JP7226283B2 - Active energy ray-curable composition, coating agent and coated article - Google Patents

Description

TECHNICAL FIELD The present invention relates to active energy ray-curable compositions, coating agents and coated articles. More specifically, it relates to an active energy ray-curable composition, a coating agent and a coated article containing an organopolysiloxane having a polymerizable functional group, carbon nanotubes and fine silica particles.

In recent years, the emergence of flexible devices represented by organic EL is remarkable. As the substrate of this device, generally, a flexible organic resin such as polyethylene terephthalate (PET) or polyimide (PI) is often used as the substrate. However, since these organic resins have high insulating properties, their surfaces are prone to electrification, causing adhesion between films, electrostatic discharge, and adsorption of dust and dirt in the air during the manufacturing and processing processes or in products. It's a problem.

Carbon nanotubes (CNT) have various physical properties such as high electrical conductivity, thermal conductivity, and heat resistance. Application to materials that do not conduct is expected. However, due to its high cohesiveness and colorability, its application to UV-curable coating agents, especially display substrates, has been limited.
For example, Patent Documents 1 and 2 propose compositions containing carbon nanotubes and cured products thereof. However, although these cured products exhibit good conductivity, they are not suitable for display substrates that require transparency because they have light-shielding properties and coloring properties.

On the other hand, in the outermost layer of a touch panel, which is an image display device for a flexible device, a coating material that has excellent bending resistance to the extent that it can be folded in two while maintaining surface hardness, and that has good followability with the underlying substrate. is required.
As such materials, coating agents containing silica fine particles are generally known to have high surface hardness and durability. In addition, by appropriately selecting the surface-modifying functional group, particle size, etc., and adjusting the content in the composition, the silica fine particles suppress aggregation between silica fine particles in the composition and aggregation with other dispersions. good dispersion stability is expected for carbon nanotubes.
For example, Patent Literature 3 discloses that carbon nanotubes can be stably dispersed in a colloidal silica fine particle dispersion without aggregating or sedimenting. However, since the dispersion medium is water, it is difficult to develop resins and coating agents, and there is a problem that it is difficult to evaluate physical properties such as conductivity.

Japanese Patent No. 5689320 Japanese Patent No. 5268050 JP 2012-224521 A

The present invention has been made in view of the above circumstances, and provides an active energy ray-curable composition, a coating agent and a coating that provide a cured product and a coating film having excellent antistatic properties, transparency, surface hardness and flex resistance. The purpose is to provide goods.

The present inventors have made intensive studies to achieve the above object, and as a result, have found an active energy ray-curable composition containing an organopolysiloxane having a urethane bond and a (meth)acryloyloxy group, a carbon nanotube, and fine silica particles. However, they found that the above problems could be solved, and completed the present invention. In the present invention, the (meth)acryloyloxy group means an acryloyloxy group or a methacryloyloxy group.

（式中、Ｒ¹およびＲ²は、互いに独立して炭素原子数１～１０の２価の炭化水素基を表し、Ｒ³は、水素原子またはメチル基を表す。）

（式中、Ｒ⁴は、互いに独立して水素原子、ハロゲン原子で置換されていてもよい炭素原子数１～８のアルキル基、フェニル基、（メタ）アクリロイルオキシプロピル基またはグリシドキシプロピル基を表す。）
２． さらに、活性エネルギー線によりラジカルを発生する重合開始剤を含有する１記載の活性エネルギー線硬化性組成物、
３． さらに、（Ａ）成分以外の重合性不飽和化合物を含有する１または２記載の活性エネルギー線硬化性組成物、
４． １～３のいずれかに記載の活性エネルギー線硬化性組成物からなるコーティング剤、
５． ４記載のコーティング剤から製作される硬化膜、
６． 基材と、この基材の少なくとも一方の面に直接または少なくとも１種の中間層を介して積層された硬化膜とを有し、前記硬化膜が、５記載の硬化膜である被覆物品
を提供する。 That is, the present invention
1. (A) Organopolysiloxane having structural units represented by the following general formula (I) and structural units represented by the following general formula (II), (B) carbon nanotubes, and (C) activation energy containing silica fine particles a radiation curable composition,

(In the formula, R ¹ and R ² independently represent a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ³ represents a hydrogen atom or a methyl group.)

(In the formula, R ⁴ is each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms optionally substituted by a halogen atom, a phenyl group, a (meth)acryloyloxypropyl group or a glycidoxypropyl group. represents.)
2. The active energy ray-curable composition according to 1, further comprising a polymerization initiator that generates radicals by active energy rays,
3. 3. The active energy ray-curable composition according to 1 or 2, further comprising a polymerizable unsaturated compound other than the component (A),
4. A coating agent comprising the active energy ray-curable composition according to any one of 1 to 3,
5. A cured film produced from the coating agent according to 4,
6. A coated article comprising a substrate and a cured film laminated directly or via at least one intermediate layer on at least one surface of the substrate, wherein the cured film is the cured film according to 5. do.

Since the active energy ray-curable composition of the present invention provides a cured product and a coating film having excellent antistatic properties, transparency, surface hardness, and flex resistance, it can be applied to flexible devices such as organic EL, surface layers of touch panels, and the like. Useful as a coating agent.

The present invention will be specifically described below.
The active energy ray-curable composition according to the present invention is
(A) an organopolysiloxane having a structural unit represented by the following general formula (I) and a structural unit represented by the following general formula (II);
(B) carbon nanotubes,
(C) Contains silica fine particles.

[1] Component (A) The component (A) of the present invention is an organopolysiloxane having a structural unit represented by the following general formula (I) and a structural unit represented by the following general formula (II).

In formula (I), R ¹ and R ² independently represent a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ³ represents a hydrogen atom or a methyl group.
In formula (II), R ⁴ is each independently a hydrogen atom, an optionally halogen-substituted alkyl group having 1 to 8 carbon atoms, a phenyl group, a (meth)acryloyloxypropyl group or glycidoxy represents a propyl group.

The divalent hydrocarbon group having 1 to 10 carbon atoms for R ¹ and R ² may be linear, branched or cyclic, and specific examples include methylene, ethylene, trimethylene, propylene, tetramethylene, hexa linear, branched or cyclic alkylene groups such as methylene, decamethylene and cyclohexylene groups; and arylene groups such as phenylene and xylylene groups.
Among these, an alkylene group having 1 to 5 carbon atoms is preferable, an alkylene group having 1 to 4 carbon atoms is more preferable, and an ethylene group and a trimethylene group are still more preferable.

The alkyl group having 1 to 8 carbon atoms for R ⁴ may be linear, branched or cyclic, and specific examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i- Butyl, t-butyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl groups and the like, and these alkyl groups have some or all of their hydrogen atoms substituted with halogen atoms. may be
Halogen atoms include fluorine, chlorine, bromine and iodine atoms. Halogen-substituted alkyl groups include chloromethyl, 3-chloropropyl and 3,3,3-trifluoropropyl groups.
Among these, R ⁴ is preferably each independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, more preferably a methyl group or a phenyl group.

In particular, the compatibility with the polymerizable unsaturated compound, the curability of the curable composition containing the organopolysiloxane, and the hardness, crack resistance, flex resistance, and water resistance of the cured product obtained from the composition from the viewpoint of general formula (I), R ¹ is a trimethylene group, R ² is an ethylene group, R ³ is a hydrogen atom, and R ⁴ is a methyl group in general formula (II). is preferred.

The proportion of the structural unit represented by formula (I) in component (A) is preferably 10 to 50 mol%, more preferably 20 to 50 mol%. If this unit is too small, the resulting organopolysiloxane compound may have insufficient compatibility with other components. It may have poor scratch resistance, crack resistance and bending resistance.
The proportion of the structural unit represented by formula (II) is preferably 10 to 70 mol%, more preferably 20 to 60 mol%. If this unit is too small, the organopolysiloxane compound will have a high viscosity, which may be undesirable from the viewpoint of workability and processability. If it is too large, the resulting cured product may have poor hardness.

If necessary, SiO _4/2 units, R ⁴ SiO _3/2 units (R ⁴ is the same as above, hereinafter the same), R ⁴ ₂ SiO _2/2 units, R ⁵ O _1/2 units (R ⁵ represents a hydrogen atom, a methyl, ethyl, n-propyl or i-propyl group).
When these units are contained, the proportion of SiO _4/2 units in component (A) is preferably 20 mol % or less, more preferably 10 mol % or less. If it is too large, the resulting cured product may be inferior in crack resistance and flex resistance.
The proportion of R ⁴ SiO _3/2 units is preferably 40 mol % or less, more preferably 20 mol % or less. The proportion of R ⁴ ₂ SiO _2/2 units is preferably 60 mol % or less, more preferably 50 mol % or less. If the ratio of these structural units is too high, the resulting cured product may be inferior in crack resistance and flex resistance.
The ratio of R ⁵ O _1/2 units is preferably 30 mol % or less, and is effective in suppressing the condensation reaction due to the condensable functional group, and improves the crack resistance, water resistance, and weather resistance of the resulting cured product. Taking this into account, it is more preferably 10 mol % or less.
The total amount of structural units of formula (I) and formula (II) and optionally other structural units is 100 mol %.

The (A) component organopolysiloxane may be a single compound or a mixture of a plurality of compounds having different compositions.

Although the average molecular weight of the organopolysiloxane of component (A) is not particularly limited, it can be used to improve the stability of the organopolysiloxane over time and the hardness and resistance of the cured product of the active energy ray-curable composition containing the organopolysiloxane. From the viewpoint of improving flexibility, the polystyrene equivalent weight average molecular weight by gel permeation chromatography (GPC) is preferably 500 to 100,000, more preferably 700 to 10,000.

The viscosity of the organopolysiloxane of component (A) is not particularly limited, but considering workability and processability, the viscosity at 25° C. measured by a rotational viscometer is 200 to 50,000 mPa·s. is preferred, and 300 to 5,000 mPa·s is more preferred.
Furthermore, the organopolysiloxane of the component (A) has a non-volatile content of 96% by mass or more, excluding organic solvents, etc., in order to suppress the deterioration of the appearance and the deterioration of the mechanical properties due to the generation of voids when the composition is cured. is preferred.

The (A) component organopolysiloxane can be produced according to a general organopolysiloxane production method, for example, by condensing a hydrolyzable silane containing an organic group having a urethane bond and a (meth)acryloyloxy group. can be obtained.
Specific production methods include, for example, a hydrolyzable silane represented by the following formula (III), a hydrolyzable silane represented by the following formula (IV) and/or a hydrolytic condensate thereof, and if necessary and other hydrolyzable silanes and hydrolytic condensation in the presence of a catalyst to produce organopolysiloxane.

In the formula, R ¹ to R ⁴ have the same meanings as above. Each X independently represents a chlorine atom or an alkoxy group having 1 to 6 carbon atoms.
As the alkoxy group having 1 to 6 carbon atoms for X, the alkyl group therein may be linear, branched or cyclic. Specific examples thereof include methoxy, ethoxy, n-propoxy, isopropoxy, n- butoxy, t-butoxy, n-pentyloxy groups and the like.

Examples of the silane compound represented by formula (IV) include trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, triphenylmethoxysilane, triphenylethoxysilane, and the like. Moreover, hexamethyldisiloxane etc. are mentioned as these hydrolysis condensates.
The amount of these silane compounds and/or hydrolyzed condensates thereof to be added is preferably 0.5 to 3 mol, more preferably 0.5 to 2 mol, per 1 mol of the silane of formula (III).

Other hydrolyzable silanes used as necessary are not particularly limited as long as they can produce organopolysiloxane by hydrolytic condensation together with the hydrolyzable silane represented by the above formula (III). not something.
Specific examples include dimethyldimethoxysilane, diethyldimethoxysilane, diphenyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, diphenyldiethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane, and methyltrimethoxysilane. ethoxysilane, ethyltriethoxysilane, phenyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- glycidoxypropylmethyldiethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltri Alkoxysilanes such as ethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-acryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane and hydrolytic condensation thereof things are mentioned.

The amount of other hydrolyzable silanes and/or hydrolytic condensates thereof used as necessary is preferably 0.1 to 3 mol, more preferably 0, per 1 mol of the silane of formula (III). .5 to 2 mol.

The catalyst used for condensation is not particularly limited, but acidic catalysts are preferred, and specific examples include hydrochloric acid, formic acid, acetic acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid, benzoic acid, acetic acid, and lactic acid. , carbonic acid, methanesulfonic acid, trifluoromethanesulfonic acid and the like.
The amount of the catalyst to be used is not particularly limited, but considering the rapid progress of the reaction and the ease of removal of the catalyst after the reaction, the amount is 0.0002 to 0.00 per 1 mol of the total hydrolyzable silane. A range of 0.5 molar is preferred.

Water is usually added during the hydrolytic condensation. The amount ratio between the hydrolyzable silane and the water required for the hydrolytic condensation reaction is not particularly limited. Considering easiness, it is preferable to use 0.1 to 10 mol of water with respect to 1 mol of the total hydrolyzable silane.
The reaction temperature during hydrolytic condensation is not particularly limited, but in consideration of improving the reaction rate and preventing decomposition of the organic functional group of the hydrolyzable silane, -10 to 150°C is preferred. preferable.

In addition, you may use an organic solvent in the case of hydrolysis condensation. Specific examples of organic solvents include methanol, ethanol, propanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, toluene, xylene, hexane, heptane and the like.

[2] Component (B) The carbon nanotube of component (B) is not particularly limited, but may be a single-walled carbon nanotube, a multi-walled carbon nanotube in which a plurality of layers are concentrically overlapped, or a coil of these. Among them, single-walled carbon nanotubes are preferred because of their high electrical conductivity.

The carbon nanotubes of component (B) may be used as a mixture dispersed in polydimethylsiloxane or vinyl ether-terminated polydimethylsiloxane.

The carbon nanotubes of the component (B) can be obtained as commercial products. vinyl ether-terminated polydimethylsiloxane containing 10% by mass of single-walled carbon nanotubes), TUBALL MATRIX 201 (fatty acid glycidyl ester containing 10% by mass of single-walled carbon nanotubes), TUBALL MATRIX 202 (aliphatic carboxylic acid ester derivative containing 10% by mass of single-walled carbon nanotubes) , TUBALL MATRIX 204 (methacrylic acid ester derivative containing 10% by mass of single-walled carbon nanotubes), TUBALL MATRIX 301 (ethoxylated alcohol containing 10% by mass of single-walled carbon nanotubes) (both manufactured by Kusumoto Kasei Co., Ltd.), and the like.

The amount of the carbon nanotubes used as the component (B) is It is preferably 0.02 to 0.2% by mass, more preferably 0.05 to 0.1% by mass, based on the non-volatile content excluding organic solvents and the like.

[3] Component (C) Silica fine particles of component (C) are not particularly limited, but are sol-gel produced by hydrolytic condensation using tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, etc. as starting materials. silica and the like.
As the silica fine particles, porous silica fine particles, hollow silica fine particles, and composite metal oxides of aluminum, magnesium, zinc, zirconium, titanium, etc. and silicon may be used. A low refractive index effect is also expected for hollow or porous fine particles.

As the (C) component silica fine particles, those having an average particle diameter of 1 to 100 nm can be suitably used. The average particle size of the silica fine particles of component (C) is more preferably 5 to 50 nm, still more preferably 10 to 40 nm, from the viewpoint of suitably adjusting the dispersion stability of the silica fine particles and the viscosity of the curable composition.

The fine silica particles of component (C) are preferably those surface-modified with active energy ray-curable reactive groups. Such surface-modified silica fine particles have improved dispersion stability in the composition, and are fixed in the polymer matrix by irradiation with active energy rays to cause a cross-linking reaction.
Examples of surface-modified silica fine particles include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, and 3-glycidoxysilane. Examples include silica fine particles surface-treated with a silane coupling agent such as propyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane.
Further, for the purpose of further improving the dispersion stability of silica fine particles in the active energy ray-curable composition, the bending resistance and transparency of the cured product, or for the purpose of alleviating curing shrinkage, 7-octenyltrimethoxysilane, 7-octenyltriethoxysilane, 8-glycidoxyoctyltrimethoxysilane, 8-glycidoxyoctyltriethoxysilane, 8-acryloxyoctyltrimethoxysilane, 8-acryloxyoctyltriethoxysilane, 8-methacryloxysilane The surface of silica fine particles may be treated with a long-chain spacer type silane coupling agent such as octyltrimethoxysilane, 8-methacryloxyoctyltriethoxysilane.
These silane coupling agents may be used in combination of two or more if necessary, and may be used in combination with surface treatment of silica fine particles with methyltrimethoxysilane, methyltriethoxysilane, hexamethyldisilazane, or the like. .

The silica fine particles used in the present invention can be used as a dispersion in which silica fine particles are dispersed in the component (A). Also, it may be used as a composition in which silica fine particles are dispersed in other polymerizable unsaturated compounds. Such compositions are commercially available, for example, NANOCRYL C150 (dispersion in trimethylolpropane triacrylate), NANOCRYL C165 (dispersion in propoxylated pentaerythritol tetraacrylate) (both from Evonik). , SIRHDDA30%-E06, SIRHDDA30%-E01, SIRTPGDA30%-P01, and SIRTPGDA30%-P02 (all manufactured by CIK Nanotech Co., Ltd.).

In the active energy ray-curable composition of the present invention, the blending ratio of the components (A) to (C) is not particularly limited, but the slipperiness, hardness, crack resistance, and bending resistance of the resulting resin or coating are In consideration of further improving the properties, the mass ratio is preferably 0.02 to 6 parts by mass of component (B) and 50 to 150 parts by mass of component (C) with respect to 100 parts by mass of component (A). 0.5 to 5 parts by mass of component and 80 to 120 parts by mass of component (C) are more preferable.

[4] Other Components The active energy ray-curable composition of the present invention may contain, in addition to the components (A) to (C) described above, if necessary, a polymerization initiator that generates radicals by means of active energy rays. good.
The polymerization initiator is not particularly limited as long as it is an initiator that generates radical species by active energy rays. It can be appropriately selected from polymerization initiators and used.
Specific examples include benzophenone, benzyl, Michler's ketone, thioxanthone derivatives, benzoin ethyl ether, diethoxyacetophenone, benzyl dimethyl ketal, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenyl ketone, acylphosphine oxide derivatives. , 2-methyl-1-{4-(methylthio)phenyl}-2-morpholinopropan-1-one, 4-benzoyl-4'-methyldiphenylsulfide, 2,4,6-trimethylbenzoyldiphenylphosphine, etc. These may be used singly or in combination of two or more.

Commercially available photopolymerization initiators can be used, and examples of commercially available products include Omnirad 1173, Omnirad MBF, Omnirad 127, Omnirad 184, Omnirad 369, Omnirad 379, Omnirad 379EG, Omnirad 651, Omnirad 754, and Omnirad 784. , Omnirad 819, Omnirad 819DW, Omnirad 907, Omnirad 2959, and Omnirad TPO (all manufactured by IGM Resins BV).

When a photopolymerization initiator is blended, the amount used should be 0.1 to 20% by mass is preferable.

Moreover, the active energy ray-curable composition of the present invention may further contain other polymerizable unsaturated compounds in addition to the component (A).
Other polymerizable unsaturated compounds include 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, ethylene oxide-modified bisphenol A di(meth)acrylate, trimethylolpropane tri(meth)acrylate. , pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, pentaerythritol tri(meth)acrylate, 3-(meth)acryloyloxyglycerol mono(meth)acrylate, urethane Acrylate, epoxy acrylate, ester acrylate and the like. These may be used individually by 1 type, or may use 2 or more types together.

When other polymerizable unsaturated compounds are used, the amount used is preferably 1 to 1,000 parts by weight per 100 parts by weight of the organopolysiloxane of component (A).

The active energy ray-curable composition of the present invention further comprises metal oxide fine particles, a silicone resin, a silane coupling agent, a diluent solvent, a plasticizer, a filler, a sensitizer, a light absorber, a light stabilizer, and a polymerization inhibitor. Additives such as agents, heat ray reflectors, antistatic agents, antioxidants, antifouling agents, water repellent agents, antifoaming agents, coloring agents, thickeners, leveling agents, etc. It may be included as long as it does not damage it.

[5] Production method The active energy ray-curable composition of the present invention is obtained by uniformly mixing the components described above according to a conventional method.
Examples of devices that can be used for mixing include three-roll mills, two-roll mills, side grinders, colloid mills, Gaurin monogenizers, disper, etc., and devices based on these can be used. I don't mind. Alternatively, manual mixing may be performed using a spatula, a stirring rod, or the like.

[6] Coating Agents and Coated Articles The active energy ray-curable composition of the present invention described above can be suitably used as a coating agent, and is directly or at least one other layer on at least one surface of a substrate. A coated article in which a film is formed can be obtained by applying the composition through the (intermediate layer) and curing it.
Moreover, the cured product of the active energy ray-curable composition of the present invention can also be suitably used as a film.

Examples of the base material include, but are not limited to, plastic moldings, wood-based products, ceramics, glass, metals, and composites thereof.
In addition, the surface of these substrates has been treated with chemical conversion treatment, corona discharge treatment, plasma treatment, acid or alkaline solution, and decorative plywood coated with a different type of paint on the surface of the base material. can also be used.

Furthermore, the substrate surface on which other functional layers have been formed in advance may be coated with the coating agent of the present invention. A shielding layer and the like may be mentioned, and any one layer or a plurality of layers thereof may be formed in advance on the substrate.

The coated article has a surface on which a coating film made of the coating agent of the present invention is formed, and further a deposition layer by a CVD (chemical vapor deposition) method, a hard coat layer, an antirust layer, a gas barrier layer, a waterproof layer, and a heat ray shielding layer. It may be coated with one or more layers such as a layer, an antifouling layer, a photocatalyst layer, an antistatic layer, and the like.
Furthermore, the coated article has a hard coat layer, an antirust layer, a gas barrier layer, a waterproof layer, a heat ray shielding layer, an antifouling layer, It may be coated with one or more layers such as a photocatalyst layer and an antistatic layer.

The coating agent of the present invention is applied to the surfaces of articles whose surfaces require scratch resistance and abrasion resistance, especially various display elements such as liquid crystal displays, CRT displays, plasma displays, and EL displays. By forming a cured film, it is possible to impart antistatic properties, scratch resistance, abrasion resistance, and flex resistance to these surfaces.
The method of applying the coating agent may be appropriately selected from known methods, and various coating methods such as bar coater, brush coating, spraying, immersion, flow coating, roll coating, curtain coating, spin coating, and knife coating may be used. can be used.

As the light source for curing the active energy ray-curable composition (coating agent), a light source containing light having a wavelength in the range of 200 to 450 nm, such as a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a xenon lamp, carbon An arc lamp etc. are mentioned. Although the irradiation dose is not particularly limited, it is preferably 10 to 5,000 mJ/cm ² , more preferably 20 to 1,000 mJ/cm ² .
The curing time is usually 0.5 seconds to 2 minutes, preferably 1 second to 1 minute.

The film thickness of the cured film using the active energy ray-curable composition is preferably 0.01 to 50 μm, more preferably 1 to 20 μm, even more preferably 5 to 15 μm, in consideration of transparency.

Hereinafter, the present invention will be described more specifically with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples.
In the following, the non-volatile content is a value measured according to JIS K 5601-1-2:2008. The weight average molecular weight is a polystyrene-equivalent value measured by GPC (gel permeation chromatography, HLC-8220 manufactured by Tosoh Corporation) using tetrahydrofuran (THF) as a developing solvent. Viscosity is the value at 25° C. with a rotational viscometer.

[1] Synthesis of organopolysiloxane (A-1) [Synthesis Example 1]
1,285.6 g (4.0 mol) of the compound represented by the following formula (V) synthesized with reference to the method described in Example 1 of JP-A-2010-189294, 360.7 g of dimethyldimethoxysilane ( 3.0 mol), 487.1 g (3.0 mol) of hexamethyldisiloxane, and 8.6 g of methanesulfonic acid were mixed in a reactor. C. for 4 hours. 43.0 g of Kyoward 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) was added and neutralized by stirring for 2 hours. Volatile components such as methanol were distilled off under reduced pressure, toluene and mirabilite solution were added, and after washing with water, toluene was distilled off and pressure filtration was performed.
The resulting organopolysiloxane (A-1) had a viscosity of 1,210 mPa·s, a nonvolatile content of 98.4% by mass, and a weight average molecular weight of 1,380.
As a result of calculation from the measured values of the NMR spectrum, the ratio of the structural unit of formula (I) was 30 mol%, the ratio of the structural unit of formula (II) was 23 mol%, and the ratio of (CH ₃ ) ₂ SiO _2/2 units. was 46 mol % and the proportion of CH ₃ O _1/2 units was 1 mol %.

[2] Production of active energy ray-curable composition (coating composition) [Examples 1-1 to 1-8, Comparative Examples 1-1 to 1-8]
Organopolysiloxane (A-1) obtained in Synthesis Example 1, TUBALL MATRIX 601 (polydimethylsiloxane containing 10% by mass of single-walled carbon nanotubes, manufactured by Kusumoto Kasei Co., Ltd.), NANOCRYL C150 (silica particles with a particle diameter of 20 nm 50 wt% trimethylolpropane triacrylate (TMPTA) dispersion of Evonik), NANOCRYL C165 (50 wt% propoxylated pentaerythritol tetraacrylate (PPTTA) dispersion of silica particles with a particle size of 20 nm, Evonik) , Omnirad 1173 (radical photopolymerization initiator, manufactured by IGM Resins B.V.), and 1,6-hexanediol diacrylate (HDDA, manufactured by Osaka Organic Chemical Industry Co., Ltd.) in Table 1. Part) to prepare a coating agent.

[3] Characterization of coated articles [Examples 2-1 to 2-8, Comparative Examples 2-1 to 2-8]
The compositions obtained in Examples 1-1 to 1-8 and Comparative Examples 1-1 to 1-8 were coated on a PET film (Cosmo Shine A4300, manufactured by Toyobo Co., Ltd.) using a bar coater. It was applied to a thickness of 10 μm, irradiated with light from a high-pressure mercury lamp so that the cumulative irradiation dose was 600 mJ/cm ² , and cured to produce a coated article.
The appearance of each cured film of the coated article was observed, and surface resistance, haze, adhesion, pencil hardness and bending resistance were evaluated. Table 2 shows the results.
(1) Observation of Appearance When a lump was visually observed on the surface due to agglomeration or the like, it was judged as NG. In addition, when the appearance was NG, the evaluation of the physical properties shown below was discontinued.
(2) Surface resistance value The surface resistance value was measured using a resistivity meter (Hiresta UP MCP-HT450, manufactured by Mitsubishi Chemical Corporation) in accordance with JIS K6911 at 20 to 26°C and humidity of 40 to 50% RH. Measured under conditions.
(3) Haze (cloudiness)
Haze was measured using a turbidity meter (NDH2000, manufactured by Nippon Denshoku Industries Co., Ltd.) according to JIS K-7136.
(4) Adhesion Test A cross-cut test with 25 squares was conducted according to JIS K5600-5-6 to evaluate the adhesion between the PET film and the cured film. It was expressed as (the number of squares remaining without peeling)/25.
(5) Pencil hardness Measured with a load of 750 g according to JIS K5600-5-4.
(6) Bending resistance Measured using a cylindrical mandrel (type 1) in accordance with JIS K5600-5-1, regarding bending resistance, OK for coated articles that did not crack in the 2 mmφ test, crack The coated article in which this occurred was evaluated as NG.

As shown in Table 2, of Examples 2-1 to 2-8 obtained by curing the active energy ray-curable compositions (coating agents) obtained in Examples 1-1 to 1-8. It can be seen that the cured film has antistatic properties, transparency, surface hardness, and flex resistance.

Claims (7)

(A) an organopoly having 46 to 60 mol% of structural units represented by the following general formula (I) , structural units represented by the following general formula (II) and structural units represented by the following general formula (V) An active energy ray-curable composition comprising siloxane, (B) carbon nanotubes, and (C) fine silica particles.

(In the formula, R ¹ and R ² independently represent a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ³ represents a hydrogen atom or a methyl group.)

(In the formula, each R ⁴ independently represents an alkyl group having 1 to 8 carbon atoms.)

(In the formula, R ⁴ is the same as above.) The mixing ratio of components (A) to (C) is 0.02 to 6 parts by mass of component (B) and 50 to 150 parts by mass of component (C) per 100 parts by mass of component (A). Active energy ray-curable composition. 3. The active energy ray-curable composition according to claim 1 , further comprising a polymerization initiator that generates radicals upon exposure to active energy rays. 4. The active energy ray-curable composition according to any one of claims 1 to 3, further comprising a polymerizable unsaturated compound other than component (A). A coating agent comprising the active energy ray-curable composition according to any one of claims 1 to 4 . A cured film made from the coating agent according to claim 5 . having a substrate and a cured film laminated directly or via at least one intermediate layer on at least one surface of the substrate;
A coated article, wherein the cured film is the cured film according to claim 6 .