KR20100085854A - Photocurable resin composition and article having cured coating thereof - Google Patents

Abstract

PURPOSE: A photo-crosslinking resin is provided to ensure high transparency and anti-static property. CONSTITUTION: A photo-crosslinking resin composition is: a compound containing three or more (meth)acryl group; a compound containing one or two (meth)acryl group; inorganic oxide microparticle; and an ionic compound of R^1R^2R^3R^4N^+X^-.

Description

The article which has a photocurable resin composition and its cured film TECHNICAL FIELD

BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to an article having a photocurable resin composition used for coatings, coatings, and the like and a cured coating thereof, and more particularly, a curing stability having good storage stability, high transparency, high hardness, scratch resistance, and antistatic properties. It relates to an article having a photocurable resin composition that provides a coating and a cured coating thereof.

Synthetic resins, such as polymethyl methacrylate resin, polycarbonate resin, polystyrene resin, cyclic polyolefin resin, polyethylene terephthalate resin, and triacetyl cellulose resin, have advantages such as light weight, transparency, and ease of processing. Therefore, such synthetic resins have recently been used in various fields such as optical disks such as CDs and DVDs, display windows such as liquid crystals and EL panels, and various functional films.

In order to improve the scratch resistance of these surfaces, it is generally carried out to form a transparent and scratch resistant hard coating on the recording and / or reproduction beam incident side surface of the medium. The hard coating is formed in a cage in which a compound having two or more photoreactive groups such as (meth) acryloyl groups and alkoxysilanes having photoreactive groups such as (meth) acryloyl groups are hydrolyzed and condensed in the presence of a basic catalyst. A composition containing a siloxane compound having a structure (Japanese Patent Laid-Open No. 2002-363414, Japanese Patent Laid-Open No. 2004-143449: Patent Documents 1 and 2), a reactant of an alkoxysilane having a photoreactive group and colloidal silica, and the like. Is applied to the surface of the medium and cured by irradiation of active energy rays such as ultraviolet rays.

Moreover, addition of various antistatic agents is examined for the purpose of the improvement of antistatic property. Reactant of polyether modified silicone and lithium perchlorate (Japanese Patent Laid-Open No. 5-320626: Patent Document 3), Reactant of polyfunctional acrylic and lithium perchlorate (Patent No. 3673590: Patent Document 4), polyfunctional Although a mixture of acrylate and (CF ₃ SO ₂ ) ₂ NLi (Japanese Patent Laid-Open No. 9-278831, Japanese Patent Laid-Open No. 2001-288325: Patent Documents 5 and 6) has been proposed, scratch resistance Insufficient

Therefore, for the purpose of improving scratch resistance, a mixture of silica and silane hydrolyzate with (CF ₃ SO ₂ ) ₂ NLi (Japanese Patent Laid-Open No. 2005-146110, Japanese Patent Laid-Open No. 2006-70120, Japanese Laid-Open Patent Publication) Publication No. 2008-222951: Patent Documents 7 to 9) have been proposed, but containing a solvent.

Japanese Patent Laid-Open No. 2002-363414 Japanese Patent Laid-Open No. 2004-143449 Japanese Patent Laid-Open No. 5-320626 Japanese Patent No. 3673590 Japanese Patent Laid-Open No. 9-278831 Japanese Patent Laid-Open No. 2001-288325 Japanese Patent Laid-Open No. 2005-146110 Japanese Patent Laid-Open No. 2006-70120 Japanese Patent Laid-Open No. 2008-222951

This invention is made | formed in view of the said situation, and aims at providing the photocurable resin composition which provides the cured film which is excellent in storage stability, high transparency, and excellent in scratch resistance and antistatic property, and the article which has its cured film. It is done.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the said objective, (1) the inorganic oxide fine particle whose average particle diameter is 80 nm or less, (2) the compound containing 3 or more of (meth) acryl groups, (3) (meth) Although it contains the compound containing one or two acryl groups, (4) the aliphatic amine type ionic compound shown below, and (5) radical type photoinitiator, although it does not contain a solvent substantially, storage stability is The film formed by curing the photocurable resin composition having good viscosity at 500 ° C. or less and excellent coating workability at 25 ° C. has good adhesiveness to the supporting substrate, high transparency, scratch resistance, and antistatic property. Discovering excellent things, the present invention was completed.

Therefore, this invention provides the article which has a photocurable resin composition and its cured film shown below.

[Claim 1]

(1) inorganic oxide fine particles having an average particle diameter of 80 nm or less,

(2) a compound containing three or more (meth) acryl groups,

(3) a compound containing one or two (meth) acryl groups;

^{(4) R 1 R 2 R} 3 R 4 N + X - (R 1, R 2, R 3, R 4 is _{CH 3, C 2 H 5,} C 2 H 4 OCH 3, C 6 H 13, C 8 An ionic compound represented by H ₁₇ , wherein each group may be the same or different, X is a group selected from N (SO ₂ CF ₃ ) ₂ , BF ₄ , PF ₆ ),

(5) radical type photoinitiator

It is made to contain, (1) component is 25-70 mass parts, (2) component is 20-70 mass parts, and (3) component among 100 mass parts of total of (1), (2), and (3) component It is 5-30 mass parts, (4) component is 0.05-3 mass parts and (5) component is 1-8 mass parts with respect to a total of 100 mass parts of (1), (2), (3) component, It does not contain a solvent substantially, and the viscosity in 25 degreeC is 500 mPa * s or less, The photocurable resin composition characterized by the above-mentioned.

[Claim 2]

The photocurable resin composition of Claim 1 whose inorganic oxide fine particles whose average particle diameter of (1) component is 80 nm or less are silica fine particles.

[Claim 3]

The photocurable resin composition according to claim 2, wherein the silica fine particles are treated with a silane coupling agent containing a (meth) acryl group.

[Claim 4]

The component according to any one of claims 1 to 3, wherein component (4) and component (5) are mixed with a mixture in which component (1) is previously dispersed in component (2) and / or component (3). Photocurable resin composition.

[Claim 5]

An article in which a cured film of the photocurable resin composition according to any one of claims 1 to 4 is formed.

The photocurable resin composition of this invention mixes an ionic compound with the inorganic oxide fine particle disperse | distributed in the (meth) acryl-group containing compound, and the effect of both antistatic property and dispersion stability by the synergistic effect of an inorganic oxide fine particle and an ionic compound is shown. Even if it does not mix | blend a solvent substantially, the film | membrane which is excellent in storage stability, high transparency, and abrasion resistance and antistatic property is obtained.

The photocurable resin composition of the present invention

(1) inorganic oxide fine particles having an average particle diameter of 80 nm or less,

(2) a compound containing three or more (meth) acryl groups,

(3) a compound containing one or two (meth) acryl groups;

(4) aliphatic amine-based ionic compounds,

(5) radical type photoinitiator

It contains and does not contain a solvent substantially, and the viscosity in 25 degreeC is 500 mPa * s or less.

(1) inorganic oxide fine particles

Examples of the (1) inorganic oxide fine particles of the present invention include oxide fine particles such as Si, Ti, Al, Zn, Zr, In, Sn, Sb, Ce, Fe, or these composite oxide fine particles. Specific examples of the metal oxide fine particles include fine particles such as silica, alumina, zirconia, titania, and cerium oxide.

The average particle diameter of these inorganic oxide fine particles is 80 nm or less, Preferably it is 50 nm or less. If a size larger than 80 nm is used, stability deteriorates, particulate matter appears in the film, and transparency may be impaired. In addition, the minimum thereof is 10 nm or more normally. In addition, in this invention, an average particle diameter can be measured by the particle size distribution measuring apparatus by a dynamic light scattering photon correlation method.

As especially preferable inorganic oxide fine particles, it is more preferable if it is a silica fine particle and an average particle diameter is 50 nm or less. The silica fine particles may also be hollow or porous, in which effects such as low refractive index are expected. A commercial item can be used as such an inorganic oxide fine particle, For example, ELECOM ST-1003SIV (made by Nikki Shokubai Kasei Co., Ltd.) etc. is mentioned.

Among the silica fine particles, those surface-modified by a hydrolyzable silane compound having an active energy ray reactive group are preferably used. These reactive silica fine particles cause crosslinking reactions and are fixed in the polymer matrix by active energy ray irradiation when curing the composition.

Here, as a hydrolyzable silane compound which has an active energy ray reactive group, the silane coupling agent containing a (meth) acryl group is mentioned, Specifically, (gamma) -methacryloxypropyl trimethoxysilane and (gamma) -methacryloxypropyl trie Oxysilane, γ-methacryloxypropyltrichlorosilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropylmethyldichlorosilane, γ-methacryloxy Propyldimethylmethoxysilane, γ-methacryloxypropyldimethylethoxysilane, γ-methacryloxypropyldimethylchlorosilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-acrylic Oxypropyltrichlorosilane, γ-acryloxypropylmethyldimethoxysilane, γ-acryloxypropylmethyldiethoxysilane, γ-acryloxypropylmethyldichlorosilane, γ- Krilloxypropyldimethylmethoxysilane, γ-acryloxypropyldimethylethoxysilane, γ-acryloxypropyldimethylchlorosilane, γ-acryloxymethyltrimethoxysilane, γ-acryloxymethyltriethoxysilane, γ-acrylic Oxymethyltrichlorosilane, γ-acryloxymethylmethyldimethoxysilane, γ-acryloxymethylmethyldiethoxysilane, γ-acryloxymethylmethyldichlorosilane, γ-acryloxymethyldimethylmethoxysilane, γ-acryloxymethyl Dimethylethoxysilane and (gamma) -acryloxymethyldimethylchlorosilane can be illustrated.

The amount of surface modification of the hydrolyzable silane compound having an active energy ray reactive group is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, particularly preferably 1 to 5% by mass.

As a method of surface modification by the hydrolyzable silane compound which has an active energy ray reactive group, the method of hydrolyzing the hydrolyzable silane compound which has an active energy ray reactive group in presence of silica microparticles | fine-particles is mentioned, but the active energy ray reactive group which by-produces at that time Since the hydrolyzate of the hydrolyzable silane compound which has is a cause of deterioration in storage stability or a decrease in hardness, such hydrolyzate should be removed.

It disperse | distributes in the state of a primary particle in the compound containing three or more (2) (meth) acryl groups which mention these (1) inorganic oxide microparticles, or (3) the compound containing one or two (meth) acryl groups It is preferable to use one, and it exists in primary particles, and the film with favorable external appearance, such as transparency, can be obtained.

Specifically, after the method of physically dispersing the inorganic oxide fine particles in the (meth) acryl group-containing compound using a dispersing agent or a dispersing device, or adding the (meth) acryl group-containing compound to the solution in which the inorganic oxide fine particles are dispersed, the original The method of distilling a dispersing agent off is mentioned.

(2) Compounds containing three or more (meth) acryl groups

Compound which contains three or more (2) (meth) acryl groups of this invention becomes a main component of a curable component with (1) inorganic oxide microparticles and (3) the compound containing one or two (meth) acryl groups This forms the matrix of the film obtained after hardening.

The compound containing three or more (meth) acryl groups disperse | distributes the inorganic oxide fine particle of (1) component, and is a binder component, The hardened | cured material which is excellent in abrasion resistance and high hardness is obtained by the said compound.

The (meth) acryl group-containing compound of the component (2) is a compound having three or more (meth) acryl groups in a molecule, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, Methoxylate pentaerythritol tetra (meth) acrylate, ethoxylate pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythrate Lithol tri (meth) acrylate, isocyanate isocyanurate, etc. are mentioned. Moreover, although polymer components, such as a trifunctional or more than urethane acrylate, polyester acrylate, and the hydrolysis-condensation product of the hydrolyzable silane compound which has an active energy ray reactive group, are mentioned, it is not necessarily limited to this.

Only 1 type may be used for these compounds and they may use 2 or more types together.

(3) Compounds containing one or two (meth) acryl groups

The compound containing one or two (3) (meth) acryl groups of the present invention becomes a main component of the curable component together with the compound containing (1) inorganic oxide fine particles and (2) three or more (meth) acryl groups. This forms the matrix of the film obtained after hardening.

In particular, it is a component for decreasing viscosity, and a component for improving adhesiveness with polymethyl methacrylate resin, polycarbonate resin, polystyrene resin, cyclic polyolefin resin, polyethylene terephthalate resin, triacetyl cellulose resin and the like.

In order for (3) component to reduce a viscosity, it is preferable that the viscosity in 25 degreeC is 100 mPa * s or less, especially 50 mPa * s or less. Although a minimum in particular is not restrict | limited, Usually, it is 1 mPa * s or more. In addition, a viscosity can be measured with a rotational viscometer (it is the same hereafter).

In order that especially this (meth) acryl group containing compound may improve adhesiveness, it is preferable to have functional groups, such as a hydroxyl group and an epoxy group, in a molecule | numerator. Moreover, it is preferable that skin irritation PII value is 4.0 or more. In addition, the skin irritation PII value of each compound can be investigated by literature etc.

For example, hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di ( Although meth) acrylate, diacrylate isocyanurate, ethylene oxide modified bisphenol A di (meth) acrylate, etc. are mentioned, It is not necessarily limited to this.

Only 1 type may be used for these compounds and they may use 2 or more types together.

The compounding quantity of (1) component is 25-70 mass parts in a total of 100 mass parts of (1) component, (2) component, and (3) component, Preferably it is 35-60 mass parts, and the compounding quantity of (2) component is It is 20-70 mass parts in a total of 100 mass parts of (1) component, (2) component, and (3) component, Preferably it is 30-55 mass parts, The compounding quantity of (3) component is (1) component (2 It is 5-30 mass parts, Preferably it is 10-20 mass parts in 100 mass parts of total of a component and (3) component.

If the compounding quantity of (1) component is less than 25 mass parts in total of 100 mass parts of (1) component, (2) component, and (3) component, hardness will fall and sufficient abrasion resistance will not be obtained, and if it exceeds 70 mass parts , The appearance of the coating is deteriorated. Moreover, when the compounding quantity of (2) component is less than 20 mass parts, dispersion stability will worsen and a film external appearance will worsen, and when it exceeds 70 mass parts, hardness will fall. Adhesiveness worsens that the compounding quantity of (3) component is less than 5 mass parts, and when it exceeds 30 mass parts, hardness will fall.

(4) aliphatic amine-based ionic compounds

In the present ^{invention, (4) R 1 R 2} R 3 R 4 N + X - (R 1, R 2, R 3, R 4 is _{CH 3, C 2 H 5,} C 2 H 4 OCH 3, C 6 Aliphatic amine ions represented by H ₁₃ , C ₈ H ₁₇ , each group may be the same or different, and X is a group selected from N (SO ₂ CF ₃ ) ₂ , BF ₄ , PF ₆ ) The acidic compound is used as an antistatic agent having good compatibility and solubility. In addition, there is an effect of improving dispersibility, by adding it, it is possible to suppress aggregation and sedimentation during storage, and to prevent the coating from becoming cloudy.

Among these, the aliphatic amine type ionic compound which is liquid at normal temperature (usually 5-40 degreeC, especially 25 degreeC) is especially preferable.

Here, R ¹ to R ⁴ is a group selected from CH ₃ , C ₂ H ₅ , C ₂ H ₄ OCH ₃ , C ₆ H ₁₃ , C ₈ H ₁₇ , each group may be the same or different. X is a group selected from N (SO ₂ CF ₃ ) ₂ , BF ₄ , and PF ₆ .

Specific examples of the aliphatic amine ionic compound represented by R ¹ R ² R ³ R ⁴ N ⁺ X ^- include the following ones.

_{(C 2 H 5) 4 N} + BF 4 -, (CH 3) (C 2 H 5) 3 N + BF 4 -, (CH 3) (C 2 H 5) 2 (C 2 H 4 OCH 3) N ^{_{+ BF 4 -, (CH 3}} ) 3 (C 6 H 13) N + BF 4 -, (CH 3) (C 8 H 17) 3 N + BF 4 -, (C 2 H 5) 4 N + PF 6 _{^{-, (CH 3) (C}} 2 H 5) 3 N + PF 6 -, (CH 3) (C 2 H 5) 2 (C 2 H 4 OCH 3) N + PF 6 -, (CH 3) 3 ( ^{_{C 6 H 13) N + PF}} 6 -, (CH 3) (C 8 H 17) 3 N + PF 6 -, (C 2 H 5) 4 N + (CF 3 SO 2) 2 N -, (CH 3 _{) (C 2 H 5) 3} N + (CF 3 SO 2) 2 N -, (CH 3) (C 2 H 5) 2 (C 2 H 4 OCH 3) N + (CF 3 SO 2) 2 N - _{, (CH 3) 3 (C} 6 H 13) N + (CF 3 SO 2) 2 N -, (CH 3) (C 8 H 17) 3 N + (CF 3 SO 2) 2 N -

When the said ionic compound is used, the surface resistance of hardened | cured material becomes 10 ¹² ohms or less at the time of initial stage and high temperature, high humidity, and sufficient dust adhesion prevention effect is acquired. In addition, in this invention, surface resistance value can be measured with a high resistivity resistivity meter.

The compounding quantity of (4) component is 0.05-3 mass parts with respect to a total of 100 mass parts of (1) component, (2) component, and (3) component, Preferably it is 0.1-2.5 mass parts, Especially preferably, it is 0.1-2.5 parts 2 parts by mass. If the amount is too small, the antistatic effect is not obtained, and the stability is also deteriorated. If there is too much compounding quantity, hardness will fall.

(5) radical type photoinitiator

The composition of this invention contains (5) radical type photoinitiator. As a radical type photoinitiator, it can select from normal things, such as an acetophenone type, a benzoin type, an acyl phosphine oxide type, a benzophenone type, and a thioxanthone type. Specifically, benzophenone, benzyl, Michler's ketone, thioxanthone derivative, benzoin ethyl ether, diethoxy acetophenone, benzyl dimethyl ketal, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenyl Ketones, acylphosphine oxide derivatives, 2-methyl-1- {4- (methylthio) phenyl} -2-morpholinopropane-1-one, 4-benzoyl-4'-methyldiphenylsulfide, 2, 4, 6-trimethyl benzoyl diphenyl phosphine etc. are mentioned. These may be used independently or may be used in combination of 2 or more type.

Among these, benzyldimethyl ketal, 1-hydroxycyclohexylphenyl ketone, hydroxydimethylacetophenone, 2-methyl-1- {4- (methylthio) phenyl} -2-morpholinopropan-1-one, 4 -Benzoyl-4'-methyldiphenylsulfide and 2,4,6-trimethylbenzoyldiphenylphosphine are preferable at the point that surface hardenability is favorable.

The compounding quantity of a radical type photoinitiator is 1-8 mass parts with respect to a total of 100 mass parts of (1) component, (2) component, and (3) component, Preferably it is 2-6 mass parts. If the amount is too small, the curability deteriorates. If the amount is too large, the adhesion decreases.

In the photocurable resin composition of the present invention, a silane coupling agent, a polymerization inhibitor, an antioxidant, an ultraviolet absorber, a light stabilizer, an antifoaming agent, a leveling agent, a surface tension lowering agent, and the like, as necessary, are not impaired. Although it contains, there is no problem, but it does not contain a solvent substantially. Here, substantially free means that it is acceptable to contain 3 mass% or less, especially 1 mass% or less in a composition.

Although the composition of this invention is obtained by mixing each said component uniformly according to a conventional method, in this invention, said (1) component is previously mixed with (2) component or (3) component, and this and the remaining component are mixed It is preferable.

In addition, these compositions are adjusted so that the viscosity in 25 degreeC may be 500 mPa * s or less. Preferably it is 300 mPa * s or less. If the viscosity is too high, coating workability deteriorates, and Joule nonuniformity tends to occur. Moreover, it is preferable that the viscosity at 25 degrees C of this composition is 10 mPa * s or more.

The photocurable resin composition of the present invention can be applied to the surface of an optical information medium such as an optical disk, an optical recording disk, a magneto-optical recording disk such as a reproduction-only optical disk, an optical magnetic recording disk, and the like, in which abrasion resistance and antistatic property are required on the surface thereof. By applying to the surface of the reproduction beam incident side or the surface of various display elements such as an optical lens, an optical filter, an anti-reflection film, an anti-reflection film underlayer, and a liquid crystal display, a CRT display, a plasma display, an EL display, and the like, these are hardened films. The surface scratch resistance and antifouling property can be provided, and the article which has this hardened film can be excellent in scratch resistance, abrasion resistance, and antistatic property.

As a method of forming the film of the said photocurable resin composition, a film can be manufactured by a roll coating method, a spin coating method, etc.

It is preferable that the film thickness of the formed film exists in the range of 0.1-50 micrometers, especially 0.5-30 micrometers. If the film thickness is too thin, wear resistance may decrease, and if too thick, crack resistance may decrease.

As a light source for curing the photocurable resin composition, a light source containing light having a wavelength in the range of 200 to 450 nm, for example, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, a xenon lamp, a carbon arc lamp, or the like can be used. . The irradiation amount is not particularly limited, but is preferably 10 to 5,000 mJ / cm 2, particularly 20 to 1,000 mJ / cm 2. The curing time is usually 0.5 seconds to 2 minutes, preferably 1 second to 1 minute.

[Example]

Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited to the following Example. In addition, in the following example, a viscosity is the value measured with the rotational viscometer.

Example 1

80 mass parts of ethoxylate pentaerythritol tetraacrylate in which (gamma) -methacryloxypropyl trimethoxysilane-treated silica was disperse | distributed (hereinafter S-PETTA; silica concentration 50 mass%, silica particle diameter 30 nm), hexanediol diacryl rate (hereinafter, HDODA, PII value 5.5) 20 parts by _{mass, (CH 3) (C 8} H 17) 3 N + (CF 3 SO 2) 2 N - ( hereinafter, MTOTFSI) 0.2 parts by mass of Darocure 1173 (the , 311 parts of 2-hydroxy-2-methyl-1-phenylpropan-1-one, a radical photoinitiator, Ciba Specialty Chemicals, brand name) are mixed, and the viscosity at 25 degrees C is 180 mPa. The photocurable resin composition which is s was obtained. This composition was apply | coated to polycarbonate so that it might be set to 5 micrometers in thickness, the light was irradiated for 2 second with 80 W high pressure mercury lamp (integrated irradiation amount 200mJ / cm <2>), and it hardened | cured and the transparent film was obtained.

The evaluation shown below was performed using the obtained film | membrane. These results are shown in Table 1.

Preservation Stability:

After 14 days of 40 degreeC, it was visually judged whether there exists a sediment, and the following reference | standard evaluated.

○: no sediment

×: with sediment

Film transparency:

It put into 100 cc beaker, and it visually judged, and evaluated by the following reference | standard.

○: transparent

△: barely whitening

×: White flower

Abrasion Resistance, Wear Resistance:

In accordance with ASTM D 1044, a wear test (500 g load, 100 revolutions) of the cured film was performed using a taber abrasion tester (using abrasion wheel CS-10F), and the turbidity of the cured film before and after the abrasion test was measured by a turbidimeter (NDH2000, It measured using Nippon Denshoku Kogyo Co., Ltd.), and made the haze before the haze-wear test after abrasion test the (Haze) ((DELTA haze is good in abrasion resistance and abrasion resistance in the case of 15 or less).

Surface resistance:

It measured in 25 degreeC and the atmosphere of 50% RH using the high-resistance resistivity meter (Hyster UP MCP-HT450 type | mold, the diamond instrument company make).

Half-life:

It measured in 25 degreeC and the atmosphere of 50% RH using the charged charge attenuation measuring device (Stachyl Onest meter, the Shiseido Seidenki Co., Ltd. product).

Adhesiveness:

The following reference | standard evaluated by the checkerboard tick tape peeling test.

○: no abnormality

×: There is a peeling point

In the taber abrasion test, the Δ haze was 8, and the wear resistance was high. Moreover, the surface resistance value was low as 5x10 ¹² ohms, and the half life was short, less than 60 second.

[Examples 2 and 3 and Comparative Examples 1 to 7]

In the same manner, as shown in Tables 1 and 2 below, the formulation was changed to obtain a film and evaluated. These results are shown in Tables 1 and 2.

S-PETTA: ethoxylate pentaerythritol tetraacrylate in which γ-methacryloxypropyltrimethoxysilane-treated silica is dispersed, silica concentration 50 mass%, silica particle diameter 30 nm

S-PETTA-2: ethoxylate pentaerythritol tetraacrylate in which γ-methacryloxypropyltrimethoxysilane-treated silica is dispersed, silica concentration 50 mass%, silica particle diameter 120 nm

HDODA: Hexanedioldiacrylate

THFFA: tetrahydrofurfuryl acrylate

_{MTOTFSI: (CH 3) (C} 8 H 17) 3 N + (CF 3 SO 2) 2 N -

D1173: Darocure 1173, 2-hydroxy-2-methyl-1-phenylpropan-1-one, the Ciba specialty chemicals company make, brand names

PGM: Propylene Glycol Monomethyl Ether

Claims (5)

(1) inorganic oxide fine particles having an average particle diameter of 80 nm or less,
(2) a compound containing three or more (meth) acryl groups,
(3) a compound containing one or two (meth) acryl groups;
^{(4) R 1 R 2 R} 3 R 4 N + X - (R 1, R 2, R 3, R 4 is _{CH 3, C 2 H 5,} C 2 H 4 OCH 3, C 6 H 13, C 8 An ionic compound represented by H ₁₇ , wherein each group may be the same or different, X is a group selected from N (SO ₂ CF ₃ ) ₂ , BF ₄ , PF ₆ ),
(5) radical type photoinitiator
It is made to contain, (1) component is 25-70 mass parts, (2) component is 20-70 mass parts, and (3) component among 100 mass parts of total of (1), (2), and (3) component It is 5-30 mass parts, (4) component is 0.05-3 mass parts and (5) component is 1-8 mass parts with respect to a total of 100 mass parts of (1), (2), (3) component, It does not contain a solvent substantially, and the viscosity in 25 degreeC is 500 mPa * s or less, The photocurable resin composition characterized by the above-mentioned. The photocurable resin composition of Claim 1 whose inorganic oxide fine particles whose average particle diameter of (1) component is 80 nm or less are silica fine particles. The photocurable resin composition according to claim 2, wherein the silica fine particles are treated with a silane coupling agent containing a (meth) acryl group. The component according to any one of claims 1 to 3, wherein component (4) and component (5) are mixed with a mixture in which component (1) is previously dispersed in component (2) and / or component (3). Photocurable resin composition. The cured film of the photocurable resin composition of any one of Claims 1-3 is formed.