KR20110097676A - Photocurable resin composition and article having cured coating thereof, and method for preparation thereof - Google Patents

Abstract

A photocurable resin composition having high hardness, excellent transparency, antistatic property, storage stability, moisture heat resistance, and wet heat resistance, and no whitening regardless of the conveyance speed of the coating line during curing by light irradiation, and curing thereof An article having a coating and a method of manufacturing the same are provided.
(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 4 is _{CH 3, C 2 H 5,} C 2 H 4 OCH 3, C 6 H 13 or C ₈ H _17, X is N Ionic compound represented by (SO ₂ CF ₃ ) ₂ , BF ₄ or PF ₆ ),
^{(5) Li + Y - (} Y is _{ClO 4, SO 2 CF 3,} SO 2 C 2 F 5, N (SO 2 CF 3) 2, N (SO 2 C 2 F 5) 2, BF 4 or PF ₆ Ionic compounds represented by
(6) radical type photoinitiator
Photocurable resin composition which contains in a specific ratio.

Description

Article which has photocurable resin composition and its cured film, its manufacturing method {PHOTOCURABLE RESIN COMPOSITION AND ARTICLE HAVING CURED COATING THEREOF, AND METHOD FOR PREPARATION THEREOF}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an article having a photocurable resin composition for use in paints, coatings, and the like, and to a cured coating thereof, and more particularly, to a substrate having high hardness, transparency, antistatic properties, storage stability, and moist heat conditions. It is excellent in the adhesiveness, and at the time of hardening by light irradiation, the resin composition which does not produce whitening irrespective of the conveyance speed of a coating line, and the article which has its cured film, and its manufacturing method are related.

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 easy processing. Thus, such synthetic resins have recently been used in various fields such as optical discs 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 performed to form a hard coat that is transparent and has scratch resistance on the recording and / or reproduction beam incident side surface of the medium.

Formation of the hard coat is a cage in which a compound having two or more photoreactive groups such as (meth) acryloyl group in the molecule or alkoxysilane having photoreactive groups such as (meth) acryloyl group is 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 Literatures 1 and 2), a composition containing a reactant of an alkoxysilane and colloidal silica having a photoreactive group, and the like It apply | coats to a surface and hardens it by irradiation of active energy rays, such as an ultraviolet-ray. For the purpose of improving these antistatic properties, the addition of various antistatic agents has been studied. Reactant of polyether modified silicone and lithium perchlorate (Japanese Patent Laid-Open No. 5-320625: Patent Document 3), Reactant of polyfunctional acrylic and lithium perchlorate (Japanese Patent No. 3673590: Patent Document 4), polyfunctional acrylic Although a mixture of a rate and (CF ₃ SO ₂ ) ₂ NLi (Japanese Patent Laid-Open No. 9-278831, Japanese Patent Laid-Open Nos. 2001-288325: Patent Literatures 5 and 6) has been proposed, scratch resistance is insufficient.

Therefore, for the purpose of improving the 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 Patent Laid-Open 2008- 222951 (Patent Documents 7 to 9) have been proposed, but since the solvent is contained, a facility for treating the solvent at the time of curing is required, resulting in a large facility cost burden.

Japanese Patent Laid-Open No. 2002-363414 Japanese Patent Laid-Open No. 2004-143449 Japanese Patent Laid-Open No. 5-320625 Japanese Patent No. 3673590 Japanese Patent Laid-Open No. 9-278831 Japanese Patent Laid-Open No. 2001-288325 Japanese Patent Publication No. 2005-146110 Japanese Patent Publication No. 2006-70120 Japanese Patent Publication No. 2008-222951

This invention is made | formed in view of the said situation, It is high hardness, is excellent in adhesiveness to a base material under transparency, antistatic property, storage stability, moist heat resistance, and moist heat conditions, and conveyance of a coating line at the time of hardening by light irradiation. It aims at providing the photocurable resin composition which whitening does not produce regardless of a speed | rate, the article which has its hardened film, and its manufacturing method.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly examined in order to achieve the said objective, As a result, (1) inorganic oxide microparticles whose average particle diameter is 80 nm or less, (2) the compound containing three or more (meth) acryl groups, (3) (meth A compound containing one or two acrylic groups, (4) an aliphatic amine ionic compound shown below, (5) a lithium ionic compound shown below, and (6) a radical photoinitiator are contained at a specific ratio. The photocurable resin composition which is excellent in storage stability and does not produce whitening irrespective of the conveyance speed of a coating line at the time of hardening by light irradiation, and the film formed by hardening this composition is made under the conditions of wet heat conditions with respect to a support gas. It was found that the adhesion was good, the transparency was high, and the scratch resistance and the antistatic property were excellent. Moreover, in this case, it discovered that this photocurable resin composition can be used suitably in the state which does not contain a solvent substantially, and reached | attained this invention.

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

[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 is a group selected from H _17, may be the same or different and each group. X is N (SO ₂ CF ₃₎ an ionic compound represented by the formula _2, BF _4, or a group selected from PF _6.),

^{(5) Li + Y - (} Y is _{ClO 4, SO 2 CF 3,} SO 2 C 2 F 5, N (SO 2 CF 3) 2, N (SO 2 C 2 F 5) 2, BF 4 or PF ₆ Ionic compounds represented by

(6) radical type photoinitiator

Containing, (1) 25-70 mass parts of (1) components, 20-70 mass parts of (2) components, and (3) component in 100 mass parts of total of (1), (2), and (3) component It is this 5-30 mass parts, 0.05-4 mass parts of (4) components, 0.1-7 mass parts of (5) components with respect to 100 mass parts of total of (1), (2), (3) component, (6) Photocurable resin composition whose component is 1-8 mass parts.

[Claim 2]

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

[Claim 3]

The photocurable resin composition of Claim 2 in which a silica microparticle is processed with the silane coupling agent containing a (meth) acryl group.

[Claim 4]

It does not contain a solvent substantially, and the viscosity in 25 degreeC is 300 mPa * s or less, The photocurable resin composition in any one of Claims 1-3 characterized by the above-mentioned.

[Claim 5]

(1) The component which mixes (4), (5), and (6) component in the mixture which disperse | distributed the component to (2) component and / or (3) component previously, It is characterized by any of Claims 1-4. The photocurable resin composition of Claim.

[Claim 6]

The hardened film of the photocurable resin composition of any one of Claims 1-5 is formed, the total light transmittance is 85% or more, Haze is 2% or less, the load 500g and 100 rotations in the taper abrasion test by ASTM D1044. An article having a rate of change of Haze of 8% or less and a surface resistance of 1 × 10 ¹⁵ Ω or less in the city.

[Claim 7]

The article according to claim 6, wherein the article on which the cured coating film is formed is molded from a resin composition containing 50% by mass or more of polycarbonate.

[Claim 8]

The photocurable resin composition according to any one of claims 1 to 5 is coated on the article to be treated by the microgravure method and cured by ultraviolet irradiation to form a cured film on the article to be treated. Manufacturing method.

The photocurable resin composition of this invention raises an inorganic oxide fine particle and an ionic compound by mixing a specific amount of an aliphatic amine type ionic compound and a lithium type ionic compound in the inorganic oxide fine particle disperse | distributed in the (meth) acryl group containing compound. The effect contributes to both effects of antistatic property and dispersion stability, and provides a film having good storage stability, high transparency, excellent transparency, wear resistance, antistatic property, and adhesion under moist heat conditions even without substantially mixing the solvent.

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) lithium-based ionic compounds,

(6) radical type photoinitiator

It contains.

(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 composite oxide fine particles thereof. Specific examples of the metal oxide fine particles include fine particles such as silica, alumina, zirconia, titania, and cerium oxide.

These inorganic oxide fine particles have an average particle diameter of 80 nm or less. Preferably it is 50 nm or less. If a size larger than 80 nm is used, stability deteriorates, and foreign matters in the form of particles appear on the film or the transparency is impaired. In addition, the minimum 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 a silica fine particle, and it is more preferable if an average particle diameter is 50 nm or less. Moreover, you may use the hollow and porous thing for which silica microparticles | fine-particles effect is expected, such as a low refractive index. Among the silica fine particles, those surface-modified by a hydrolyzable silane compound having an active energy ray reactive group are preferably used. Such 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 -Acryloxypropyldimethylmethoxysilane, γ-acryloxypropyldimethylethoxysilane, γ-acryloxypropyldimethylchlorosilane, γ-acryloxymethyltrimethoxysilane, γ-acryloxymethyltriethoxysilane, γ- Acryloxymethyltrichlorosilane, (gamma) -acryloxymethylmethyldimethoxysilane, (gamma) -acryloxymethylmethyl diethoxysilane, (gamma) -acryloxymethylmethyldichlorosilane, (gamma) -acryloxymethyldimethylmethoxysilane, (gamma) -acryloxy Methyl dimethyl ethoxysilane and (gamma) -acryloxymethyl dimethyl chlorosilane can be illustrated.

Moreover, the surface modification amount of the hydrolyzable silane compound which has an active energy ray reactive group is 0.1-10 mass% with respect to particle | grains, More preferably, it is 0.5-8 mass%, Especially preferably, it is 1-5 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 hydrolysable silane compound which has an active energy ray reactive group in presence of silica microparticles | fine-particles is mentioned, The active energy ray reactivity which by-produces at that time The hydrolyzate of the hydrolyzable silane compound having a group may cause deterioration in storage stability or deterioration in hardness, and thus should be removed.

These (1) inorganic oxide microparticles | fine-particles disperse | distributed as a primary particle to the compound containing three or more (2) (meth) acryl groups mentioned later, or (3) the compound containing one or two (meth) acryl groups. It is preferable to use a thing, and a film with favorable external appearance, such as transparency, can be obtained by existing as a primary particle.

Specifically, after 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, And a method of distilling off the original dispersant.

(2) A compound containing three or more (meth) acryl groups

The compound containing three or more (2) (meth) acryl groups of this invention is a main component of a curable component with the compound containing (1) inorganic oxide fine particles and (3) one or two (meth) acryl groups. It forms the matrix of the film obtained after hardening. The compound containing three or more (meth) acryl groups disperse | distributes the inorganic oxide microparticles | fine-particles of (1) component, and is a binder component, By this compound, it is excellent in abrasion resistance and the hardened | cured material of a high hardness is obtained.

The (meth) acryl group-containing compound of (2) component is a compound which has three or more (meth) acryl groups in a molecule | numerator, For example, trimethylol propane tri (meth) acrylate and pentaerythritol tetra (meth) acrylate , Methoxylate pentaerythritol tetra (meth) acrylate, ethoxylate pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, penta Erythritol 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 these.

These compounds may use only 1 type and 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 is 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. It forms the matrix of the film obtained after hardening.

In particular, it is a component for reducing the viscosity of a composition and at the same time, it is 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.

(3) In order for a component to reduce the viscosity of a composition, 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).

It is preferable that this (meth) acryl group containing compound has functional groups, such as a hydroxyl group and an epoxy group, in a molecule | numerator especially in order to improve adhesiveness. 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 ( Meta) acrylate, diacrylate isocyanurate, ethylene oxide modified bisphenol A di (meth) acrylate, and the like, but are not limited to these.

These compounds may use only 1 type and 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, Preferably it is 30-55 mass parts in 100 mass parts of total of (1) component, (2) component, and (3) component, The compounding quantity of (3) component is (1) component and (2 In 100 mass parts of total of a component and (3) component, it is 5-30 mass parts, Preferably it is 10-20 mass parts.

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, deteriorating a film external appearance, 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) fatty 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 An aliphatic amine represented by H ₁₃ , C ₈ H ₁₇ , and each group may be the same or different, X is a group selected from N (SO ₂ CF ₃ ) ₂ , BF ₄ , PF ₆ ). Systemic ionic compounds are used as antistatic agents having good compatibility and solubility. Moreover, it has the effect of improving dispersibility, and by adding it, can suppress aggregation and sedimentation at the time of storage, and can prevent whitening of a film irrespective of the conveyance speed of a coating line at the time of hardening of light irradiation. Among these, the aliphatic amine type ionic compound which is liquid at normal temperature (usually 5-40 degreeC, especially 25 degreeC) is especially preferable.

Wherein, R ¹ ~ R ⁴ is _{CH 3, C 2 H 5,} C 2 H 4 OCH 3, C 6 H 13, C 8 is a group selected from H _17, may each be the same or different groups. Also, X is a group selected from _{N (SO 2 CF 3) 2} , BF 4, 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 -

(4) The compounding quantity of a 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 mass parts. 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) lithium-based ionic compounds

In the present ^{invention, (5) Li + Y -} (Y is _{ClO 4, SO 2 CF 3,} SO 2 C 2 F 5, N (SO 2 CF 3) 2, N (SO 2 C 2 F 5) 2, The lithium-based ionic compound represented by BF ₄ and PF ₆ ) is used as an antistatic agent having good compatibility and solubility as well as an aliphatic amine-based ionic compound. Moreover, it has the effect of improving dispersibility, and by adding it, can suppress aggregation and sedimentation at the time of storage, and can prevent whitening of a film regardless of the conveyance speed of a coating line at the time of hardening of light irradiation.

Specific examples of the lithium-based ionic compound represented by Li ⁺ Y ^- include the following ones.

_{^{Li + ClO 4 -, Li +}} SO 2 CF 3 -, Li + SO 2 C 2 F 5 -, Li + N (SO 2 CF 3) 2 -, Li + N (SO 2 C 2 F 5) 2 -, _{^{Li + BF 4 -, Li +}} PF 6 -

The compounding quantity of (5) component is 0.1-7 mass parts with respect to a total of 100 mass parts of (1) component, (2) component, and (3) component, Preferably it is 0.2-5 mass parts, Especially preferably, it is 0.5- 4 mass parts. If the amount is too small, the antistatic effect is not obtained, and the coating may whiten during ultraviolet irradiation, and the stability is also deteriorated. If there is too much compounding quantity, hardness will fall.

When using the ionic compound of (4) and (5) in combination, compared with the case where each is used independently, it is excellent in the film formability and can provide the film which is excellent in surface smoothness and transparency compared with the case where it is no solvent, It was confirmed that adhesiveness was excellent. Moreover, the surface resistance value can be made low and the film excellent in antistatic property can be obtained.

(6) radical type photoinitiator

The composition of this invention contains (6) radical type photoinitiators. 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 Ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1- [4- (2-hydroxye Methoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl)- Benzyl] phenyl} -2-methyl-propane-1-one, oxyphenylacetic acid 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester and oxyphenylacetic acid 2- (2-hydroxyethoxy) ethyl Mixtures of esters, acylphosphine oxide derivatives, 2-methyl-1- {4- (methylthio) phenyl} -2-morpholinopropane-1-one, 4-benzoyl-4'-methyldiphenylsulfide, 2,4,6-trimethylbenzoyldiphenylphosphine 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, 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-methyl-1- {4- (methylthio) phenyl}- 2-morpholinopropane-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. When there is too little compounding quantity, sclerosis | hardenability will worsen, and when too much, adhesiveness will fall.

The photocurable resin composition of the present invention may further contain ionic compounds, silane coupling agents, polymerization inhibitors, antioxidants, ultraviolet absorbers, light stabilizers, antifoaming agents, leveling agents, and surfaces other than the components (4) and (5) as necessary. Although it does not interfere even if it contains the tension reducing agent etc. in the range which does not impair the objective of this invention, It is preferable that a solvent is not contained 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, the said (1) component is previously mixed with (2) component or (3) component, and this and the remaining component are mixed. It is desirable to.

Moreover, it is preferable to adjust these compositions so that the viscosity in 25 degreeC may be 300 mPa * s or less, especially 220 mPa * s or less. When the viscosity is too high, the coating workability deteriorates, and streaks and the like tend to occur. Moreover, it is preferable that the viscosity in 25 degreeC of this composition is 10 mPa * s or more.

The photocurable resin composition of this invention is an article which needs to provide abrasion resistance and antistatic property to the surface, specifically, the article shape | molded by the resin composition containing 50 mass% or more, especially 70-100 mass% of polycarbonate, Surfaces of optical information carriers, such as optical disks for exclusive use of reproduction, optical recording disks, magneto-optical recording disks, and more specifically, incident or incident surface of recording or reproduction beams, optical lenses, optical filters, anti-reflection films, anti-reflection films, and liquid crystal displays. By applying to a surface of various display elements such as a CRT display, a plasma display, an EL display, and the like, and forming a cured film, scratch resistance and antifouling property of these surfaces can be imparted, and an article having the cured film is scratch resistant and abrasion resistant. And excellent antistatic properties.

Specifically, the total light transmittance measured by a turbidimeter (NDH2000, manufactured by Nippon Denshoku Kogyo Co., Ltd.) is 85% or more, and Haze is 2% or less. The change rate of 8% or less, and the surface resistance value measured by an ultra-insulator (SM-8210 manufactured by Toa Denpaco Co., Ltd.) can be obtained a characteristic of 1 × 10 ¹⁵ Ω or less.

As a method of forming the film of the said photocurable resin composition, a film can be produced by the roll coat method, the spin coat method, the bar coat method, the microgravure method, etc. Among these, it coats by the microgravure method, and it irradiates by ultraviolet irradiation It is preferable to harden | cure and produce a film. 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 hardening a photocurable resin composition, the light source containing the light of the wavelength of the range of 200-450 nm normally, for example, high pressure mercury lamp, ultrahigh pressure mercury lamp, electrodeless lamp, metal halide lamp, xenon lamp, carbon arc etc. Can be used. Dose is preferably not particularly limited, but the 10 ~ 5,000mJ / cm ^2, particularly 20 ~ 2,000mJ / cm ^2. Curing by a light irradiator has a batch type and a conveyor type, but a high productivity conveyor type is preferable. Hardening time is 0.01 to 60 second normally, Preferably it is 0.1 to 10 second. Although the conveyance speed of a coating line in that case does not have a restriction | limiting in particular, The range of 0.1-40 m / min, especially 1-20 m / min is preferable. When the conveyance speed is low, there is a problem that productivity is poor, and when the conveyance speed is low, damage is likely to occur during conveyance.

The polycarbonate used for the resin composition for molding the article is preferably an aromatic polycarbonate resin prepared by reacting a dihydric phenol and a carbonate precursor by a solution method or a melting method, and as a representative example of the dihydric phenol, 2,2- Bis (4-hydroxyphenyl) propane (common name bisphenol A), 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis ( 4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, bis (4-hydroxyphenyl) sulfide, bis (4- Hydroxyphenyl) sulfone, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, 2,2-bis (4-hydroxy-3-methylphenyl) propane and 2,2'-methyl-4, 4'-biphenyldiol etc. are mentioned. Preferred dihydric phenols are bis (4-hydroxyphenyl) alkanes, with bisphenol A being particularly preferred.

Examples of the carbonate precursor include carbonyl halides, carbonate esters, haloformates, and the like, and specific examples thereof include phosgene, diphenyl carbonate, and dihaloformates of dihydric phenol.

In manufacturing a polycarbonate resin, the said dihydric phenol can be used individually or in combination of 2 or more types, A molecular weight regulator, a branching agent, a catalyst, etc. can be used as needed.

The molecular weight of the polycarbonate resin is 1.0 × 10 ⁴ to 10.0 × 10 ⁴ , represented by the viscosity average molecular weight, preferably 1.5 × 10 ⁴ to 4.5 × 10 ⁴ , and more preferably 1.8 × 10 ⁴ to 3.0 × 10 ⁴ . . The viscosity average molecular weight as used in this invention is calculated | required by inserting the specific viscosity ((eta) _sp ) calculated | required from the solution which melt | dissolved 0.7 g of polycarbonate resin at 20 degreeC in 100 ml of methylene chlorides by following Formula.

η _{sp /} c = [η] + 0.45 × [η] ² c (where [η] is the ultimate viscosity)

[η] = 1.23 × 10 ^-4 M ^0.83

c = 0.7

In addition, additives such as phosphite esters, phosphate esters, and phosphonic acid esters (0.001 to 0.1 mass%), triazoles, acetophenones, salicylic acid esters, etc. Even if the ultraviolet absorber (0.1-0.7 mass%), the low molecular weight polycarbonate of tetrabrom bisphenol A, tetrabrom bisphenol A, flame retardants (3-15 mass%), such as decabromo diphenyl ether, a coloring agent, a fluorescent brightener, etc. are mix | blended, do.

(Example)

EXAMPLES 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 (henceforth S-PETTA; silica concentration 50 mass%, silica particle diameter 30nm) which gamma-methacryloxypropyl trimethoxysilane-treated silica was disperse | distributed, 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 weight, Li ⁺ (CF ₃ SO _{2) 2} N ^- (hereinafter, LiTFSI) 1.8 mass parts, Darocure 1173 (hereinafter, D1173; 2- hydroxy-2-methyl-1-phenylpropan-1-one, a radical-based photopolymerization initiator, Ciba Specialty Chemicals's Co., Ltd., 3 mass parts), the photocurable resin composition whose viscosity in 25 degreeC is 193 mPa * s was obtained. The photocurable resin composition was added to an aromatic polycarbonate film (aromatic polycarbonate film having a viscosity average molecular weight of 2.3 × 10 ⁴ made of bisphenol A and phosgene; 140 mm in width and 92 μm in thickness) and subjected to microgravure coater method (number 200 made by Yasui Seiki Co., Ltd.). ), And a cured film was produced using a conveyor-type ultraviolet irradiation device (manufactured by Igrapix) having a 160W high-pressure mercury lamp. At that time, the conveyance speed was 2 m / min, and the integrated irradiation amount was 1,000 mJ / cm ² . Evaluation shown below was performed using the obtained transparent film. These results are shown in Table 1.

Preservation stability:

It was visually judged whether there was a sediment after 40 degreeC and 14 days, and the following reference | standard evaluated.

○: no sediment

×: With sediment

Film transparency:

The cured film was measured using a turbidity meter (NDH2000, manufactured by Nippon Denshoku Kogyo Co., Ltd.) in accordance with JIS K 7105 to evaluate the total light transmittance and Haze. As a standard of whitening, 85% or more of total light transmittance and Haze 2% or less which did not have a problem practically were made into the pass.

Scratch 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 tapered abrasion tester (using abrasion ring CS-10F), and the haze of the cured film before and after the abrasion test was measured with a turbidimeter (NDH2000, Nippon). It measured using Tenshoku Kogyo Co., Ltd., and made Haze before Haze-wear test after abrasion test as (DELTA Haze) ((DELTA Haze is good in abrasion resistance and abrasion resistance when it is 8 or less.).

Surface resistance value:

It measured in 25 degreeC and the atmosphere of 50% RH using the super insulation system (SM-8210 by Toad Denpaco Co., Ltd.).

Wet Heat Adhesion:

After standing for 24 hours in an atmosphere of 60 ° C. and 95% RH, after leaving for 24 hours at room temperature, a 10 × 10 cell was formed on the coated surface in accordance with JIS K 5400, and a cellophane tape was attached and pulled upwards. The peeling situation was confirmed.

○: no abnormality

X: There are 1 or more spaces where at least 1/3 of the spaces are peeled off

In the tapered abrasion test, ΔHaze was 4, which also showed high wear resistance. The surface resistance value was as low as 1 × 10 ¹² Ω.

Examples 2 to 8 and Comparative Examples 1 to 12

Likewise, as shown in Tables 1 and 2 below, the formulations were changed to obtain a film and to be evaluated. These results are shown in Tables 1 and 2.

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

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

HDODA: Hexanediol diacrylate

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

_{^{LiTFSI: Li + (CF 3 SO}} 2) 2 N -

D1173: Tarocure 1173, 2-hydroxy-2-methyl-1-phenylpropan-1-one, product made in Chiba Specialty Chemicals,

Claims (8)

(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 is a group selected from H _17, may be the same or different and each group. X is N (SO ₂ CF ₃₎ an ionic compound represented by the formula _2, BF _4, is a group selected from PF _6.),
^{(5) Li + Y - (} Y is _{ClO 4, SO 2 CF 3,} SO 2 C 2 F 5, N (SO 2 CF 3) 2, N (SO 2 C 2 F 5) 2, BF 4, PF 6 Ionic compounds represented by
(6) radical type photoinitiator
(1) 25-70 mass parts of (1) component, 20-70 mass parts of (2) component, and (3) component in 100 mass parts of total of (1), (2), (3) component It is this 5-30 mass parts, 0.05-4 mass parts of (4) components, 0.1-7 mass parts of (5) components with respect to 100 mass parts of total of (1), (2), (3) component, (6) Photocurable resin composition whose component is 1-8 mass parts. The photocurable resin composition according to claim 1, wherein the inorganic oxide fine particles having an average particle diameter of the component (1) of 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 photocurable resin composition of any one of Claims 1-3 which does not contain a solvent substantially and the viscosity in 25 degreeC is 300 mPa * s or less. (4), (5), and (6) component in any one of Claims 1-4 in the mixture which previously disperse | distributed (1) component to (2) component and / or (3) component. It is made by mixing, The photocurable resin composition characterized by the above-mentioned. The cured film of the photocurable resin composition in any one of Claims 1-5 is formed, the total light transmittance is 85% or more, Haze is 2% or less, and the load in the taper abrasion test by ASTMD1044. An article having a rate of change of Haze at 500 g and 100 revolutions of 8% or less and a surface resistance of 1 × 10 ¹⁵ Ω or less. The article according to claim 6, wherein the article on which the cured film is formed is molded by a resin composition containing 50% by mass or more of polycarbonate. The curable film is formed on the to-be-processed article by coating the photocurable resin composition in any one of Claims 1-5 on the to-be-processed article by the microgravure method, and hardening by ultraviolet irradiation. The manufacturing method of the article to make.