the commercial spray dryer which can spray the said silica particle in the atmosphere of about 270-800 degreeC, for example. Here, when spraying the said silica particle at high temperature, you may wash | clean the silica particle with the said alcohol, or the acid.

Also in the method of baking the said silica particle, you may wash | clean the silica particle with the said alcohol, or the acid.

As needed, the range of 60-150 degreeC is preferable and, as for the drying temperature which dries silica microparticles after the said washing | cleaning, the range of 80-130 degreeC is more preferable.

Dry silica particles are calcined to remove all organic matter remaining on the silica particles. This removes the alkylamine used as the template. As conditions of a baking process, the range of 400-1,000 degreeC is preferable, and the range of 500-800 degreeC is more preferable. Moreover, as baking time, it is preferable that it is 30 minutes or more, and it is more preferable that it is 1 hour or more. By performing this baking process, since all the organic substance which remain | survives in a silica particle can be removed, it can be set as porous silica which has a pore in a silica particle surface.

It is preferable to grind | pulverize when particle | grains aggregate after baking. As mills used for grinding, ball mills, colloid mills, conical mills, disc mills, edge mills, milling mills, hammer mills, mortars, pellet mills, jet mills, longitudinal impactor (VSI) mills, willy mills, roller mills, etc. Can be mentioned.

Moreover, since self-aggregation of a silica particle can be prevented and dispersibility to an organic solvent or resin improves, the hydroxyl group of the silanol group which exists in the surface of the porous silica particle obtained after the said baking process by a surface treating agent. It is preferable to surface-treat and to substitute a hydrophobic group. As a method of performing this surface treatment, the porous silica is immersed in the solution which melt | dissolved the surface treating agent in the solvent, for example, and the method of heating as needed is mentioned. As a solvent used for this surface treatment, methanol, ethanol, isopropyl alcohol, benzene, toluene, xylene, N, N- dimethylformamide, hexamethyldisiloxane, etc. are mentioned, for example. In addition, as a surface treating agent used for surface modification, a silane compound and a silazane compound, for example, methyl trimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, and dimethyldiethoxysilane , Phenyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, trifluoropropyltrimethoxysilane, hexamethyldisiloxane, trimethylmethoxysilane, ethyltrimethoxysilane, Trimethylethoxysilane, dimethyl diethoxysilane, hexamethyldisilazane, "Dow Corning 2634 Coating" (manufactured by Dore Dow Corning Co., Ltd.) which is a perfluoropolyether having a methoxysilane terminal, and an ethoxysilane terminal "Fluorolink S10" (made by Solvay Solecsys) etc. which are perfluoro polyethers are mentioned. In particular, by surface treatment with the silazane compound, porous silica particles surface-modified with the silazane compound can be obtained. Specifically, the porous silica particles surface-modified with the silazane compound can be obtained by adding the step of surface modifying the porous silica particles obtained after the step 2 (step of removing the alkylamine from the silica particles). As a silazane compound used here, hexamethyldisilazane is preferable.

When surface modification of the surface of a porous silica particle with a silazane compound, it is preferable to use a catalyst. As this catalyst, Inorganic acids, such as hydrochloric acid, a sulfuric acid, 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; Organic bases such as triethylamine and pyridine; Metal alkoxides, such as triisopropoxy aluminum and tetrabutoxy zirconium, etc. are mentioned. Among these, since the production stability and storage stability of the dispersion liquid of porous silica particle (A) become favorable, an acid catalyst (inorganic acids, organic acids) is used. As the inorganic acid, methanesulfonic acid, oxalic acid, phthalic acid, malonic acid and acetic acid are preferable as the organic acid, and particularly preferred is acetic acid.

As a method of modifying the surface of a porous silica particle, the method of immersing porous silica in the solution which melt | dissolved the surface modifier in the solvent, for example, and heating as needed is mentioned. As a solvent used for this surface modification, methanol, ethanol, isopropyl alcohol, benzene, toluene, xylene, N, N- dimethylformamide, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. are mentioned, for example. .

The amount of the surface modifying agent used during surface modification of the porous silica particles is based on 100 parts by mass of the porous silica particles (A) in order to ensure that the porous silica particles (A) do not secondary aggregate and are stable as primary particles. Although the range of 0.3-60 mass parts is preferable, the surface modifying agent has a more preferable range which is 0.5-50 mass parts.

In addition, it is preferable to grind | pulverize the aggregated particle | grains of porous silica particle (A) at the same time as said surface modification, and to make it the dispersion liquid of a primary particle state.

Porous silica particles can be obtained by passing through the steps 1 and 2 described above. The particle shape, average particle diameter, average pore diameter, and specific surface area of the obtained porous silica particles can be measured by the following measuring method.

[Particle shape]

Particle shape can be confirmed by observing using a field emission scanning electron microscope (FE-SEM) (for example, "JSM6700" by the Nippon Denshi Corporation).

[Average particle size]

An average particle diameter can be confirmed by observing using a field emission scanning electron microscope (FE-SEM) (for example, "JSM6700" by Nippon Denshi Corporation).

[Average pore diameter]

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

[Specific surface area]

A specific surface area can be measured by a BET method using a pore distribution measuring apparatus (for example, Shimadzu Corporation "ASAP2020").

By the said measuring method, the particle shape, average particle diameter, average pore diameter, and specific surface area of the obtained porous silica particle (A) can be measured. The porous silica particles used in the present invention are porous silica particles having a substantially spherical appearance, and the average particle diameter can be controlled by adjusting the amount of ammonia used as described above, and preferably in the range of 50 to 300 nm. The range of 100-250 nm is more preferable. Moreover, the range of 80-150 nm is preferable, and, as for the volume average diameter of a porous silica particle (A), the range of 90-120 nm is more preferable. In addition, the average pore diameter and specific surface area of a porous silica particle (A) can be controlled by the kind and usage-amount of an alkylamine, The thing of the range of 1-4 nm is obtained about an average pore diameter, About the thing of the range of 40-900 m <2> / g is obtained.

Moreover, since the cured coating film which coats and forms the active-energy-ray-curable composition containing the said porous silica particle (A) to the film mentioned later is more preferable, the particle size distribution of porous silica particle (A) is narrower. desirable. Therefore, the variation coefficient CV, which is an index indicating the particle size distribution of the porous silica particles (A), is preferably in the range of 0 to 40%, more preferably in the range of 0 to 35%. In view of the ease of production of the porous silica particles (A), the lower limit of the coefficient of variation is preferably 5%, more preferably 10%, still more preferably 15%, and particularly preferably 20%. In addition, a variation coefficient is computed by following formula (1), and the standard deviation in following formula (1) is computed by following formula (2). In addition, d84% in following formula (2) shows 84% diameter in volume particle size distribution, and d16% shows 16% diameter in volume particle size distribution.

[1]

As described above, the porous silica particles (A) having the volume average diameter and the coefficient of variation are subjected to surface modification of the silica particles obtained after the step 2 (step of removing the alkylamine from the silica particles) with a surface modifier. It can be obtained by including the step in the production method of the present invention. The particle shape and specific surface area of the obtained porous silica particle (E) can be measured by the above-mentioned method, and the peak of a volume average diameter, a coefficient of variation, and a pore diameter distribution can be measured by the following measuring method.

[Volume averaging and coefficient of variation]

The volume average diameter can be measured using a particle size distribution meter (for example, "Zeta potential and particle size measuring system ELSZ-2" manufactured by Otsuka Denshi Co., Ltd.) using the laser Doppler method. In addition, a variation coefficient is calculated | required by said formula (1) from the volume average diameter and standard deviation measured with the said apparatus.

[Peak of pore size distribution]

The peak of pore diameter distribution can be measured using a pore distribution measuring apparatus (for example, Shimadzu Corporation "ASAP2020"), and is a peak value of the pore diameter distribution obtained.

Next, the polyfunctional (meth) acrylate (B) which has a hydroxyl group used for the active energy ray curable composition of this invention is demonstrated. The polyfunctional (meth) acrylate (B) is a compound having a hydroxyl group and two or more (meth) acryloyl groups. As such a polyfunctional (meth) acrylate (B), for example, trimethylolpropanedi (meth) acrylate, ethylene oxide modified trimethylolpropanedi (meth) acrylate, and propylene oxide modified trimethylolpropanedi (meth) acryl Mono or di (meth) acrylates of trihydric alcohols such as acrylate, glycerin di (meth) acrylate, bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate, or these Mono and di (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaeryte having a hydroxyl group in which a part of the hydroxyl group of the compound is modified with ε-caprolactone The compound which has one hydroxyl group, such as a rititol penta (meth) acrylate, and three or more (meth) acryloyl groups, or a hydroxyl group which these compounds have is epsilon -caprolactone The polyfunctional (meth) acrylate which has a hydroxyl group modified | denatured by these is mentioned. Among these polyfunctional (meth) acrylates (B), since the anti blocking property of a film can be improved more and the physical property of a cured coating film is also favorable, pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) ) Acrylates are preferred. In addition, these polyfunctional (meth) acrylates (B) may be used independently or may be used together 2 or more types.

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

Moreover, in the active energy ray curable composition of this invention, in addition to the said polyfunctional (meth) acrylate (B), the polyfunctional (meth) acrylate (C) which does not have a hydroxyl group, an active energy ray curable monomer (D), active You may mix | blend an energy-beam curable resin (E) etc.

As a polyfunctional (meth) acrylate (C) which does not have the said hydroxyl group, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, water Polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, and average number of average molecular weights in the range of 150-1000 Polypropylene glycol di (meth) acrylate in the range of 150-1000 molecular weight, neopentyl glycol di (meth) acrylate, 1,3-butanedioldi (meth) acrylate, 1,4-butanedioldi (meth) Acrylate, 1, 6- hexanediol di (meth) acrylate, hydroxy pivalic acid ester neopentyl glycol di (meth) acrylate, bisphenol A di (meth) acrylate, trimethylol propane tree (meta ) Acrylate, ditrimethylol propane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dicyclopentenyldi (meth) acrylate, and the like. . Among these, since the hardness of a cured coating film is especially excellent, the trifunctional or more than trifunctional polyfunctional (methaacrylate, such as a trimethylol propane tri (meth) acrylate, a pentaerythritol tetra (meth) acrylate, and a dipentaerythritol hexa (meth) acrylate) ) Acrylates are preferred. The polyfunctional (meth) acrylate (C) which does not have these hydroxyl groups may be used independently, or may be used together 2 or more types.

Mass ratio [(B) / (C)] of the polyfunctional (meth) acrylate (B) which has the said hydroxyl group, and the polyfunctional (meth) acrylate (C) which does not have the said hydroxyl group is the said porous silica particle (A) Can be localized on the surface of the coating film of the active energy ray-curable composition of the present invention, and anti-blocking property can be improved, and therefore, the range of 10/90 to 90/10 is preferable, and 20/80 The range of -80/20 is more preferable, and the range of 30/70-70/30 is further more preferable.

As said active energy ray curable monomer (D), for example, methyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, octyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate Aliphatic alkyl (meth) acrylate, glycerol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycidyl (meth) acryl, etc. Late, allyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2- (diethylamino) ethyl (meth) acrylate, 2- (dimethylamino) ethyl (meth) acrylate, γ- ( Meta) acryloxypropyltrimethoxysilane, 2-methoxyethyl (meth ) Acrylate, methoxydiethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, phenoxyethyl (Meth) acrylate, phenoxydipropylene glycol (meth) acrylate, phenoxy polypropylene glycol (meth) acrylate, polybutadiene (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, polyethylene glycol- Polybutylene glycol (meth) acrylate, polystyrylethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) Acrylate, isobornyl (meth) acrylate, methoxylated cyclodecatriene (meth) acrylate, phenyl (meth) a Relate; Maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-octylmaleimide, N-dodecylmaleimide, N-stearyl Maleimide, N-phenylmaleimide, N-cyclohexylmaleimide, 2-maleimideethyl-ethylcarbonate, 2-maleimide ethyl-propylcarbonate, N-ethyl- (2-maleimideethyl) carbamate, N, Maleimide, such as N-hexamethylene bis maleimide, polypropylene glycol bis (3-maleimide propyl) ether, bis (2-maleimide ethyl) carbonate, and 1, 4- dimaleimide cyclohexane, etc. are mentioned. have. These active energy ray curable monomers (D) may be used independently or may be used together 2 or more types.

As said active energy ray curable resin (E), for example, urethane (meth) acrylate resin, unsaturated polyester resin, epoxy (meth) acrylate resin, polyester (meth) acrylate resin, and acrylic (meth) acrylate Resin, resin which has a maleimide group, etc. are mentioned.

The urethane (meth) acrylate resin used here includes resins having a urethane bond and a (meth) acryloyl group obtained by reacting an aliphatic polyisocyanate compound or an aromatic polyisocyanate compound with a (meth) acrylate compound having a hydroxyl group. Can be.

As said aliphatic polyisocyanate compound, for example, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, 2-methyl-1,5-pentanedi Isocyanate, 3-methyl-1,5-pentane diisocyanate, dodecamethylene diisocyanate, 2-methylpentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene di Isocyanate, isophorone diisocyanate, norbornane diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tetramethyl xylylene diisocyanate, cyclohexyl diisocyanate, etc. are mentioned. have. Moreover, as an aromatic polyisocyanate compound, tolylene diisocyanate, 4,4'- diphenylmethane diisocyanate, xylylene diisocyanate, 1, 5- naphthalene diisocyanate, tridine diisocyanate, p-phenylene diisocyanate, etc. are mentioned. .

On the other hand, as an acrylate compound which has a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxy, for example. Butyl (meth) acrylate, 1,5-pentanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, hydroxy pivalate neopentyl glycol Mono (meth) acrylates of dihydric alcohols such as mono (meth) acrylate; Trimethylolpropanedi (meth) acrylate, ethylene oxide modified trimethylolpropanedi (meth) acrylate, propylene oxide modified trimethylolpropanedi (meth) acrylate, glycerin di (meth) acrylate, bis (2- (meth) Mono or di (meth) acrylates of trihydric alcohols such as acryloyloxyethyl) hydroxyethyl isocyanurate, or mono and di having a hydroxyl group in which some of the hydroxyl groups of these compounds are modified with ε-caprolactone (Meth) acrylates; Compound which has one hydroxyl group and 3 or more (meth) acryloyl groups, such as pentaerythritol tri (meth) acrylate, ditrimethylol propane tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate, or Polyfunctional (meth) acrylate which has a hydroxyl group which modified | denatured some hydroxyl groups which these compounds have by (epsilon) -caprolactone; (Meth) acrylates having oxyalkylene chains such as dipropylene glycol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate compound; (Meth) acrylate compounds having an oxyalkylene chain having a block structure such as polyethylene glycol-polypropylene glycol mono (meth) acrylate and polyoxybutylene-polyoxypropylene mono (meth) acrylate; (Meth) acrylate compounds having an oxyalkylene chain having a random structure such as poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate and poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate Can be.

Reaction of said aliphatic polyisocyanate compound or aromatic polyisocyanate compound, and the (meth) acrylate compound which has a hydroxyl group can be performed by a conventional method in presence of a urethanization catalyst. Specific examples of the urethanization catalyst that can be used herein include amines such as pyridine, pyrrole, triethylamine, diethylamine and dibutylamine, phosphines such as triphenylphosphine and triethylphosphine, and dibutyltin. Organotin compounds such as dilaurate, octyl tin trilaurate, octyl tin diacetate, dibutyl tin diacetate, tin octylate, and organometallic compounds such as zinc octylate.

Among these urethane (meth) acrylate resins, those obtained by reacting an aliphatic polyisocyanate compound with a (meth) acrylate compound having a hydroxyl group are particularly excellent in transparency of the cured coating film, and have good sensitivity to active energy rays and excellent curability. Therefore, it is preferable. Moreover, as a (meth) acrylate compound which has the said hydroxyl group, since the polyfunctional (meth) acrylate compound which has two or more (meth) acryloyl groups is excellent in the hardness of a cured coating film, it is preferable.

The said unsaturated polyester resin is curable resin obtained by polycondensation of (alpha), (beta)-unsaturated dibasic acid or its acid anhydride, aromatic saturated dibasic acid or its acid anhydride, and glycols, and (alpha), (beta)-unsaturated dibasic acid or its Examples of the acid anhydride include maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chloromaleic acid, and esters thereof. Examples of the aromatic saturated dibasic acid or its acid anhydride include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, tetrahydro phthalic anhydride, endo methylenetetrahydro phthalic anhydride, halogenated phthalic anhydride and esters thereof. Examples of the aliphatic or alicyclic saturated dibasic acids include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid, hexahydro phthalic anhydride, and esters thereof. Examples of the glycols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 2-methylpropane-1,3-diol, neopentyl glycol, triethylene glycol, tetra Ethylene glycol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, ethylene glycol carbonate, 2,2-di- (4-hydroxypropoxydiphenyl) propane, and the like. In addition, oxides, such as ethylene oxide and a propylene oxide, can also be used similarly.

As said epoxy (meth) acrylate resin, (meth) acrylic acid is mentioned to the epoxy group of epoxy resins, such as a bisphenol-A epoxy resin, a bisphenol F-type epoxy resin, a phenol novolak-type epoxy resin, and a cresol novolak-type epoxy resin, for example. The thing obtained by making it react is mentioned.

As said polyester (meth) acrylate resin, what is obtained by making (meth) acrylic acid react with the hydroxyl group of a polyester polyol, for example is mentioned.

As said acryl (meth) acrylate resin, for example, glycidyl methacrylate and other (meth) acrylate monomers are polymerized as needed and the acrylic resin which has an epoxy group is obtained, and the epoxy group (meth ) What is obtained by making acrylic acid react is mentioned.

As resin which has the said maleimide group, the bifunctional maleimide urethane compound obtained by urethanizing N-hydroxyethyl maleimide and isophorone diisocyanate, the bifunctional maleimide ester obtained by esterifying maleimide acetic acid and polytetramethylene glycol The polyfunctional maleimide ester compound obtained by esterifying the compound, the tetraethylene oxide adduct of maleimide caproic acid and pentaerythritol, the polyfunctional maleimide ester compound obtained by esterifying a maleimide acetic acid and a polyhydric alcohol compound, etc. are mentioned. . These active energy ray curable resins (E) may be used independently or may be used together 2 or more types.

In the active energy ray-curable composition of the present invention, since the antiblocking property of the film of the present invention to be described later can be improved in the amount of the porous silica particles (A), the components (B) to (E) described above. The range of 1-50 mass parts is preferable with respect to 100 mass parts of total amounts, The range of 1-20 mass parts is more preferable, The range of 1-10 mass parts is more preferable.

The film of this invention makes a base material a film, and has a cured coating film formed by coating the active energy ray curable composition of this invention on at least one surface. Here, the manufacturing method of the film of this invention is demonstrated. First, after coating the active energy ray curable composition of this invention to a base film, in order to harden the said active energy ray curable composition and to form a cured coating film, an active energy ray is irradiated. As this active energy ray, ionizing radiation, such as an ultraviolet-ray, an electron beam, (alpha) rays, (beta) rays, (gamma) rays, is mentioned. When irradiating an ultraviolet-ray as an active energy ray and making it a cured coating film, it is preferable to add a photoinitiator (F) to the said active energy ray curable composition, and to improve curability. Moreover, if necessary, a photosensitizer (G) can be further added and curability can be improved. On the other hand, when ionizing radiation such as an electron beam, α-ray, β-ray, γ-ray, etc. is used, it hardens quickly without using a photopolymerization initiator or a photosensitizer, and therefore, it is not particularly necessary to add a photopolymerization initiator or a photosensitizer.

As said photoinitiator (F), an intramolecular cleavage type | mold photoinitiator and a hydrogen extraction type | mold photoinitiator are mentioned. Examples of the intramolecular cleavage type photopolymerization initiators include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, and 1- (4-isopropylphenyl) -2-. Hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-2 -Morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- [2-oxo-2-phenylacet Acetophenone type compounds, such as a methoxyethoxy] ethyl ester and 2- (2-hydroxyethoxy) ethyl ester; Benzoin such as benzoin, benzoin methyl ether, benzoin isopropyl ether; Acylphosphine oxide compounds such as 2,4,6-trimethylbenzoindiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; Benzyl, methylphenylglyoxyester and the like.

On the other hand, as a hydrogen drawing type | mold photoinitiator, benzophenone, the methyl 4-phenylbenzophenone o-benzoyl benzoate, 4,4'- dichloro benzophenone, hydroxy benzophenone, 4-benzoyl-4'-methyl- Benzophenone type compounds, such as diphenyl sulfide, an acrylate benzophenone, a 3,3 ', 4,4'- tetra (t-butylperoxycarbonyl) benzophenone, and a 3,3'- dimethyl- 4-methoxy benzophenone ; Thioxanthone compounds such as 2-isopropyl thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone and 2,4-dichloro thioxanthone; Aminobenzophenone compounds such as Michler's ketone and 4,4'-diethylaminobenzophenone; 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, etc. are mentioned.

As the photosensitizer (G), for example, amines such as aliphatic amines and aromatic amines, urea such as o-tolylthiourea, sodium diethyldithiophosphate, and s-benzylisothiuronium-p- Sulfur compounds such as toluenesulfonate, and the like.

As for the usage-amount of these photoinitiators (F) and a photosensitizer (G), 0.01-20 mass parts is respectively preferable with respect to 100 mass parts of non volatile components in an active energy ray curable composition, 0.1-15 mass% is more preferable 0.3-7 mass parts is more preferable.

In addition, the active energy ray-curable composition of the present invention, depending on the purpose of use, characteristics, and the like, adjusts the viscosity and refractive index, or adjusts the color tone of the coating film and other paint properties within a range that does not impair the effects of the present invention. And various compounding materials, for example, various organic solvents, acrylic resins, phenol resins, polyester resins, polystyrene resins, urethane resins, urea resins, melamine resins, alkyd resins, epoxy resins, and polyamide resins for the purpose of adjusting the coating film properties. , Various kinds of resins such as polycarbonate resin, petroleum resin, fluororesin, PTFE (polytetrafluoroethylene), polyethylene, polypropylene, carbon, titanium oxide, alumina, copper, silica fine particles and other organic or inorganic particles, polymerization initiator , Polymerization inhibitor, antistatic agent, antifoaming agent, viscosity modifier, light stabilizer, weather stabilizer, heat stabilizer, antioxidant, antirust , May also be added slip agents, wax, gloss-adjusting agent, mold release agent, a compatibilizer (相 溶化 劑), conductivity adjusting agent, pigment, dye, dispersant, dispersion stabilizer, silicone-based, and hydrocarbon based surfactants.

In each said compounding component, an organic solvent is useful at the time of adjusting the solution viscosity of the active-energy-ray-curable composition of this invention suitably, and especially in order to perform thin film coating, it becomes easy to adjust a film thickness. As an organic solvent which can be used here, For example, aromatic hydrocarbons, such as toluene and xylene; Alcohol compounds such as methanol, ethanol, isopropanol and t-butanol; Ester compounds such as ethyl acetate and propylene glycol monomethyl ether acetate; Ketone compounds, such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, etc. are mentioned. These solvents may be used alone or in combination of two or more thereof.

Although the usage-amount of an organic solvent changes with the film thickness and viscosity made into the use and the objective here, it is preferable that it is the range of 0.5 to 10 times by mass with respect to the total mass of a hardening component.

Although the active energy ray-curable composition of this invention is obtained by mixing each said component, it is filtration as needed in order to prevent the coating film defect by the foreign material mixing which arises at the time of coating film preparation of the said obtained composition. desirable. At this time, several micrometers or less are preferable, as for the diameter of the filter used for filtration, 5 micrometers or less are more preferable, and 1 micrometer or less is more preferable.

As an active energy ray which hardens the active energy ray curable composition of this invention, as above-mentioned, ionizing radiations, such as an ultraviolet-ray, an electron beam, (alpha) ray, (beta) ray, (gamma) ray, are mentioned as a specific energy source or a hardening apparatus, for example Sterilization lamps, UV fluorescent lamps, carbon arc, xenon lamps, high pressure mercury lamps for radiation, medium or high pressure mercury lamps, ultrahigh pressure mercury lamps, electrodeless lamps, metal halide lamps, LEDs, natural light, etc. Ultraviolet rays, an electron beam by a scanning type, curtain type electron beam accelerator, etc. are mentioned. Since the apparatus is simple, it is preferable to use an apparatus that generates ultraviolet rays.

The base film used by the film of this invention may be a film form, or a sheet form may be sufficient, and the thickness has the preferable range of 20-500 micrometers. Moreover, as a material of the said base film, resin with high transparency is preferable, For example, Polyester-based resin, such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate; Polyolefin resins such as polypropylene, polyethylene, and polymethylpentene-1; Cellulose resins such as cellulose acetate (diacetyl cellulose, triacetyl cellulose and the like), cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate propionate butyrate, cellulose acetate phthalate and cellulose nitrate; Acrylic resins such as polymethyl methacrylate; Vinyl chloride resins such as polyvinyl chloride and polyvinylidene chloride; Polyvinyl alcohol; Ethylene-vinyl acetate copolymers; polystyrene; Polyamide; Polycarbonate; Polysulfone; Polyethersulfone; Polyether ether ketone; Polyimide resins such as polyimide and polyetherimide; Norbornene-based resin (e.g., `` Zenooa '' manufactured by Nihon Xeon Co., Ltd.), modified norbornene-based resin (e.g. (`` Aton '', manufactured by JSR Corporation), cyclic olefin copolymer (e.g. And "Apel" manufactured by Mitsui Chemical Co., Ltd.), etc. Moreover, you may use what bonded two or more types of base materials which consist of these resins.

As a coating method to the base material of the active energy ray curable composition of this invention, for example, a gravure coater, a roll coater, a comma coater, a knife coater, an air knife coater, a curtain coater, a kiss coater, a shower coater, a wheel coater, a spin coater, Coating methods using dipping, screen printing, spraying, an applicator, a bar coater, etc. are mentioned.

When the active energy ray curable composition of the present invention contains an organic solvent, after coating the active energy ray curable composition to the base film, the organic solvent is volatilized and irradiated with the porous material before irradiating the active energy ray. In order to segregate silica (A) on the coating film surface, it is preferable to heat or dry at room temperature. Although it will not specifically limit, if it is a condition which volatilizes an organic solvent as conditions of heat drying, Usually, it is preferable to heat-dry in time in 1 to 10 minutes in the range of temperature of 50-100 degreeC.

By operating as mentioned above, the film of this invention is obtained.

[Example]

An Example and a comparative example are given to the following, and this invention is demonstrated in more detail. In addition, the characteristic value of the synthesized porous silica particle was measured by the following method.

[Particle shape]

The particle shape was confirmed by observing at 50,000 times using the field emission scanning electron microscope (FE-SEM) ("JSM6700" by Nippon Denshi Corporation).

[Volume averaging and coefficient of variation]

The volume average diameter was measured using a particle size distribution meter ("Zeta potential and particle size measuring system ELSZ-2" by Otsuka Denshi Co., Ltd.) using the laser Doppler method. In addition, the variation coefficient was calculated | required by following formula (1) from the volume average diameter and standard deviation measured with the said apparatus. In addition, the standard deviation in following formula (1) was calculated | required by following formula (2). In addition, d84% in following formula (2) shows 84% diameter in volume particle size distribution, and d16% shows 16% diameter in volume particle size distribution.

[Number 2]

[Peak of pore size distribution]

The peak of pore diameter distribution was made into the peak value of the pore distribution obtained by measuring using the pore distribution measuring apparatus (Shimadzu Corporation "ASAP2020").

[Specific surface area]

The specific surface area was measured by the BET method using a pore distribution measuring device (ASAP2020, Shimadzu Corporation).

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

Into 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 mass% ammonia water were added and mixed uniformly by stirring (Liquid II). Maintained. Further, 34.3 g of tetramethoxysilane, 45.1 g of methanol, and 9.3 g of laurylamine were uniformly mixed in another container (I liquid). I liquid was injected into II liquid over 120 minutes, maintaining the inside of flask at 20 degreeC. The reaction was continued for 60 minutes at 20 degreeC after completion | finish of injection of I liquid. After completion of the reaction, the reaction solution was centrifuged at 10,000 rpm for 10 minutes, the supernatant was discarded, and the precipitate was taken out.

To the precipitate obtained above was added 200 g of methanol and mixed to obtain a suspension. The suspension was centrifuged at 10,000 rpm for 10 minutes, the symbol was discarded and the precipitate was washed with methanol. This methanol wash was also repeated two more times. The precipitate thus obtained was dried at 120 ° C. for 6 hours to obtain a white powder. The obtained white powder was put into an electric furnace, and it heated up to 600 degreeC at the temperature increase rate of 2 degree / min from 25 degreeC in air atmosphere, and baked at 600 degreeC for 3 hours. The calcined powder was cooled and then ground by mortar to obtain 12 g of white porous silica particles. The obtained porous silica particles were observed with a field emission scanning electron microscope (FE-SEM), whereby the particle shape was spherical. In addition, the peak of the pore diameter distribution of the obtained porous silica particle 1 was 1.8 nm, and the specific surface area by BET method was 216 m <2> / g.

5 g of the porous silica particles obtained above were mixed with 44.5 g of isopropanol and dispersed for 5 minutes at an output 300 W using an ultrasonic homogenizer ("US-600T" manufactured by Nippon Seiki Seisakusho Co., Ltd.). 0.5 g and 0.5 g of hexamethyldisilazane were added and dispersed for 30 minutes at a processing pressure of 130 MPa using a wet jet mill ("Nanojetbar JN-10" manufactured by Tsunemitsu Co., Ltd.). The obtained dispersion was poured into a 200 ml four-necked flask equipped with a thermometer and a stirring blade, and heated to reflux for 60 minutes. After centrifuging the reaction solution at 10,000 rpm for 10 minutes, the supernatant was discarded to obtain a precipitate. 50 g of isopropanol was added to the precipitate and dispersed for 5 minutes at an output 300 W using an ultrasonic homogenizer ("US-600T" manufactured by Nippon Seiki Seisakusho Co., Ltd.). Filtration was carried out using a 5C filter paper and a Kiriyama funnel (manufactured by Yugen Chemical Co., Ltd.), to obtain a dispersion of porous silica particles (1) having a solid content of 7.9% by mass.

The volume average diameter of the porous silica particles 1 in the dispersion of the obtained porous silica particles 1 was 139 nm, and the variation coefficient was 22%.

(Example 1)

227.8 parts by mass of the dispersion of the porous silica particles (1) obtained in Synthesis Example 1 (containing 18 parts by mass of the porous silica particles (1)), and a mixture of polyfunctional acrylates (dipentaerythritol pentaacrylate (hereinafter referred to as "DPPA") 3 mass parts of 55 mass% and dipentaerythritol hexaacrylate (it abbreviates as "DPHA" hereafter) 45 mass%; hereafter abbreviated as "polyfunctional acrylate (1)) 364 mass parts, photopolymerization 18 parts by mass of an initiator ("irgacure 184", 1-hydroxycyclohexylphenyl ketone manufactured by BASF Japan; abbreviated as "Irg.184" below) and 390.2 parts by mass of isopropanol are uniformly mixed, and an active energy The precurable composition (1) was obtained.

(Example 2)

A mixture of polyfunctional acrylates (a mixture of 35 mass% of DPPA and 65 mass% of DPHA; hereafter abbreviated as "multifunctional acrylate (2)") instead of the polyfunctional acrylate (1) used in Example 1 Except using a mass part, it carried out similarly to Example 1 and obtained the active energy ray curable composition (2).

(Example 3)

Instead of the polyfunctional acrylate (1) used in Example 1, a mixture of polyfunctional acrylate (pentaerythritol triacrylate (hereinafter abbreviated as "PE3A") 70% by mass) and pentaerythritol tetraacrylate (hereinafter referred to as , Abbreviated as "PE4A") 30 mass%; hereafter abbreviated as "polyfunctional acrylate (3)", it carried out similarly to Example 1 except using 364 mass parts, and an active energy ray curable composition (3) Got.

(Example 4)

Instead of the polyfunctional acrylate (1) used in Example 1, a mixture of polyfunctional acrylate (60% by mass of PE3A and 40% by mass of PE4A; hereafter abbreviated as "polyfunctional acrylate (4)") 364 Except using a mass part, it carried out similarly to Example 1 and obtained the active energy ray curable composition (4).

(Example 5)

A mixture of polyfunctional acrylates (mixture of 30 mass% PE3A and 70 mass% PE4A; hereafter abbreviated as "multifunctional acrylate (5)") instead of the polyfunctional acrylate (1) used in Example 1 Except using a mass part, it carried out similarly to Example 1 and obtained the active energy ray curable composition (5).

(Comparative Example 1)

Instead of the porous silica particles 1 used in Example 1, 18 parts by mass of solid silica ("Shistar KE-P10" manufactured by Nihon Shokubai Co., Ltd., particle diameter 100 to 200 nm, surface untreated) were used. And except having changed the compounding quantity of isopropanol into 600 mass parts from 390.2 mass parts, it carried out similarly to Example 1, and obtained active energy ray curable composition (R1).

(Comparative Example 2)

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

(Comparative Example 3)

Ethylene oxide modified trimethylolpropane triacrylate (triacrylate obtained by adding 3 mol of ethylene oxide to trimethylolpropane; instead of polyfunctional acrylate (1) used in Example 1; hereinafter abbreviated as "EO-TMPTA") ) Except having used 364 mass parts), it carried out similarly to Example 1 and obtained active energy ray curable composition (R3).

(Comparative Example 4)

Instead of the polyfunctional acrylate (1) used in Example 1, it carried out similarly to Example 1 except having used 364 mass parts of ditrimethylol propane tetraacrylates (it abbreviates as "DTMPTA" hereafter), and an active energy ray curable composition (R4) was obtained.

Table 1 shows the compositions of the active energy ray curable compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 4 described above.

[Table 1]

(Example 6)

[Production of Evaluation Film]

The active energy ray-curable composition (1) obtained in Example 1 was coated on a polyethylene terephthalate (PET) film substrate having a thickness of 100 μm using a wire bar coater # 24, and dried at 25 ° C. for 10 seconds. It dried for 1 minute in 80 degreeC dryer. Then, it hardened | cured using the ultraviolet curing device (in nitrogen atmosphere, a fusion lamp (H valve, ultraviolet irradiation amount 300J / m <2>), and the film for evaluation was produced).

[Evaluation of Anti-Blocking]

The cured coating film surfaces of the film for evaluation obtained above or the cured coating film surface of the film for evaluation and a base material surface (the opposite surface of a cured coating film) were contacted, and anti blocking property was evaluated according to the following 5 steps of criteria.

5: Do not take

4: If you rub strongly, it takes a little bit.

3: If you rub lightly, it takes a little bit.

2: It takes

1: stick.

[Measurement of Haze Values and Evaluation of Transparency]

About the film for evaluation obtained above, it measured with the haze meter ("NDH2000" by Nippon Denshoku Kogyo Co., Ltd.), and evaluated the transparency according to the following five steps of criteria from the obtained haze value.

5: Haze value is less than 0.5.

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

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

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

1: Haze value is 10.0 or more.

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

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, and the film for evaluation After preparation, evaluation of anti blocking property and transparency was performed.

Table 2 shows the evaluation results of the above-described anti blocking properties and transparency.

[Table 2]

From the above result, it turned out that the film which has a cured coating film of the active energy ray curable compositions (1)-(5) of this invention of Examples 1-5 has high anti blocking property and has high transparency.

On the other hand, Comparative Example 1 is an example in which solid silica particles having a small particle diameter and not having pores on the surface of the silica particles are used. The transparency is high, but the coating film surface is caught, and the anti blocking property is insufficient.

Comparative Example 2 is an example in which solid silica particles having a large particle diameter and no pores on the surface of silica particles were used. The antiblocking property was good, but the haze value was 7.5% and the transparency was insufficient.

The comparative examples 3 and 4 used the polyfunctional acrylate which does not have a hydroxyl group, without using the polyfunctional acrylate which has a hydroxyl group. Although transparency was high, the coating film surface was caught and anti blocking property was inadequate.

Claims (6)

After adding the mixed liquid (liquid I) containing tetraalkoxysilane, alkylamine, and alcohol to the mixed liquid (liquid II) containing ammonia, alcohol, and water, and obtaining a silica particle by the hydrolysis and condensation reaction of tetraalkoxysilane, The active energy characterized by containing the porous silica particle (A) which has a pore on the surface obtained by removing an alkylamine from the said silica particle, and the polyfunctional (meth) acrylate (B) which has a hydroxyl group. Precurable compositions. The method of claim 1,
The active energy ray curable composition in which the said porous silica particle (A) was surface-modified by hexamethyldisilazane. 3. The method according to claim 1 or 2,
The active energy ray curable composition in which the said polyfunctional (meth) acrylate (B) is pentaerythritol tri (meth) acrylate and / or dipentaerythritol penta (meth) acrylate. 4. The method according to any one of claims 1 to 3,
Moreover, as a polyfunctional (meth) acrylate (C) which does not have a hydroxyl group, the mass ratio of the polyfunctional (meth) acrylate (B) which has the said hydroxyl group, and the polyfunctional (meth) acrylate (C) which does not have a hydroxyl group [( B) / (C)] is in the range of 10/90 to 90/10. Hardened | cured material obtained by hardening | curing the active-energy-ray-curable composition in any one of Claims 1-4. At least one surface of a base film has a cured coating film of the active energy ray curable composition of any one of Claims 1-4, The film characterized by the above-mentioned.