TWI470350B - A photohardenable resin composition and an article having a hardened film - Google Patents

Description

Photocurable resin composition and article having the same

The present invention relates to a photocurable resin composition for coating, coating, etc., and an article having the same, and more particularly to a storage stability, high transparency, high hardness, and resistance A photocurable resin composition of a hardened film excellent in abrasion resistance and antistatic property, and an article having a cured film.

a synthetic resin such as polymethyl methacrylate resin, polycarbonate resin, polystyrene resin, cyclic polyolefin resin, polyethylene terephthalate resin or triethylene glycol resin, which is lightweight ‧The advantages of transparency, easy processing and so on. Therefore, in recent years, such a synthetic resin has been used in various fields such as a display screen such as a CD, a DVD, or the like, a display screen such as a liquid crystal or an EL panel, and various functional films.

In order to improve the scratch resistance of the surfaces, a hard coating layer which is transparent and scratch-resistant is formed on the recording side surface of the recording and/or reproducing light beam of the medium. The hard coating layer is formed by a compound containing a photoreactive group having two or more (meth)acryl groups in the molecule or an alkoxy group having a photoreactive group such as a (meth)acryl group. A oxane compound having a cage structure in which a hydrazine is hydrolyzed and condensed in the presence of a basic catalyst (Japanese Laid-Open Patent Publication No. 2002-363414, JP-A-2004-143449: Patent Document 1, 2), or has a photoreaction A composition such as a reaction product of alkoxy decane and colloidal cerium oxide is applied to the surface of the medium, and is cured by irradiation with an active energy ray such as ultraviolet rays.

In addition, for the purpose of improving the antistatic property, it is reviewed that various antistatic agents are added. A reaction product of a polyether-modified fluorenone and lithium perchlorate (Japanese Patent Laid-Open No. Hei 5-320626: Patent Document 3) or a reaction product of a polyfunctional acrylate and lithium perchlorate (Japanese Patent No. 3673590: Patent Document 4), a mixture of a polyfunctional acrylate and (CF ₃ SO ₂ ) ₂ NLi (Japanese Patent Laid-Open No. Hei 9-278831, JP-A-2001-288325: Patent Document 5, 6) is proposed, but it is resistant to abrasion. Sex is not sufficient.

Therefore, a mixture of cerium oxide and decane hydrolyzate and (CF ₃ SO ₂ ) ₂ NLi is used for the purpose of improving the scratch resistance (Japanese Unexamined Patent Publication No. Hei No. Hei No. 2005-146110, No. 2006-70120, JP-A-2008- Japanese Patent Publication No. 222951: Patent Documents 7 to 9) is proposed, but it is a solvent.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] JP-A-2002-363414

[Patent Document 2] JP-A-2004-143449

[Patent Document 3] JP-A-H05-320626

[Patent Document 4] Patent No. 3673590

[Patent Document 5] JP-A-9-278831

[Patent Document 6] JP-A-2001-288325

[Patent Document 7] JP-A-2005-146110

[Patent Document 8] JP-A-2006-70120

[Patent Document 9] JP-A-2008-222951

In view of the above, the present invention provides a photocurable resin composition which has good storage stability, high transparency, and imparts a scratch-resistant film having excellent scratch resistance and antistatic property, and has a hardening property. The purpose of the film is for the purpose.

As a result of repeating the review, the present inventors have found that (1) inorganic oxide fine particles having an average particle diameter of 80 nm or less and (2) compounds containing three or more (meth)acryl groups are contained. (3) a compound containing one or two (meth)acryl groups, (4) an aliphatic amine-based ionic compound shown below, and (5) a radical photopolymerization initiator, and in spite of the substance The film which does not contain a solvent, and which has good stability, and has a viscosity of 500 mPa·s or less at 25 ° C and a photocurable resin composition excellent in coating workability, is excellent in adhesion to the support substrate. The invention is excellent in transparency, excellent in scratch resistance and antistatic property, and the present invention has been achieved.

Therefore, the present invention provides a photocurable resin composition shown below and an article having the cured film thereof.

[Request 1]

A photocurable resin composition characterized by

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

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

(3) a compound containing one or two (meth) propylene groups,

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

(5) The radical photopolymerization initiator is formed, and in the total of 100 parts by mass of the components (1), (2), and (3), the component (1) is 25 to 70 parts by mass, and the component (2) is 20 to 70 parts by mass, and the component (3) is 5 to 30 parts by mass, and the component (4) is 0.05 to 3 parts by mass based on 100 parts by mass of the components (1), (2), and (3), ( 5) The component is 1 to 8 parts by mass, and substantially contains no solvent, and has a viscosity at 25 ° C of 500 mPa ‧ or less.

[Request 2]

The photocurable resin composition according to claim 1, wherein the inorganic oxide fine particles of the component (1) having an average particle diameter of 80 nm or less are cerium oxide fine particles.

[Request 3]

The photocurable resin composition according to claim 2, wherein the cerium oxide fine particles are treated by a (meth)acryl-based decane coupling agent.

[Request Item 4]

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

[Request 5]

An article formed by the hardened film of the photocurable resin composition according to any one of claims 1 to 4, wherein the article is formed.

The photocurable resin composition of the present invention is obtained by mixing an ionic compound in the inorganic oxide fine particles dispersed in the (meth)acryl group-containing compound so that the inorganic oxide fine particles and the ionic compound are in phase. The effect of both the antistatic property and the dispersion stability is imparted to the effect, and even if the solvent is not used, a film excellent in storage stability, high transparency, and excellent in abrasion resistance and antistatic property can be obtained.

[Formation of the Invention]

The photocurable resin composition of the present invention contains

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

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

(3) a compound containing one or two (meth) propylene groups,

(4) an aliphatic amine-based ionic compound,

(5) A radical photopolymerization initiator which does not substantially contain a solvent and has a viscosity at 25 ° C of 500 mPa ‧ s or less.

(1) Inorganic oxide microparticles

(1) The inorganic oxide fine particles of the present invention include, for example, oxide fine particles of Si, Ti, Al, Zn, Zr, In, Sn, Sb, Ce, Fe, or the like, or composite oxide fine particles or the like. Specific examples of the metal oxide fine particles include fine particles such as cerium oxide, aluminum oxide, zirconium oxide, titanium oxide, and cerium oxide.

The inorganic oxide fine particles have an average particle diameter of 80 nm or less, preferably 50 nm or less. When the use is larger than 80 nm, the stability is deteriorated, and particulate foreign matter is visible on the film, and the transparency is impaired. Further, the lower limit thereof is usually 10 nm or more. Further, in the present invention, the average particle diameter system can be measured by a particle size distribution measuring apparatus using a dynamic light scattering photon correlation method.

Particularly preferable inorganic oxide fine particles are cerium oxide fine particles, and those having an average particle diameter of 50 nm or less are more preferable. Further, the cerium oxide microparticles may have a hollow or porous effect such as a low refractive index. As such inorganic oxide fine particles, a commercially available product such as ELECOM ST-1003SIV (made by Nikko Catalyst) can be used.

Among the cerium oxide microparticles, it is preferred to use a hydrolyzable decane compound having an active energy ray-reactive group for surface modification. Such a reactive cerium oxide microparticle is subjected to a crosslinking reaction by irradiation with an active energy ray when the composition is cured to be fixed in a polymer matrix.

Here, examples of the hydrolyzable decane compound having an active energy ray-reactive group include a (meth) propylene group-containing decane coupling agent, and specifically, γ-methyl propylene methoxy propyl trimethoxide is exemplified. Baseline, γ-methacryloxypropyltriethoxydecane, γ-methylpropenyloxypropyltrichlorodecane, γ-methylpropenyloxypropylmethyldimethoxydecane γ-Methyl propylene methoxy propyl methyl diethoxy decane, γ-methyl propylene methoxy propyl methyl dichloro decane, γ-methyl propylene methoxy propyl dimethyl methoxy Base decane, γ-methacryloxypropyl dimethyl ethoxy decane, γ-methyl propylene methoxy propyl dimethyl chloro decane, γ-propylene methoxy propyl trimethoxy decane, Γ-propylene methoxypropyl triethoxy decane, γ-propylene methoxy propyl trichloro decane, γ-propylene methoxy propyl methyl dimethoxy decane, γ-acryloxypropyl propyl Methyl diethoxy decane, γ-propylene methoxy propyl methyl dichloro decane, γ-propylene methoxy propyl dimethyl methoxy decane, γ-propylene methoxy propyl dimethyl oxygen Decane, γ-propylene methoxypropyl dimethyl chlorodecane, γ-propylene methoxymethyl trimethoxy decane, γ-propylene methoxymethyl triethoxy decane, γ-acryloxy group Trichloromethane, γ-propylene methoxymethyl methyl dimethoxy decane, γ-propylene methoxymethyl methyl diethoxy decane, γ-propylene methoxymethyl methyl dichloro decane And γ-propylene methoxymethyl dimethyl methoxy decane, γ-propylene methoxymethyl dimethyl ethoxy decane, γ-propylene methoxymethyl dimethyl chloro decane.

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

In the method of surface modification of the hydrolyzable decane compound having an active energy ray-reactive group, a method of hydrolyzing a hydrolyzable decane compound having an active energy ray-reactive group in the presence of cerium oxide microparticles is exemplified. The hydrolyzate of the hydrolyzable decane compound having an active energy ray-reactive group in the by-products has to be eliminated because the storage stability is deteriorated or the hardness is lowered.

It is preferable to use such (1) inorganic oxide fine particles as a primary particle dispersed in the following (2) a compound containing three or more (meth)acryl groups, or (3) one or two. Among the (meth)acryl-based compounds, a film having a good appearance such as transparency can be obtained by being present as primary particles.

Specifically, a method of physically dispersing the inorganic oxide fine particles in a compound containing a (meth)acryl group as a dispersing agent or a dispersing device, or adding a solution in a solution in which the inorganic oxide fine particles are dispersed may be mentioned. After the (meth)acryl-based compound, the dispersant is distilled off.

(2) Compounds containing more than 3 (meth) propylene groups

(2) The compound containing three or more (meth) propylene groups of the present invention is cured together with (1) inorganic oxide fine particles and (3) a compound containing one or two (meth) propylene groups. The main component of the component is a matrix formed on the film obtained after curing.

The compound containing three or more (meth) propylene groups is a binder component which disperses the inorganic oxide fine particles of the component (1), and the compound is excellent in abrasion resistance and hardness. Object.

(2) A compound containing a (meth)acryl group as a component, and a compound having three or more (meth)acryl groups in the molecule, and examples thereof include trimethylolpropane tri(meth)acrylate and pentaerythritol IV. (Meth) acrylate, methoxylated pentaerythritol tetra(meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, di-trimethylolpropane tetra (meth) acrylate, dipentaerythritol Hexa(meth)acrylate, pentaerythritol tri(meth)acrylate, triacrylated isocyanate, and the like. Further, a polymer component such as a trifunctional or higher urethane acrylate, a polyester acrylate, or a hydrolysis condensate of a hydrolyzable decane compound having an active energy ray-reactive group may be used, but it is not limited only. These are the same.

These compounds may be used alone or in combination of two or more.

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

(3) The compound containing one or two (meth)acrylyl groups of the present invention is cured together with (1) inorganic oxide fine particles and (2) a compound containing three or more (meth)acryl groups. The main component of the component is a matrix formed on the film obtained after curing.

In particular, the component for lowering the viscosity is also used to make polymethyl methacrylate resin, polycarbonate resin, polystyrene resin, cyclic polyolefin resin, polyethylene terephthalate resin. A component for improving the adhesion of triacetyl phthalocyanine resin or the like.

(3) The component has a viscosity at 25 ° C of 100 mPa ‧ s or less, particularly 50 mPa ‧ s or less, in order to lower the viscosity. Although the lower limit is not particularly limited, it is usually 1 mPa ‧ or more. Further, the viscosity can be measured by a rotary viscosity agent (the same applies hereinafter).

The compound containing a (meth)acryl group is particularly preferably a functional group having a hydroxyl group, an epoxy group or the like in the molecule in order to enhance the adhesion. Further, it is preferred that the skin irritation PII value is 4.0 or more. Further, the skin irritation PII value of each compound can be found by literature or the like.

For example, hydroxyethyl (meth) acrylate, epoxy propyl (meth) acrylate, tetrahydroindenyl (meth) acrylate, 1,6-hexane diol di (meth) acrylate And triethylene glycol di(meth)acrylate, diacrylated isocyanate, ethylene oxide modified bisphenol A di(meth)acrylate, etc., but are not limited thereto.

These compounds may be used alone or in combination of two or more.

(1) The amount of the component is 25 to 70 parts by mass, preferably 35 to 60 parts by mass, based on 100 parts by mass of the total of the components (1) and (2) and (3), and (2) The amount of the component is 20 to 70 parts by mass, preferably 30 to 55 parts by mass, and (3) of the total amount of the component (1) and the component (2) and the component (3). The amount of the component is 5 to 30 parts by mass, preferably 10 to 20 parts by mass, per 100 parts by mass of the total of the component (1) and the component (3).

When the amount of the component (1) and the component (3) is less than 25 parts by mass, the hardness is lowered, and sufficient abrasion resistance cannot be obtained. When it exceeds 70 mass parts, the appearance of a film deteriorates. In addition, when the amount of the component (2) is less than 20 parts by mass, the dispersion stability is deteriorated and the appearance of the film is deteriorated, and if it exceeds 70 parts by mass, the hardness is lowered. When the amount of the component (3) is less than 5 parts by mass, the adhesion is deteriorated, and if it exceeds 30 parts by mass, the hardness is lowered.

(4) Aliphatic amine ionic compounds

In the present invention, (4) is R ¹ R ² R ³ R ⁴ N ⁺ X ^- (R ¹ , R ² , R ³ , and R ^{4 are} derived from CH ₃ , C ₂ H ₅ , C ₂ H ₄ OCH ₃ , C ₆ H ₁₃ , C ₈ H ₁₇ selected groups, the respective groups may be the same or different. X is an aliphatic amine represented by N(SO ₂ CF ₃ ) ₂ , BF ₄ , PF ₆ selected) An ionic compound is an antistatic agent which is excellent in compatibility and solubility. Further, since the effect of improving the dispersibility is obtained, aggregation or sedimentation during storage can be suppressed by addition, and the film can be prevented from being cloudy.

Among these, an aliphatic amine-based ionic compound which is liquid at normal temperature (usually 5 to 40 ° C, particularly 25 ° C) is particularly preferable.

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

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

(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 ionic compound is used, the surface resistance value of the cured product is 10 ¹² Ω or less at the initial stage and at the time of high temperature and high humidity, and a sufficient anti-dust adhesion effect can be obtained. Further, in the present invention, the surface impedance value can be measured by a high impedance impedance meter.

(4) The amount of the component is 0.05 to 3 parts by mass, preferably 0.1 to 2.5 parts by mass, particularly preferably 0.1, based on 100 parts by mass of the total of the components (1) and (2) and (3). ~ 2 parts by mass. If the amount of the collocation is too small, the antistatic effect cannot be obtained, and further, the stability is also deteriorated. If the amount is too much, the hardness will decrease.

(5) Free radical photopolymerization initiator

The composition of the present invention contains (5) a radical photopolymerization initiator. The radical photopolymerization initiator may be selected from the group consisting of acetophenone-based, benzoin-based, phosphonium-based oxide-based, diphenylketone-based, and thioxanthone-based. Specific examples thereof include diphenyl ketone, benzophenone, Michler's ketone, thioxanthone derivative, benzoin ethyl ether, diethoxyacetophenone, benzyldimethyl group. Ketal, 2-hydroxy-2-methylethyl phenyl ketone, 1-hydroxycyclohexyl phenyl ketone, fluorenylphosphine oxide derivative, 2-methyl-1-{4-(methylthio)benzene -2-}-2-fosfolinylpropan-1-one, 4-benzylidene-4'-methyldiphenyl sulfide, 2,4,6-trimethylbenzhydryldiphenylphosphine Wait. These may be used alone or in combination of two or more.

Among these, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, hydroxy dimethyl acetophenone, 2-methyl-1-{4-(methylthio)phenyl }-2-oxalinylpropan-1-one, 4-benzylidene-4'-methyldiphenyl sulfide, 2,4,6-trimethylbenzimidyldiphenylphosphine It is preferred that the surface hardenability is good.

The amount of the radical photopolymerization initiator is from 1 to 8 parts by mass, preferably from 2 to 6 parts by mass, per 100 parts by mass of the total of the components (1) and (2) and (3). If the amount of the collocation is too small, the hardenability deteriorates, and if it is too much, the adhesion is lowered.

The photocurable resin composition of the present invention may further contain a decane coupling agent, a polymerization inhibiting agent, an antioxidant, an ultraviolet absorber, a light stabilizer, or a consumer, without departing from the object of the present invention. A foaming agent, a leveling agent, a surface tension reducing agent, etc., but the solvent is substantially absent. Here, the term "substantially does not mean" is allowed to be contained in a ratio of 3% by mass or less, particularly preferably 1% by mass or less, based on the composition.

In the composition of the present invention, the above components are obtained by uniform mixing according to a usual method. However, in the present invention, the component (1) is previously mixed with the component (2) or the component (3), and then This is preferably mixed with the remaining ingredients.

Further, these compositions are adjusted so as to have a viscosity at 25 ° C of 500 mPa ‧ or less, preferably 300 mPa ‧ or less. If the viscosity is too high, the coating workability is deteriorated, and rib unevenness is likely to occur. Further, it is preferred that the composition has a viscosity at 25 ° C of 10 mPa ‧ s or more.

The photocurable resin composition of the present invention is applied to an article having an abrasion resistance and an antistatic property, and particularly a light information such as a replaying dedicated optical disc, an optical recording disc, or a magneto-optical recording disc. The surface of the media, in more detail, the recording or reproduction of the incident side surface of the beam, or optical lens, optical filter, anti-reflection film, anti-reflection film underlayer film, and liquid crystal display, CRT display, plasma display, EL display On the surface of various display elements and the like, and by forming a hardened film, scratch resistance and antifouling properties can be imparted to such surfaces, and articles having such a cured film are resistant to abrasion and abrasion. And excellent in antistatic properties.

In the method of forming the film of the photocurable resin composition, a film can be produced by a roll coating method, a spin coating method, or the like.

The film thickness of the film formed is preferably from 0.1 to 50 μm, particularly preferably from 0.5 to 30 μm. If the film thickness is too thin, the abrasion resistance may be lowered, and if it is too thick, the crack resistance may be lowered.

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

[Examples]

Hereinafter, the present invention will be specifically described by showing examples and comparative examples, but the present invention is not limited to the examples described below. Further, in the following examples, the viscosity is a value measured by a rotary viscosity agent.

[Example 1]

Ethoxylated pentaerythritol tetraacrylate (hereinafter referred to as S-PETTA; cerium oxide concentration: 50% by mass, cerium oxide particle diameter: 30 nm) in which cerium oxide treated with γ-methacryloxypropyltrimethoxydecane is dispersed 80 parts by mass of hexanediol diacrylate (hereinafter, HDODA, PII value: 5.5) 20 parts by mass, (CH ₃ )(C ₈ H ₁₇ ) ₃ N ⁺ (CF ₃ SO ₂ ) ₂ N ^- (below, MTOTFSI) 0.2 parts by mass, Darocure 1173 (hereinafter referred to as D1173; 2-hydroxy-2-methyl-1-phenylpropan-1-one, a radical photopolymerization initiator, manufactured by Ciba Specialty Chemicals Co., Ltd., trade name) 3 parts by mass were mixed to obtain a photocurable resin composition having a viscosity at 25 ° C of 180 mPa ‧ s. This composition was coated on a polycarbonate to have a thickness of 5 μm, and irradiated with an 80 W high-pressure mercury lamp for 2 seconds (accumulated irradiation amount: 200 mJ/cm ² ) to be cured to obtain a transparent film.

Using the obtained film, the evaluation shown below was performed. The results of these are shown in Table 1.

Save stability:

After 40 days and 14 days, the presence or absence of sediment was visually judged and evaluated based on the following criteria.

○: no sediment

×: There is sediment

Film transparency:

The measurement was visually judged by placing in a 100 cc beaker, and evaluation was performed based on the following criteria.

○: transparent

△: slightly whitened

×: whitening

Scratch resistance, wear resistance:

The abrasion test of the hardened film (500 g load, 100 turns) was carried out using a TABER abrasion tester (using the wear wheel CS-10F) based on ASTM D 1044, and the turbidity of the hardened film before and after the abrasion test was measured using a turbidimeter ( NDH2000, manufactured by Nippon Denshoku Industries Co., Ltd., and measured (the turbidity after the abrasion test minus the turbidity before the abrasion test) was ΔHaze (when ΔHaze was 15 or less, the scratch resistance and the abrasion resistance were good).

Surface resistance value:

The measurement was carried out in an atmosphere of 25 ° C and 50% RH using a high-impedance impedance meter (Hiresta UP MCP-HT450 type, manufactured by DIA Instruments).

half life:

The measurement was carried out in an atmosphere of 25 ° C and 50% RH using a charged charge decay degree measuring instrument (STATIC HONEST METER, manufactured by SHISHADO ELECTRONICS CO., LTD.).

Adhesion:

The board was peeled and tested by the checkerboard tape and evaluated on the basis of the following criteria.

○: No abnormality

×: There is a stripping place

In the TABER abrasion test, if ΔHaze is 8, the abrasion resistance is also high. Further, the surface resistance value is as low as 5 × 10 ¹² Ω, and the half life is also as short as less than 60 seconds.

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

Similarly, the film was changed and the film was obtained as shown in the following Tables 1 and 2, and evaluated. The results of these are shown in Tables 1 and 2.

S-PETTA: ethoxylated pentaerythritol tetraacrylate in which cerium oxide treated with γ-methyl propylene methoxy propyl trimethoxy decane is dispersed, cerium oxide concentration: 50% by mass, cerium oxide particle diameter: 30 nm

S-PETTA-2: ethoxylated pentaerythritol tetraacrylate having cerium oxide treated by γ-methyl propylene methoxy propyl trimethoxy decane, cerium oxide concentration of 50% by mass, and cerium oxide particle diameter of 120 nm

HDODA: Hexanediol diacrylate

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, manufactured by Ciba Specialty Chemicals Co., Ltd., trade name

PGM: propylene glycol monomethyl ether

Claims (5)

A photocurable resin composition comprising (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, and (3) one or Two (meth)acrylyl compounds, (4) R ¹ R ² R ³ R ⁴ N ⁺ X ^- (R ¹ , R ² , R ³ , R ⁴ are from CH ₃ , C ₂ H ₅ , C ₂ H ₄ OCH ₃ , C ₆ H ₁₃ , C ₈ H ₁₇ selected groups, the respective groups may be the same or different; X is selected from N(SO ₂ CF ₃ ) ₂ , BF ₄ , PF ₆ And (5) a total of 100 parts by mass of the components (1), (2), and (3), wherein the component (1) is 25 to 70, and the ionic compound (5) is a radical photopolymerization initiator. The mass fraction, the component (2) is 20 to 70 parts by mass, the component (3) is 5 to 30 parts by mass, and the total of the components (1), (2), and (3) is 100 parts by mass, and the component (4) is It is 0.05 to 3 parts by mass, and the component (5) is 1 to 8 parts by mass, and substantially contains no solvent, and has a viscosity at 25 ° C of 500 mPa ‧ s or less. The photocurable resin composition according to the first aspect of the invention, wherein the inorganic oxide fine particles of the component (1) having an average particle diameter of 80 nm or less are cerium oxide fine particles. The photocurable resin composition according to the second aspect of the invention, wherein the cerium oxide fine particles are treated by a (meth)acryl-based decane coupling agent. The photocurable resin composition according to any one of the items 1 to 3, wherein the component (1) is previously dispersed in the mixture of the component (2) and/or the component (3). It is made by mixing (4) and (5) components. An article formed by the hardened film of the photocurable resin composition according to any one of the first to fourth aspects of the invention.