JP5157046B2 - Antistatic curable composition and cured film thereof - Google Patents

Description

  The present invention relates to a curable composition and a cured film thereof. More specifically, it has excellent coating properties and various base materials [for example, plastic (polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin. , Norbornene resins, etc.), metal, wood, paper, glass, slate, etc.], excellent antistatic properties and transparency on the surface of the substrate, high hardness and high refractive index and resistance The present invention relates to a curable composition capable of forming a coating film having excellent scratch resistance and adhesion to a substrate and a low refractive index layer, and a cured film thereof.

In recent years, it has excellent coating properties as a protective coating material for preventing scratches (scratching) on various substrate surfaces and preventing contamination; adhesives and sealing materials for various substrates; and a binder material for printing inks. Forms a cured film with excellent hardness, scratch resistance, abrasion resistance, low curl, adhesion, transparency, chemical resistance, antistatic properties, and coating surface appearance on the surface of various substrates There is a need for curable compositions.
In addition to the above requirements, curable compositions capable of forming a cured film having a high refractive index are required in addition to the above requirements in applications of antireflection films such as film-type liquid crystal elements, touch panels, and plastic optical components.

  In order to satisfy such a demand, various compositions have been proposed. The composition has excellent coating properties as a curable composition, and has a high hardness and a high refractive index when used as a cured film. It has excellent scratch resistance and adhesion to the substrate and the low refractive index layer used in the laminate described later. Furthermore, when the laminate is formed by laminating a low refractive index film on the cured film, the low reflectance is obtained. At the present time, it has not yet been obtained that has the properties of having antistatic properties and transparency.

  For example, Patent Document 1 describes a conductive coating agent composed of ultrafine powder of a conductive filler and an ultraviolet curable resin as a binder, and this coating agent forms a coating cured film without increasing the temperature. It is possible to easily form a conductive coating cured film on a transparent substrate having no heat resistance. As the conductive filler, it is described that titanium oxide doped with antimony is particularly preferable in terms of dispersibility and low haze. And it is described using an acrylic resin, a urethane resin, or a silicone resin as an ultraviolet curable resin. However, there is no description suggesting that it is preferable to use a urethane resin to improve the adhesion to the substrate. Further, the conductive coating agent described in Patent Document 1 does not contain a solvent.

  Patent Document 2 includes a (meth) acrylic acid ester mixture (A), a photopolymerization initiator (B), an ethylenically unsaturated group-containing urethane oligomer (C), a colloidal silica sol (D), and a diluent (E). A photosensitive resin composition for a hard coat agent and a hard coat film comprising the same are described, and it is described that the obtained film has good pencil hardness, curl, and adhesion to a substrate. However, the inorganic particles ((D) above) used in the examples are only silica particles, and the silica particles are not subjected to surface modification of the particles. Moreover, since the silica particle is used, electroconductivity is not provided.

  Patent Documents 3 and 4 disclose a curable composition containing tin-containing indium oxide (ITO) particles, and a cured film (laminated body) having high conductivity obtained by curing the composition.

JP, 7-196956, A Claims 1, 4, 5, paragraph number 0022, Table 1 JP, 2002-233501, A Claim, paragraph number 0037 JP-A-6-232586 JP 7-242843 A

The present invention has been made in view of the above-mentioned problems, has excellent coating properties, has high hardness and high refractive index on the surface of various substrates, and has scratch resistance, substrate and low resistance. It aims at providing the curable composition which can form the coating film (coating film) excellent in adhesiveness with a refractive index layer, and the hardened | cured material excellent in antistatic property and transparency.
That is, in the past, high conductivity was achieved by using only a large amount of expensive tin-containing indium oxide (ITO) particles as described in Patent Document 3, but tin-containing indium oxide (ITO) ) Since the particle content is large, there are problems such as a decrease in transmittance and an increase in haze. Furthermore, tin-containing indium oxide (ITO) particles alone could not achieve a high refractive index exceeding 1.65. An object of this invention is to provide the curable composition which can form the cured film which can achieve high refractive index, high transparency, and the outstanding antistatic function simultaneously.

  In order to achieve the above object, the inventors of the present invention have made extensive researches and combined tin-containing indium oxide (ITO) particles with oxide particles of a specific element and an organic compound containing a polymerizable unsaturated group. By using a curable composition containing particles, it has excellent antistatic properties and transparency even when the ITO content is reduced, and has a higher refractive index than that of tin-containing indium oxide (ITO) particles alone. The present inventors have found that a film can be formed and completed the present invention.

The present invention provides the following curable composition, a cured film thereof, and a method for producing the cured film.
[1] The following components (A) to (D):
(A) Tin-containing indium oxide fine particles (B) Oxide particles (Ba) of at least one element selected from the group consisting of zirconium, titanium, aluminum, cerium, tin and zinc, and an organic compound containing a polymerizable unsaturated group Particles formed by bonding (Bb) (C) A compound having two or more polymerizable unsaturated groups in the molecule (D) A curable composition containing a photopolymerization initiator.
[2] The total of the components (A) to (D) is 100% by mass, the component (A) is 7 to 40% by mass, and the component (B) is blended at a rate of 20 to 60% by mass. The curable composition according to the above [1].
[3] The curable composition according to the above [1] or [2], wherein a primary particle diameter of the tin-containing indium oxide fine particles is within a range of 1 to 20 nm.
[4] The organic compound containing a polymerizable unsaturated group (Bb) described above in any one of [1] to [3] having a group represented by the following formula (1) in addition to the polymerizable unsaturated group. Curable composition.
-Y-C (= V) -NH- (1)
[In the formula (1), Y represents NH, O (oxygen atom) or S (sulfur atom), and V represents O or S. ]
[5] A cured film obtained by curing the curable composition according to any one of [1] to [4].
[6] The cured film according to the above [5], which has a surface resistance value of 1 × 10 ¹² Ω / □ or less.
[7] A method for producing a cured film, comprising a step of irradiating the curable composition according to any one of [1] to [4] with radiation to cure the composition.

  According to the present invention, it has excellent coating properties, and has a high hardness and a high refractive index on the surface of various substrates, as well as antistatic properties, a substrate, a low refractive index layer, other hard coat layers and the like. The curable composition which can form the coating film (coating film) excellent in adhesiveness and transparency, and its cured film can be provided.

Hereinafter, embodiments of the curable composition, the cured film, and the laminate of the present invention will be specifically described.
I. Curable composition The curable composition of the present invention (hereinafter sometimes referred to as "the composition of the present invention")
(A) Tin-containing indium oxide fine particles (hereinafter sometimes referred to as “tin-containing indium oxide particles (A)” or “(A) component”),
(B) An oxide particle (Ba) of at least one element selected from the group consisting of zirconium, titanium, aluminum, cerium, tin and zinc is bonded to an organic compound (Bb) containing a polymerizable unsaturated group. Particles (hereinafter sometimes referred to as “reactive particles (B)” or “component (B)”),
(C) a compound containing two or more polymerizable unsaturated groups in the molecule (hereinafter, also referred to as “polymerizable unsaturated group-containing compound (C)” or “(C) component”)), and (D) light Polymerization initiator (hereinafter sometimes referred to as “photopolymerization initiator (D)” or “(D) component”)
It is characterized by containing.

Hereinafter, each structural component of the curable composition of this invention is demonstrated concretely.
1. Tin-containing indium oxide fine particles (A)
The tin-containing indium oxide fine particles (A) used in the present invention are components for imparting conductivity (antistatic properties) to a cured film obtained by curing the composition of the present invention.

  The tin-containing indium oxide fine particles (A) used in the present invention are not particularly limited, but are preferably powdery or solvent-dispersed sol. In the case of a solvent dispersion sol, the dispersion medium is preferably an organic solvent from the viewpoint of compatibility with other components and dispersibility. Examples of such an organic solvent include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, and γ-butyrolactone. , Esters such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbons such as benzene, toluene and xylene; dimethylformamide and dimethylacetamide And amides such as N-methylpyrrolidone. Of these, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene and xylene are preferred.

The primary particle diameter of the tin-containing indium oxide particles (A) is preferably in the range of 1 to 20 nm, and more preferably in the range of 5 to 15 nm. When the primary particle diameter exceeds 20 nm, the transparency when cured is reduced, or the surface state when coated is likely to deteriorate. Various surfactants and amines may be added to improve the dispersibility of the particles.
The primary particle diameter of the tin-containing indium oxide particles (A) can be measured, for example, as the number average particle diameter by observation with a transmission electron microscope. When the particles are not spherical, the average of the major axis and the minor axis is the particle diameter, and when the ratio of the major axis / minor axis is 2 or more, the minor axis is the particle diameter.

  The shape of the tin-containing indium oxide particles (A) is spherical, hollow, porous, rod-like, plate-like, fibrous, or indeterminate, and preferably spherical. The usage form of the tin-containing indium oxide particles (A) can be used in a state of being dispersed in a dry powder, water or an organic solvent. For example, a dispersion of fine oxide particles known in the art as the solvent dispersion sol of the above tin-containing indium oxide can be directly used. In particular, the use of a solvent-dispersed sol of tin-containing indium oxide particles is preferred in applications that require excellent transparency in the cured product.

Examples of the solvent-dispersed sol of tin-containing indium oxide include, for example, trade name: Hout Foam NID-20 (primary particle size: 13 nm; isopropanol dispersion), manufactured by C-I Kasei Co., Ltd. Primary particle size: 25 nm; ethanol dispersion), trade name: Pastoran (primary particle size: 30 nm; methanol dispersion) manufactured by Mitsui Mining Co., Ltd.
As an aqueous dispersion sol of tin-containing indium oxide, trade name: Pastoran (primary particle diameter: 30 nm) manufactured by Mitsui Kinzoku Mine Co., Ltd. can be exemplified.
Examples of the tin-containing indium oxide powder include products manufactured by Fuji Chemical Co., Ltd., Mitsui Metal Mine Co., Ltd., Mitsubishi Materials Corporation.

The compounding amount of the component (A) in the composition of the present invention is usually in the range of 7 to 40% by mass, preferably 10 to 40% by mass, with the total of components (A) to (D) as 100% by mass. Within range. When the content of the component (A) is less than 7% by mass, sufficient antistatic properties may not be obtained, and when it exceeds 40% by mass, the transparency of the resulting cured film may be impaired. is there.
In addition, the quantity of (A) component means solid content, and when the (A) component is used with the form of a solvent dispersion | distribution sol, the quantity of a solvent is not included in the compounding quantity.

2. Reactive particles (B)
The reactive particles (B) constituting the component (B) of the present invention are oxide particles of at least one element selected from the group consisting of zirconium, titanium, aluminum, cerium, tin and zinc (hereinafter referred to as “oxide particles”). (Ba) ") and an organic compound containing a polymerizable unsaturated group (hereinafter sometimes referred to as" organic compound (Bb) ") (preferably, a group containing the group represented by the formula (1)) Reactive particles obtained by reacting an organic compound).
By using the reactive particles (B), good scratch resistance and high transparency can be maintained, and the resulting cured film can have a high refractive index.

(1) Oxide particles (Ba)
The oxide particles (Ba) used in the present invention are at least one element selected from the group consisting of zirconium, titanium, aluminum, cerium, tin and zinc, from the viewpoint of the colorlessness of the cured film of the resulting curable composition. Oxide particles.

  Examples of these oxide particles (Ba) include particles of alumina, zirconia, titanium oxide, zinc oxide, tin oxide, cerium oxide, and the like. Among them, alumina and zirconia particles are preferable from the viewpoint of high hardness, and zirconia is preferable from the viewpoint of scratch resistance. These can be used alone or in combination of two or more. Furthermore, the oxide particles (Ba) are preferably in the form of powder or solvent dispersion sol. In the case of a solvent dispersion sol, the dispersion medium is preferably an organic solvent from the viewpoint of compatibility with other components and dispersibility. Examples of such an organic solvent include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, and γ-butyrolactone. , Esters such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbons such as benzene, toluene and xylene; dimethylformamide and dimethylacetamide And amides such as N-methylpyrrolidone. Of these, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene and xylene are preferred.

The number average particle diameter of the oxide particles (Ba) is preferably 0.001 μm to 2 μm, more preferably 0.001 μm to 0.2 μm, and particularly preferably 0.001 μm to 0.1 μm. When the number average particle diameter exceeds 2 μm, the transparency when cured is lowered, or the surface state when it is coated tends to deteriorate. Various surfactants and amines may be added to improve the dispersibility of the particles.
The number average particle diameter of the oxide particles (Ba) can be measured by, for example, a dynamic light scattering particle size distribution measuring apparatus manufactured by Horiba, Ltd.

  Moreover, as an aqueous dispersion product of alumina, product names manufactured by Nissan Chemical Industries, Ltd .: Alumina sol-100, -200, -520; As an isopropanol dispersion product of alumina, product names manufactured by Sumitomo Osaka Cement Co., Ltd .: AS- As a toluene dispersion product of alumina, manufactured by Sumitomo Osaka Cement Co., Ltd. Product name: AS-150T; As a zirconia toluene dispersion product, manufactured by Sumitomo Osaka Cement Co., Ltd. Product name: HXU-110JC; Alumina, titanium oxide As a powder and solvent dispersion such as tin oxide, zinc oxide, etc., manufactured by CI Kasei Co., Ltd. Product name: Nanotech; As an aqueous dispersion sol of tin oxide containing antimony, manufactured by Ishihara Sangyo Co., Ltd. Product name: SN-100D ; As ITO powder, product manufactured by Mitsubishi Materials Corporation; As cerium oxide aqueous dispersion, manufactured by Taki Chemical Co., Ltd. : Nidoraru, and the like can be given.

The oxide particles (Ba) have a spherical shape, a hollow shape, a porous shape, a rod shape, a plate shape, a fiber shape, or an indefinite shape, and preferably a spherical shape. The specific surface area of the oxide particles (Ba) (by the BET specific surface area measurement method using nitrogen) is preferably 10 to 1000 m ² / g, and more preferably 100 to 500 m ² / g. These oxide particles (Ba) can be used in a dry state, or dispersed in water or an organic solvent. For example, a dispersion of fine oxide particles known in the art as a solvent dispersion sol of the above oxide can be used directly. In particular, use of a solvent-dispersed sol of an oxide is preferable in applications that require excellent transparency in a cured product.

  The refractive index of the oxide particles (Ba) (the refractive index of 589 nm (Na-D line), measurement temperature 25 ° C.) is usually in the range of 1.2 to 3.0, preferably 1.3 to 2.5, More preferably, it is 1.4-2.2. The refractive index of the cured film can be set in an appropriate range by selecting the type of oxide particles according to the use of the obtained cured film.

(2) Organic compound (Bb)
The organic compound (Bb) used in the present invention is a compound containing a polymerizable unsaturated group in the molecule, and further a group [—Y—C (= V) —NH—] represented by the formula (1). It is preferable that it is a specific organic compound containing. Further, it includes a [—O—C (═O) —NH—] group, and further includes a [—O—C (═S) —NH—] group and a [—S—C (═O) —NH—] group. It is preferable that at least one of these is included. Moreover, it is preferable that this organic compound (Bb) is a compound which has a silanol group in a molecule | numerator, or a compound which produces | generates a silanol group by hydrolysis.

(I) Polymerizable unsaturated group The polymerizable unsaturated group contained in the organic compound (Bb) is not particularly limited, and examples thereof include acryloyl group, methacryloyl group, vinyl group, propenyl group, butadienyl group, styryl group, and ethynyl. Preferred examples include a group, a cinnamoyl group, a maleate group and an acrylamide group.
This polymerizable unsaturated group is a structural unit that undergoes addition polymerization with active radical species.

(Ii) The group represented by the formula (1) The group [—Y—C (═V) —NH—] represented by the formula (1) contained in the specific organic compound is specifically [—O—C (═O) —NH—], [—O—C (═S) —NH—], [—S—C (═O) —NH—], [—NH—C (═O) —NH—]. , [—NH—C (═S) —NH—], and [—S—C (═S) —NH—]. These groups can be used individually by 1 type or in combination of 2 or more types. Among them, from the viewpoint of thermal stability, [—O—C (═O) —NH—] group, [—O—C (═S) —NH—] group and [—S—C (═O) — It is preferable to use in combination with at least one of the NH-] groups.
The group [—Y—C (═V) —NH—] represented by the formula (1) generates an appropriate cohesive force due to hydrogen bonding between molecules, and has excellent mechanical strength and group when cured. It is considered that it gives properties such as adhesion to the material and heat resistance.

(Iii) Silanol group or group that generates a silanol group by hydrolysis The organic compound (Bb) is a compound having a silanol group in the molecule (hereinafter sometimes referred to as “silanol group-containing compound”) or a silanol group by hydrolysis. It is preferable that it is a compound (hereinafter, sometimes referred to as “silanol group-generating compound”). Examples of such a silanol group-forming compound include compounds in which an alkoxy group, an aryloxy group, an acetoxy group, an amino group, a halogen atom, and the like are bonded to a silicon atom. An alkoxy group or an aryloxy group is bonded to a silicon atom. Bonded compounds, that is, alkoxysilyl group-containing compounds or aryloxysilyl group-containing compounds are preferred.
The silanol group-generating site of the silanol group or the silanol group-generating compound is a structural unit that binds to the oxide particles (Ba) by a condensation reaction or a condensation reaction that occurs following hydrolysis.

(Iv) Preferred Embodiment As a preferred specific example of the organic compound (Bb), for example, a compound represented by the following formula (2) can be mentioned.

In the formula, R ¹ and R ² may be the same or different, but are a hydrogen atom or an alkyl group or aryl group having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, butyl, octyl, phenyl, A xylyl group etc. can be mentioned. In the formula, U represents O (oxygen atom) or S (sulfur atom). Here, p is an integer of 1 to 3.
Examples of the group represented by [(R ¹ O) _p R ² _3-p Si-] include a trimethoxysilyl group, a triethoxysilyl group, a triphenoxysilyl group, a methyldimethoxysilyl group, a dimethylmethoxysilyl group, and the like. Can be mentioned. Of these groups, a trimethoxysilyl group or a triethoxysilyl group is preferable.
R ³ is a divalent organic group having an aliphatic or aromatic structure having 1 to 12 carbon atoms, and may contain a chain, branched or cyclic structure.
R ⁴ is a divalent organic group, and is usually selected from divalent organic groups having a molecular weight of 14 to 10,000, preferably a molecular weight of 76 to 500.
R ⁵ is a (q + 1) -valent organic group, and is preferably selected from a chain, branched or cyclic saturated hydrocarbon group and unsaturated hydrocarbon group.
Z represents a monovalent organic group having a polymerizable unsaturated group in the molecule that undergoes an intermolecular crosslinking reaction in the presence of an active radical species. Moreover, q is preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and particularly preferably an integer of 1 to 5.

  For the synthesis of the organic compound (Bb) used in the present invention, for example, a method described in JP-A-9-100111 can be used.

  The amount of the organic compound (Bb) used in the production of the reactive particles (B) is preferably 1 to 95% by mass, with the total of the oxide particles (Ba) and the organic compound (Bb) being 100% by mass. Yes, more preferably 2 to 90% by mass. When the amount of the organic compound (Bb) is less than 1% by mass, the dispersibility of the reactive particles (B) in the composition is not sufficient, and the transparency and scratch resistance of the resulting cured product are not sufficient. When the amount of the organic compound (Bb) exceeds 95% by mass, the organic compound (Ba) becomes excessive.

The amount of component (B) in the composition of the present invention is preferably 20 to 60% by mass, more preferably 30 to 60% by mass, with the total of components (A) to (D) as 100% by mass. When the amount is less than 20% by mass, a material having a high refractive index may not be obtained. When the amount exceeds 60% by mass, the film formability may be insufficient.
The amount of the reactive particles (B) means a solid content, and when the reactive particles (B) are used in the form of a solvent-dispersed sol, the blending amount does not include the amount of the solvent.

3. Polymerizable unsaturated group-containing compound (C)
The compound used in the present invention having two or more polymerizable unsaturated groups in the molecule (hereinafter sometimes referred to as “polymerizable unsaturated group-containing compound (C)” or “(C) component”) has a composition. It is suitably used for enhancing the film formability of objects. The compound (C) is not particularly limited as long as it contains two or more polymerizable unsaturated groups in the molecule, and examples thereof include melamine acrylates, (meth) acrylic esters, and vinyl compounds. . Of these, (meth) acrylic esters are preferred.

Specific examples of the compound (C) used in the present invention are listed below.
(Meth) acrylic esters include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) Acrylate, dipentaerythritol hexa (meth) acrylate, glycerin tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethylene glycol di (meth) acrylate, 1,3-butanediol di ( (Meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate, and starting alcohols thereof Poly (meth) acrylates of adducts with ethylene oxide or propylene oxide, oligoesters (meth) acrylates having two or more (meth) acryloyl groups in the molecule, oligoethers (meth) acrylates, oligourethanes (meth) Examples include acrylates and oligoepoxy (meth) acrylates. Among these, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, and ditrimethylolpropane tetra (meth) acrylate are preferable.

  Examples of vinyl compounds include divinylbenzene, ethylene glycol divinyl ether, diethylene glycol divinyl ether, and triethylene glycol divinyl ether.

  As a commercial item of such a polymerizable unsaturated group containing compound (C), for example, Sanwa Chemical Co., Ltd. product name: Nikarac MX-302, Toagosei Co., Ltd. product name: Aronix M-400, M-408, M-450, M-305, M-309, M-310, M-315, M-320, M-350, M-360, M-208, M-210, M-215, M- 220, M-225, M-233, M-240, M-245, M-260, M-270, M-1100, M-1200, M-1210, M-1310, M-1600, M-221, M-203, TO-924, TO-1270, TO-1231, TO-595, TO-756, TO-1343, TO-902, TO-904, TO-905, TO-1330, Nippon Kayaku Co., Ltd. Product name: KAYARAD D-310, D-330, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DN-0075, DN-2475, SR-295, SR-355, SR-399E, SR-494 SR-9041, SR-368, SR-415, SR-444, SR-454, SR-492, SR-499, SR-502, SR-9020, SR-9035, SR-111, SR-212, SR -213, SR-230, SR-259, SR-268, SR-272, SR-344, SR-349, SR-601, SR-602, SR-610, SR-9003, PET-30, T-1420 , GPO-303, TC-120S, HDDA, NPGDA, TPGDA, PEG400DA, MANDA, HX- 20, HX-620, R-551, R-712, R-167, R-526, R-551, R-712, R-604, R-684, TMPTA, THE-330, TPA-320, TPA- 330, KS-HDDA, KS-TPGDA, KS-TMPTA, Kyoeisha Chemical Co., Ltd. product name: Light Acrylate PE-4A, DPE-6A, DTMP-4A and the like.

  The amount of component (C) in the composition of the present invention is preferably 1 to 70% by mass, more preferably 10 to 60% by mass, with the total of components (A) to (D) being 100% by mass. preferable.

4). Photopolymerization initiator (D)
In the composition of this invention, a photoinitiator (D) is mix | blended with the said tin containing indium oxide microparticles | fine-particles (A), reactive particle | grains (B), and a polymerizable unsaturated group containing compound (C).
Examples of the photopolymerization initiator (D) include general compounds such as a compound that generates cationic species by radiation (light) irradiation and a compound that generates active radical species by radiation (light) irradiation (radiation (photo) polymerization initiator). Can be mentioned.

As a compound which generates a cationic species by light irradiation, for example, an onium salt having a structure represented by the following formula (3) can be cited as a preferred example.
This onium salt is a compound that releases a Lewis acid by receiving light.
_{^{[R 9 a R 10 b R}} 11 c R 12 d W] e + [ML e + f] e- (3)
(In the formula (3), the cation is an onium ion, W is S, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, or N≡N—, and R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are the same or different organic groups, a, b, c and d are each an integer of 0 to 3, and (a + b + c + d) is equal to the valence of W. M is , A metal or metalloid constituting the central atom of the halide complex [ML _{e + f} ], for example, B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co, etc. L is a halogen atom such as F, Cl, Br, etc., e is the net charge of the halide complex ion, and f is the valence of M. )

Specific examples of the anion (ML _{e + f} ) in the above formula (3) include tetrafluoroborate (BF ₄ ⁻ ), hexafluorophosphate (PF ₆ ⁻ ), hexafluoroantimonate (SbF ₆ ⁻ ), hexafluoroarce. Nate (AsF ₆ ⁻ ), hexachloroantimonate (SbCl ₆ ⁻ ) and the like.

An onium salt having an anion represented by the formula [ML _f (OH) ⁻ ] can also be used. Furthermore, perchlorate ion (ClO ₄ ⁻ ), trifluoromethane sulfonate ion (CF ₃ SO ₃ ⁻ ), fluorosulfonate ion (FSO ₃ ⁻ ), toluene sulfonate ion, trinitrobenzene sulfonate anion, trinitrotoluene sulfonate An onium salt having another anion such as an acid anion may be used.

Among such onium salts, aromatic onium salts are particularly effective as the photopolymerization initiator (D). Among them, aromatic halonium salts described in JP-A-50-151996, JP-A-50-158680, etc., JP-A-50-151997, JP-A-52-30899, JP No. 56-55420, JP-A 55-125105, etc., Group VIA aromatic onium salts, JP-A No. 50-158698, etc., Group VA aromatic onium salts, JP-A-56 Oxosulfoxonium salts described in JP-A-8428, JP-A-56-149402, JP-A-57-192429 and the like, and aromatic diazonium salts described in JP-A-49-17040 The thiobililium salts described in US Pat. No. 4,139,655 are preferred. Moreover, an iron / allene complex, an aluminum complex / photolytic silicon compound-based initiator, and the like can also be mentioned.
These can be used individually by 1 type or in combination of 2 or more types.

  As a commercial item of the photoinitiator used suitably as a photoinitiator (D), Mitsui Cytec Co., Ltd. brand name: Catalyst 4050, Union Carbide make brand name: UVI-6950, UVI-6970, UVI-6974, UVI-6990, manufactured by Asahi Denka Kogyo Co., Ltd. Trade name: Adekaoptomer SP-150, SP-151, SP-170, SP-171, manufactured by Ciba Specialty Chemicals Co., Ltd. Trade name: Irgacure 261, manufactured by Nippon Soda Co., Ltd. Trade names: CI-2481, CI-2624, CI-2638, CI-2064, manufactured by Sartomer Inc. Trade names: CD-1010, CD-1011, CD-1012, Midori Chemical Co., Ltd. Product name: DTS-102, DTS-103, NAT-103, NDS-103, TPS-103, DS-103, MPI-103, BBI-103, manufactured by Nippon Kayaku Co., Ltd. trade name: can be mentioned PCI-061T, PCI-062T, PCI-020T, a PCI-022T and the like. Among these, Mitsui Cytec Co., Ltd. product names: Catalyst 4050, UVI-6970, UVI-6974, UVI-6990, Adekaoptomer SP-150, SP-170, SP-171, CD-1012, MPI- 103 is preferable because high surface curability can be exhibited when a curable composition containing these is cured.

  The radiation (photo) polymerization initiator is not particularly limited as long as it can be decomposed by light irradiation to generate radicals to initiate polymerization. For example, acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2 , 2-dimethoxy-1,2-diphenylethane-1-one, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy Roxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane -1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2 , 4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone) and the like.

  As a commercial item of a radiation (photo) polymerization initiator, for example, Ciba Specialty Chemicals Co., Ltd. trade name: Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI 1700, CGI 1750, CGI 1850, CG24-61, Darocur 1116, 1173, manufactured by BASF, Inc. Product name: Lucillin TPO, manufactured by UCB, Inc. Product name: Uvekril P36, manufactured by Fratteri Lamberti, Inc. Product names: Ezacure KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75 / B and the like.

When hardening the composition of this invention, a photoinitiator and a thermal-polymerization initiator can be used together as needed.
Preferable thermal polymerization initiators include, for example, peroxides and azo compounds. Specific examples include benzoyl peroxide, t-butyl-peroxybenzoate, azobisisobutyronitrile, and the like. it can.

  The blending amount of the photopolymerization initiator (D) in the composition of the present invention is preferably 0.01 to 20% by mass, with the total of components (A) to (D) being 100% by mass, More preferably, it is 1-10 mass%. If it is less than 0.01% by mass, the hardness when it is a cured product may be insufficient, and if it exceeds 20% by mass, the inside (lower layer) may not be cured.

5. Solvent (E)
The composition of the present invention can be used after diluted with a solvent in order to adjust the thickness of the coating film. For example, the viscosity when used as an antireflection film or a coating material is usually 0.1 to 50,000 mPa · sec (25 ° C.), preferably 0.5 to 10,000 mPa · sec (25 ° C.). .

  Examples of the solvent that can be used for adjusting the coating thickness include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate , Esters such as ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbons such as benzene, toluene and xylene Amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like.

  Although the compounding quantity of the solvent (E) in the composition of this invention is not restrict | limited in particular, It is 5-100,000 mass parts normally with respect to 100 mass parts of solid content whole quantity of the composition of this invention, Preferably it is 10-10. 10,000 parts by mass.

  In the case where the tin-containing indium oxide fine particles (A) and / or reactive particles (B) are dispersed in a dispersion medium, the dispersion medium may be used as a solvent as it is. Only another solvent may be used, or a dispersion medium and another solvent may be combined and used as the solvent (E).

6). Compound (F) having one polymerizable unsaturated group in the molecule
In the composition of the present invention, in addition to the compound having two or more polymerizable unsaturated groups in the molecule of the component (C), if necessary, a compound having one polymerizable unsaturated group in the molecule (F) can also be contained.

  Examples of the polymerizable unsaturated group possessed by the compound (F) used in the present invention include the groups described in the description of the component (C). Specific examples of the compound (F) include, for example, N-vinylpyrrolidone. , Vinyl group-containing lactams such as N-vinylcaprolactam, isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, Cyclohexyl (meth) acrylate and other alicyclic structure-containing (meth) acrylate, benzyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, acryloylmorpholine, vinylimidazole, vinylpyridine, 2-hydroxyethyl (meth) acrylate, 2-Hide Xylpropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, Sil (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, benzyl (meth) ) Acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxyethylene glycol (meth) acrylate, ethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxy Polypropylene glycol (meth) acrylate, diacetone (meth) acrylamide, isobutoxymethyl (meth ) Acrylamide, N, N-dimethyl (meth) acrylamide, t-octyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7-amino-3,7-dimethyloctyl (meth) Examples include acrylate, N, N-diethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, and the like.

  It is preferable that the compounding quantity of the compound (F) in the composition of this invention is 0.1-35 mass parts with respect to a total of 100 mass parts of (A)-(D) component, and 1-30 mass parts. It is more preferable that

7). Other components In the curable composition of the present invention, as long as the effects of the present invention are not impaired, a photosensitizer, a polymerization inhibitor, a polymerization initiation assistant, a leveling agent, a wettability improver, an interface, as necessary. An activator, a plasticizer, an ultraviolet absorber, an antioxidant, an antistatic agent, an inorganic filler, a pigment, a dye, and the like can be appropriately blended.
The composition of the present invention contains a photopolymerization initiator (D) as a polymerization initiator. In addition, a compound that generates a cationic species thermally and / or a thermally active radical species is added. A thermal polymerization initiator such as a compound to be generated can be blended.
Examples of the compound that generates a cationic species thermally include, for example, aliphatic sulfonic acid, oxyaliphatic sulfonate, aliphatic carboxylic acid, aliphatic carboxylate, aromatic carboxylic acid, aromatic carboxylate, alkylbenzene sulfone. Examples thereof include compounds such as acids, alkylbenzene sulfonates, phosphate esters, and metal salts.
These can be used individually by 1 type or in combination of 2 or more types.

  Preferable thermal polymerization initiators include, for example, peroxides and azo compounds. Specific examples include benzoyl peroxide, t-butyl-peroxybenzoate, azobisisobutyronitrile, and the like. it can.

  Moreover, it is preferable that the compounding quantity of the radical polymerization initiator used as needed in this invention is 0.01-20 mass parts with respect to a total of 100 mass parts of (A)-(D) component, More preferably, it is 0.1-10 mass parts. If it is less than 0.01 part by mass, the hardness when it is a cured product may be insufficient, and if it exceeds 20 parts by mass, it may not be cured to the inside (lower layer) when it is a cured product.

8). Preparation method of composition The composition of the present invention comprises the tin-containing indium oxide fine particles (A), the reactive particles (B), the polymerizable unsaturated group-containing compound (C), the photopolymerization initiator (D), and the necessity. Depending on the case, it can be obtained by mixing the solvent (E), the compound (F) and other additives.

9. Method of Applying Composition (Coating) The composition of the present invention is suitable for use as an antireflection film or a coating material. Examples of the base material to be antireflection or coated include plastics (polycarbonate, polymethacrylate, polystyrene). Polyester, polyolefin, epoxy, melamine, triacetyl cellulose, ABS, AS, norbornene resin, etc.), metal, wood, paper, glass, slate and the like. The shape of these substrates may be a plate, film or three-dimensional molded body, and the coating method is a normal coating method such as dipping coating, spray coating, flow coating, shower coating, roll coating, spin coating, brush coating, etc. Can be mentioned. The thickness of the coating film in these coatings is usually 0.1 to 400 μm, preferably 1 to 200 μm after drying and curing.

10. Method of Curing Composition The composition of the present invention can be cured by heat and / or radiation (light). When using heat, as the heat source, for example, an electric heater, an infrared lamp, hot air, or the like can be used. In the case of radiation (light), the radiation source is not particularly limited as long as the composition can be cured in a short time after coating. For example, as an infrared radiation source, a lamp, a resistance heating plate, Commercially available lasers, etc., as visible ray sources, sunlight, lamps, fluorescent lamps, lasers, etc., ultraviolet ray sources, mercury lamps, halide lamps, lasers, etc., and electron beam sources Using thermionic electrons generated from tungsten filaments, cold cathode method for generating metal through high voltage pulse, and secondary electron method using secondary electrons generated by collision between ionized gaseous molecules and metal electrode Can be mentioned. Examples of the source of alpha rays, beta rays, and gamma rays include fission materials such as ⁶⁰ Co. For gamma rays, a vacuum tube that collides accelerated electrons with the anode can be used. These radiations can be irradiated alone or in combination of two or more at a certain time.

II. Cured film The cured film of the present invention can be obtained by coating and curing the curable composition on various substrates, for example, plastic substrates. Specifically, after coating the composition and preferably drying the volatile component at 0 to 200 ° C., it can be obtained as a coated molded body by performing the above-described curing treatment with heat and / or radiation. . The preferable curing conditions in the case of heat are 20 to 150 ° C., and are performed within a range of 10 seconds to 24 hours. When using radiation, it is preferable to use ultraviolet rays or electron beams. In such a case, the preferable irradiation amount of ultraviolet rays is 0.01 to 10 J / cm ² , more preferably 0.1 to ² J / cm ² . Moreover, as for the irradiation conditions of a preferable electron beam, a pressurization voltage is 10-300 KV, an electron density is 0.02-0.30 mA / cm < ² >, and an electron beam irradiation amount is 1-10 Mrad.

The liquid curable composition of the present invention containing tin-containing indium oxide (ITO) fine particles (A) and reactive particles (B) as particle components is a polyester or polyethylene whose surface is subjected to easy adhesion treatment, which will be described later. Layer separation occurs when applied onto a specific substrate made of terephthalate (PET) or the like. That is, the reactive fine particles (B) are unevenly distributed on the air interface side on the side where the ITO fine particles (A) are in contact with the substrate. FIG. 1 shows an electron micrograph showing a state in which ITO fine particles (A) in a cured film obtained by curing the composition of the present invention are unevenly distributed on the substrate side. In FIG. 1, (a) is a base material side interface, (b) is an air side interface.
In the cured film of this invention, effective electroconductivity is realizable with the addition amount of a smaller component (A). In addition, the addition amount of the component (A) can be reduced and the particle size of the component (A) is small, so that light absorption / scattering by the component (A) is small and a highly transparent film can be formed. it can.

The cured film of the present invention has the characteristics that it has a high hardness and a high refractive index, and can form a coating film (film) excellent in scratch resistance and adhesion to the substrate and the low refractive index layer. Therefore, it is particularly suitably used as a hard coat or antireflection film for film type liquid crystal elements, touch panels, plastic optical components and the like.
In addition, the cured film of the present invention is excellent in antistatic properties and transparency, and is useful as an antistatic film in various plastic optical parts and the like.

  Examples of the present invention will be described in detail below, but the scope of the present invention is not limited to the description of these examples. Moreover, unless otherwise indicated, the compounding quantity of each component in an Example means the mass part and the mass%.

Production Example 1: Preparation of tin-containing indium oxide (ITO) particles (A-1) 200 parts of spherical ITO fine powder (manufactured by Fuji Chemical Co., Ltd., number average primary particle size 0.013 μm) was added to 800 parts of isopropyl alcohol. Then, dispersion was performed with glass beads for 12 hours, and the crow beads were removed to obtain 950 parts of isopropyl alcohol ITO sol (A-1). 2 g of the dispersed sol was weighed on an aluminum dish, dried on a hot plate at 175 ° C. for 1 hour, and weighed to determine the solid content, which was 20%. Further, as a result of observation of the solid matter by an electron microscope, the short axis average particle diameter was 12 nm, the long axis average particle diameter was 14 nm, and the aspect ratio was 1.2.

Production Example 2: Preparation of oxide (ZrO ₂ ) particles (Ba) 500 parts of spherical zirconia fine powder (manufactured by Sumitomo Osaka Cement Co., Ltd., number average primary particle diameter 0.01 μm) is added to 500 parts of methyl ethyl ketone (MEK). The glass beads were dispersed for 168 hours, and the crow beads were removed to obtain 910 parts of methyl ethyl ketone zirconia sol (Ba). 2 g of the dispersed sol was weighed on an aluminum dish, dried on a hot plate at 120 ° C. for 1 hour, and weighed to determine the solid content, which was 50%. Moreover, as a result of observation of this solid matter by an electron microscope, the minor axis average particle diameter was 15 nm, the major axis average particle diameter was 20 nm, and the aspect ratio was 1.3.

Production Example 3 Production of Organic Compound (Bb) Containing Polymerizable Unsaturation Group In dry air, 222 parts of isophorone diisocyanate was stirred with respect to a solution consisting of 221 parts of mercaptopropyltrimethoxysilane and 1 part of dibutyltin dilaurate. However, after dropwise addition at 50 ° C. over 1 hour, the mixture was stirred with heating at 70 ° C. for 3 hours. This is composed of NK ester A-TMM-3LM-N (manufactured by Shin-Nakamura Chemical Co., Ltd.) comprising 60% by mass of pentaerythritol triacrylate and 40% by mass of pentaerythritol tetraacrylate. 549 parts were added dropwise at 30 ° C. over 1 hour, and then heated and stirred at 60 ° C. for 10 hours to obtain an organic compound (Bb) containing a polymerizable unsaturated group. When the amount of residual isocyanate in the product was analyzed by FT-IR, it was 0.1% or less, indicating that the reaction was almost quantitatively completed. In the infrared absorption spectrum of the product, the absorption peak of 2550 Kaiser characteristic of mercapto group in the raw material and the absorption peak of 2260 Kaiser characteristic of raw material isocyanate compound disappeared, and new urethane A 1660 Kaiser peak characteristic of the bond and the S (C = O) NH- group and a 1720 Kaiser peak characteristic of the acryloxy group are observed, with an acryloxy group as the polymerizable unsaturated group It was shown that -S (C = O) NH- and an acryloxy group-modified alkoxysilane having both urethane bonds were formed. As a result, 773 parts of the compound (Bb) represented by the following formula (4) and the following formula (5) were obtained in total, and 220 parts of pentaerythritol tetraacrylate that was not involved in the reaction were mixed.

[Wherein, Acryl represents an acryloyl group, and Me represents a methyl group. ]

Production Example 4: Production of urethane (meth) acrylate (C-2) NK ester manufactured by Shin-Nakamura Chemical Co., Ltd. for a solution comprising 18.8 parts of isophorone diisocyanate and 0.2 part of dibutyltin dilaurate in a container equipped with a stirrer 93 parts of A-TMM-3LM-N (only the pentaerythritol triacrylate having a hydroxyl group is involved in the reaction) was added dropwise at 10 ° C. for 1 hour, and then at 60 ° C. for 6 hours. To give a reaction solution.
With respect to the product in the reaction solution, the amount of residual isocyanate was measured by FT-IR in the same manner as in Production Example 3. As a result, it was 0.1% by mass or less, and it was confirmed that the reaction was performed almost quantitatively. . Moreover, it confirmed that a molecule | numerator contained a urethane bond and an acryloyl group (polymerizable unsaturated group) in a molecule | numerator.
As a result, 75 parts of the compound represented by the following formula (6) was obtained, and 37 parts of pentaerythritol tetraacrylate that was not involved in the reaction were mixed.

[In the formula, Acryl represents an acryloyl group. ]

Production Example 5: Production of reactive zirconia (ZrO ₂ ) fine powder sol (B-1) 1.9 parts of an organic compound (Bb) containing a polymerizable unsaturated group produced in Production Example 3 was prepared in Production Example 2. A mixture of 142.2 parts of methyl ethyl ketone zirconia sol (Ba) (zirconia concentration 50%), 0.1 part of ion exchange water and 0.03 part of p-hydroxyphenyl monomethyl ether was stirred at 60 ° C. for 3 hours, and then ortho Reactive particles (dispersion liquid (B-1)) were obtained by adding 1.0 part of methyl formate and further heating and stirring at the same temperature for 1 hour. 2 g of this dispersion (B-1) was weighed in an aluminum dish, dried on a hot plate at 120 ° C. for 1 hour, and weighed to determine the solid content, which was 51%. Further, 2 g of the dispersion (B-1) was weighed into a magnetic crucible, pre-dried on a hot plate at 80 ° C. for 30 minutes, and baked in a muffle furnace at 750 ° C. for 1 hour. The inorganic content was determined to be 98%.

[Preparation of curable composition]
Example 1
In a container shielded from ultraviolet rays, 50.2 parts of ITO fine powder sol (A-1) prepared in Production Example 1 and 91.0 parts of reactive ZrO ₂ fine powder sol (B-1) prepared in Production Example 5 Dipentaerythritol pentaacrylate (C-1; Nippon Kayaku Co., Ltd., trade name: KAYADAR DPHA-2C) 39.96 parts, compound (C-2) represented by formula (5) prepared in Production Example 4 2.1 parts, 1.0 part of 1-hydroxycyclohexyl phenyl ketone (D-1), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (D-2) 0 .5 parts, 9.9 parts of IPA, and 5.4 parts of MEK were mixed and stirred at 30 ° C. for 2 hours to obtain a uniform solution composition. When the solid content of this composition was measured in the same manner as in Production Example 5, it was 50%.

Examples 2-8 and Comparative Examples 1-7
Except having changed into the composition shown in Table 1 or Table 2, by the method similar to Example 1, each composition of Examples 2-8 and Comparative Examples 1-7 was obtained.

[Production of cured films of Examples 1 to 7 and Comparative Examples 1 to 5]
Composition obtained in the above examples and comparative examples using a wire bar coater (# 6) on a base material (polyester film A4300 (manufactured by Toyobo Co., Ltd., film thickness: 188 μm) subjected to surface easy adhesion treatment) The product was coated and dried in an oven at 80 ° C. for 3 minutes to form a coating film, and then the coating film was applied in the air under a light irradiation condition of 0.3 J / cm ² using a metal halide lamp. Was cured with an ultraviolet ray to form a cured film having a thickness of 3 μm.

[Production of cured films of Example 8 and Comparative Examples 6 to 7]
Composition obtained in the above examples and comparative examples using a wire bar coater (# 6) on a base material (polyester film A4300 (manufactured by Toyobo Co., Ltd., film thickness: 188 μm) subjected to surface easy adhesion treatment) The product was coated and dried in an oven at 80 ° C. for 3 minutes to form a coating film, and then the coating film was applied in the air under a light irradiation condition of 0.3 J / cm ² using a metal halide lamp. Was cured with an ultraviolet ray to form a cured film having a thickness of 0.1 μm.

[Characteristic evaluation of cured film]
1. Transparency (haze)
Using a color haze meter manufactured by Suga Seisakusho Co., Ltd., the haze value (%) was measured according to ASTM D1003 and evaluated as a value including a base film. The obtained results are shown in Tables 1 and 2.

2. Refractive index The refractive index (n _D ²⁵ ) at a wavelength of 589 nm at 25 ° C. was measured using an ellipsometer. The obtained results are shown in Tables 1 and 2.

3. Conductivity (surface resistance value)
Using Hiresta UP MCT-HT450 manufactured by Mitsubishi Chemical Corporation, the surface on which the cured film of the laminate composed of the base material and the cured film was formed was set on the electrode side and measured at an applied voltage of 100V. The obtained results are shown in Tables 1 and 2.

In Tables 1 and 2, the blending amount of the ITO fine powder sol (A-1) indicates the dry weight of the fine powder (excluding the organic solvent) contained in the charged amount of the dispersion sol.
Similarly, in Tables 1 and 2, the compounding amount of the reactive ZrO ₂ fine powder sol (B-1) represents the dry weight of fine powder contained in the charged amount of the dispersed sol (excluding the organic solvent).
The contents of the abbreviations in Table 1 and Table 2 are shown below.
DPHA (C-1): dipentaerythritol pentaacrylate; trade name KAYADAR DPHA-2C; manufactured by Nippon Kayaku Co., Ltd.)
Photopolymerization initiator (D-1): 1-hydroxycyclohexyl phenyl ketone; trade name Irgacure 184; manufactured by Ciba Specialty Chemicals Co., Ltd. Photopolymerization initiator (D-2): 2-methyl-1- [4- (methylthio ) Phenyl] -2-morpholinopropan-1-one; trade name Irgacure 907; manufactured by Ciba Specialty Chemicals, Inc. MEK: methyl ethyl ketone IPA: isopropanol PGME: propylene glycol monomethyl ether

From the results of Tables 1 and 2, the following can be understood.
In Comparative Examples 1 to 7 in which either the component (A) or the component (B) or both are not blended, the surface resistance value and haze are both high or the surface resistance value is low, the haze is high and the haze is low. Since the surface resistance is high, it can be seen that conductivity and transparency are not compatible.
On the other hand, in Examples 1-8, it turns out that a cured film excellent in both the characteristic of both electroconductivity and transparency is obtained with low haze and low surface resistance value.

The curable composition of the present invention, the cured film and the laminate thereof are, for example, scratches such as plastic optical parts, touch panels, film-type liquid crystal elements, plastic containers, floor materials as building interior materials, wall materials, artificial marble, etc. Protective coating materials for preventing scratches and preventing contamination; Antireflection films for film-type liquid crystal elements, touch panels, plastic optical components, etc .; Adhesives and sealing materials for various substrates; It can be suitably used as a film.
Further, since the laminate of the present invention is excellent in antistatic properties, it can be used for the purpose of preventing the adhesion of dust for various panels such as CRT, liquid crystal display panel, plasma display panel, electroluminescence display panel, etc. It is also useful as an electromagnetic wave shield, and as an antistatic hard coat or an antireflection film for antistatic.

FIG. 1 is an electron micrograph showing a substrate-side interface in a cured film obtained by curing a curable composition containing tin-containing indium oxide (ITO) particles and zirconia (ZrO ₂ ) particles of the present invention. , ITO particles are unevenly distributed at the substrate side interface. FIG. 2 is an electron micrograph showing an air-side interface in a cured film obtained by curing a curable composition containing tin-containing indium oxide (ITO) particles and zirconia (ZrO ₂ ) particles of the present invention.

Claims (7)

The following components (A) to (D):
(A) Tin-containing indium oxide fine particles (B) Oxide particles (Ba) of at least one element selected from the group consisting of zirconium, titanium, aluminum, cerium, tin and zinc, and an organic compound containing a polymerizable unsaturated group Particles formed by bonding (Bb) (C) A compound having two or more polymerizable unsaturated groups in the molecule (D) A curable composition containing a photopolymerization initiator.   The total of said component (A)-(D) is 100 mass%, The said (A) component is mix | blended in the ratio of 7-40 mass%, and the said (B) component are 20-60 mass%. The curable composition according to 1.   The curable composition according to claim 1 or 2, wherein a primary particle diameter of the tin-containing indium oxide fine particles is within a range of 1 to 20 nm. The curable composition according to any one of claims 1 to 3, wherein the organic compound containing the (Bb) polymerizable unsaturated group has a group represented by the following formula (1) in addition to the polymerizable unsaturated group. .
-Y- C (= V) -NH- (1)
[In the formula (1), Y represents NH, O (oxygen atom) or S (sulfur atom), and V represents O or S. ]   The cured film formed by hardening the curable composition as described in any one of Claims 1-4. The cured film according to claim 5, having a surface resistance value of 1 × 10 ¹² Ω / □ or less.   The manufacturing method of the cured film which has a process which irradiates a radiation to the curable composition as described in any one of Claims 1-4, and hardens this composition.