JP5151113B2 - Curable composition, cured film and antistatic laminate - Google Patents

Description

  The present invention relates to a curable composition, a cured film obtained by curing the curable composition, and an antistatic laminate.

Conventionally, from the viewpoints of ensuring the performance of information communication equipment and safety measures, a curable composition is used on the surface of the equipment to provide a scratch-resistant and adhesive film (hard coat) or an anti-static film. (Antistatic film) is formed.
In recent years, there has been remarkable development and generalization of information communication devices, and further improvements in performance and productivity of hard coats, antistatic films and the like have been demanded.

In particular, optical articles such as plastic lenses are required to prevent dust adhesion due to static electricity and to improve the reduction in transmittance due to reflection, and display panels also prevent dust adhesion due to static electricity. Therefore, prevention of reflection on the screen has been demanded.
In response to these demands, various radiation curable materials have been proposed with a focus on high productivity and curing at room temperature.

  As such a technique, for example, a composition containing a sulfonic acid and a phosphoric acid monomer as an ion conductive component (Patent Document 1), a composition containing a chain metal powder (Patent Document 2), an oxidation A composition mainly composed of tin particles, polyfunctional acrylate, and a copolymer of methyl methacrylate and polyether acrylate (Patent Document 3), and a conductive coating composition containing a pigment coated with a conductive polymer (Patent Document 4) ) A trifunctional acrylic acid ester, a monofunctional ethylenically unsaturated group-containing compound, a photopolymerization initiator, and an optical disk material containing conductive powder (Patent Document 5), antimony-doped dispersed with a silane coupler Conductive paint containing hydrolyzate of tin oxide particles and tetraalkoxysilane, photosensitizer, and organic solvent (Patent Document 6), polymerized in the molecule Reaction product of alkoxysilane containing unsaturated group and metal oxide particles, liquid curable resin composition containing trifunctional acrylic compound and radiation polymerization initiator (Patent Document 7), primary particle diameter is 100 nm The following conductive oxide fine powder, easy-dispersible low-boiling solvent of the conductive oxide fine powder, difficult-dispersible low-boiling solvent of the conductive oxide fine powder, and formation of a transparent conductive film containing a binder resin For example (Patent Document 8).

JP 47-34539 A JP 55-78070 A Japanese Patent Laid-Open No. 60-60166 Japanese Patent Laid-Open No. 2-194071 JP-A-4-172634 Japanese Unexamined Patent Publication No. Hei 6-264209 JP 2000-143924 A JP 2001-131485 A

  However, although such conventional techniques each exhibit a certain effect, in recent years, as a cured film that is required to have all the functions of a hard coat and an antistatic film, it is not always necessary. It was not satisfactory enough.

  For example, the conventional techniques as described in the above prior art documents have the following problems. The composition described in Patent Document 1 uses an ion conductive material, but the antistatic performance is not sufficient, and the performance varies due to drying. Since the composition described in Patent Document 2 disperses a chain-like metal powder having a large particle size, transparency is lowered. Since the composition described in Patent Document 3 contains a large amount of non-curable dispersant, the strength of the cured film decreases. Since the material described in Patent Document 5 contains high-concentration chargeable inorganic particles, transparency is lowered. The paint described in Patent Document 6 has insufficient long-term storage stability. Patent Document 7 does not disclose any method for producing a composition having antistatic performance. When the transparent conductive film is formed by applying and drying the paint described in Patent Document 8, the organic matrix made of the binder composition is not provided with a cross-linked structure, so it cannot be said that the organic solvent resistance is sufficient.

  Increasing the amount of conductive particles to increase the antistatic performance can be easily conceived, but in that case, the transparency decreases due to the increase in visible light absorption by the cured film, and the UV transmittance decreases. The problems that the curability is lowered, the adhesion to the base material, and the leveling property of the coating liquid are impaired cannot be avoided. On the other hand, when the blending amount of the conductive particles is reduced, sufficient antistatic performance is not exhibited.

  The present invention has been made in view of the above-described problems, and can exhibit sufficient antistatic performance even when the amount of conductive particles is small, has excellent curability, and is applied to the surface of various substrates. Another object of the present invention is to provide a curable composition that is excellent in antistatic properties, hardness, and scratch resistance, and that can form a cured film having both transparency and surface resistance.

  As a result of diligent research to achieve the above-mentioned object, the present inventors have found that conductive particles having a specific primary particle size, compounds having a specific polymerizable unsaturated group, fluorine-based surfactants or fluorine-containing (metabolites) ) It has been found that by using a composition containing an acrylate, a photopolymerization initiator having specific light absorption characteristics, and a solvent, excellent conductivity can be exhibited even when the amount of conductive particles added is reduced. Completed the invention.

That is, the present invention provides the following curable composition, cured film, and antistatic laminate.
1. The following components (A) to (C):
(A) Particles having an average primary particle size of 10 nm to 100 nm and containing phosphorus-containing tin oxide as a main component (B) Compound having two or more polymerizable unsaturated groups in the molecule (C) Fluorine atom in the molecule The curable composition containing the compound containing this.
2. 2. The curable composition according to 1 above, wherein the component (A) is contained in a proportion of 1% by mass or more and less than 25% by mass when the total solid content excluding the organic solvent in the composition is 100% by mass.
3. 3. The curable composition according to 1 or 2 above, wherein the component (C) is a nonionic and / or anionic fluorosurfactant.
4). The curable composition according to any one of the above 1 to 3, wherein the component (B) contains a compound having 6 or more polymerizable unsaturated groups in the molecule.
5. Furthermore, (D) The curable composition in any one of said 1-4 containing the photoinitiator whose molar absorption coefficient in 313 nm is 5000 L / mol * cm or less.
6). The component (D) is 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone ), 2,2-dimethoxy-1,2-diphenylethane-1-one and 2-hydroxy-2-methyl-1-phenyl-propan-1-one, one or more selected from the group consisting of The curable composition in any one of 1-3.
7). Furthermore, (E) The curable composition in any one of said 1-6 containing the organic solvent.
8). A cured film having a surface resistance value of 10 ¹³ Ω / □ or less, obtained by curing the curable composition according to any one of 1 to 7 above.
9. The manufacturing method of the cured film which has a process which irradiates a radiation to the curable composition in any one of said 1-7, and hardens this composition.
10. An antistatic laminate comprising a substrate and a cured resin layer containing PTO particles having an average primary particle diameter of 10 nm to 100 nm, wherein at least a part of the PTO particles is a substrate of the cured resin layer An antistatic laminate that is substantially concentrated and distributed on one or both of the side interface and the interface opposite the substrate.
11. An antistatic laminate, wherein the cured resin layer is obtained by curing the curable composition according to any one of 1 to 7 above.
12 12. The antistatic laminate according to 11 above, having a surface resistance value of 10 ¹³ Ω / □ or less.
13. An antistatic laminate comprising a substrate and a cured resin layer containing PTO particles having an average primary particle diameter of 10 nm to 100 nm, wherein at least a part of the PTO particles is a substrate of the cured resin layer A method for producing an antistatic laminate that is substantially concentrated and distributed on one or both of a side interface and an interface on the opposite side of a substrate, wherein any one of 1 to 7 above is provided on the substrate. A method for producing an antistatic laminate, comprising a step of applying the curable composition described above, and a step of irradiating the curable composition with radiation to cure the composition.

According to the present invention, even if the content of the conductive particles is low, sufficient conductivity can be exhibited, and a cured film excellent in antistatic performance can be obtained. Moreover, since content of electroconductive particle is low, it is excellent in transparency, and a suitable material for using for the optical use which requires high electroconductivity and transparency simultaneously can be obtained.
The antistatic laminate of the present invention has a cured resin layer in which at least a part of the conductive particles are concentrated and distributed on the interface opposite to the base material, and the conductive particles are unevenly distributed. Even if the content of the conductive particles is low, sufficient antistatic performance is exhibited.

Hereinafter, embodiments of the present invention will be specifically described.
I. Curable composition The curable composition of this invention may contain the following component (A)-(F). Among these components, components (A) to (C) are essential components, and components (D) to (F) are optional components that can be added as necessary.
(A) Particles having an average primary particle size of 10 nm to 100 nm and containing phosphorus-containing tin oxide as a main component (B) Compound having two or more polymerizable unsaturated groups in the molecule (C) Fluorine atom in the molecule Compound (D) having a molar extinction coefficient at 313 nm of 5000 L / mol · cm or less (E) Organic solvent (F) Other additives Each component will be specifically described below.

1. Particles mainly composed of phosphorus-containing tin oxide (A) having an average primary particle diameter of 10 nm to 100 nm
The component (A) used in the present invention is an essential component for developing the conductivity of the cured film of the resulting curable composition. Particles mainly composed of phosphorus-containing tin oxide (PTO) (hereinafter referred to as “PTO particles”) can impart good antistatic performance to the resulting cured film as conductive particles.

  As a commercial item as a powder of PTO particle, the product name: ELCOM TL-30S (PTO) by a catalyst chemical industry Co., Ltd. and the product name: EP SP2 by Mitsubishi Materials Corporation can be mentioned, for example.

  The PTO particles (A) can be used in a state dispersed in a powder or a solvent, but it is preferable to use the PTO particles (A) in a state dispersed in a solvent because uniform dispersibility is easily obtained. When the PTO particles are powder, a dispersant may be used to uniformly disperse in the solvent. Examples of such a dispersant include TR701, TR702, TR704, which are surfactants manufactured by Asahi Denka Kogyo Co., Ltd.

  As a commercial item which disperse | distributed PTO particle | grains (A) in the solvent, the product name: ELCOM JX-1001PTV (PTO of propylene glycol monomethyl ether dispersion | distribution) made from a catalyst chemical industry Co., Ltd. can be mentioned, for example.

The average primary particle diameter of the PTO particles (A) is 10 to 100 nm. Preferably it is 10-50 nm. The particle diameter is measured with a transmission electron microscope. If the particle diameter is less than 10 nm, the conductivity may be insufficient, and if it exceeds 100 nm, precipitation may occur in the composition or the smoothness of the coating film may be reduced. The shape of the PTO particles is not particularly limited, and may be a spherical shape, a rod shape, a needle shape, or the like.
In addition, when the shape is elongated like a needle, the dried powder is observed with an electron microscope, and the value obtained as the number average particle size is 10-50 nm as the short axis average particle size and 100 as the long axis number average particle size. It is preferably ˜2,000 nm. If the long axis particle diameter exceeds 2,000 nm, sedimentation may occur in the composition.

The compounding quantity of the component (A) in the composition of this invention is 1 mass% or more and less than 25 mass% by making solid content whole quantity except an organic solvent into 100 mass%. Preferably, it is 1-20 mass%, More preferably, it is 2-15 mass%.
If the blending amount is less than 1% by mass, the antistatic property may be inferior, and if it is 25% by mass or more, the transparency may decrease.
Here, the compounding quantity of a component (A) says the compounding quantity as the solid content.

When the composition of the present invention is applied on a substrate and then cured by irradiation with radiation to form a cured film, the PTO particles of the component (A) are bonded to the substrate side interface of the cured film or the base of the cured film. It is distributed substantially concentrated in the vicinity of the interface opposite to the material (hereinafter referred to as “air-side interface”) or in the vicinity of both interfaces. Here, “substantially concentrated and distributed” means particles in the vicinity of the interface where the PTO particles are concentrated and other portions (the central portion of the cured film or the interface where the PTO particles are not concentrated). This means that there is a significant difference in the distribution density, and not all PTO particles in the cured film may be present near the interface. That is, it is sufficient that a portion having a relatively low distribution density of PTO particles (the number of PTO particles per unit volume) and a portion having a relatively high distribution density of PTO particles are formed in the cured film. Even if some PTO particles are present inside the cured film, it is sufficient that a region having a high distribution density of PTO particles is formed in the vicinity of the interface.
The portion where the distribution density of the PTO particles is relatively low is in contact with the base material and forms most of the thickness of the cured film. On the other hand, the portion where the distribution density of PTO particles is relatively high forms a portion occupying a thickness corresponding to one to several tens of PTO particles near the air interface, near the base material interface, or near both interfaces. Typically, however, a region in which the secondary aggregates of PTO particles are arranged substantially in the vicinity of one interface is formed. When the PTO particles having an average primary particle diameter of about 20 nm are used, the thickness of the portion where the distribution density of such PTO particles is relatively high typically cures the curable composition of the present invention. It is about 1/10 of the cured resin layer obtained. When the PTO particles are thus distributed, a surface resistance value of 10 ¹³ Ω / □ or less or better than that is obtained. Although the amount of PTO particles in the composition is low, it is considered that PTO particles are concentrated in a part of the cured film to form a conductive layer. Typical cured film cross sections observed with a transmission electron microscope are shown in FIGS. FIG. 1 (Example 2) shows a case where PTO particles are substantially concentrated on both the base material side and the opposite side interface of the base material, and FIG. This shows a case where the PTO particles are substantially concentrated on the substrate side interface.

In the present invention, the component (A) may be oxide particles surface-treated with a surface treatment agent. By performing the surface treatment, the scratch resistance of the cured product can be improved.
The surface treatment can be performed by a known method (for example, see JP-A-2003-105034).
In the present invention, a compound having two or more polymerizable unsaturated groups, a group represented by the following formula (1), and a silanol group or a group that generates a silanol group by hydrolysis can be preferably used as the surface treatment agent.
-X-C (= Y) -NH- (1)
[In the formula (1), X represents NH, O (oxygen atom) or S (sulfur atom), and Y represents O or S. ]

Examples of the polymerizable unsaturated group include a (meth) acryloyl group and a vinyl group.
Specifically, the group represented by Formula (1) includes [—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—]. It is a seed. Among these, [—O—C (═O) —NH—], [—O—C (═S) —NH—] or [—S—C (═O) —NH—] is preferable. 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, the [—O—C (═O) —NH—] group is essential, the [—O—C (═S) —NH—] group and the [—S—C (═O). ) -NH-] group is preferably used in combination. The group [—X—C (═Y) —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.

As a compound which produces | generates a silanol group, the compound which the alkoxy group, the aryloxy group, the acetoxy group, the amino group, the halogen atom, etc. couple | bonded with the silicon atom can be mentioned. A compound in which an alkoxy group or an aryloxy group is bonded to a silicon atom, that is, an alkoxysilyl group-containing compound or an aryloxysilyl group-containing compound is preferable.
The silanol group-generating site of the silanol group or the compound that generates the silanol group is a structural unit that binds to the silica particles by a condensation reaction that occurs following a condensation reaction or hydrolysis.

  Specific examples of the surface treatment agent include compounds represented by the following formula (2).

In the formula (2), R ¹ and R ² may be the same or different and each represents a hydrogen atom or an alkyl group or aryl group having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, butyl, octyl, Examples thereof include phenyl and xylyl groups. Here, j is an integer of 1 to 3.

Examples of the group represented by [(R ¹ O) _j R ² _3-j Si—] include a trimethoxysilyl group, a triethoxysilyl group, a triphenoxysilyl group, a methyldimethoxysilyl group, and a dimethylmethoxysilyl group. 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. Specific examples include methylene, ethylene, propylene, butylene, hexamethylene, cyclohexylene, phenylene, xylylene, dodecamethylene and the like.
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. Specific examples include a chain polyalkylene group such as hexamethylene, octamethylene, and dodecamethylene; an alicyclic or polycyclic divalent organic group such as cyclohexylene and norbornylene; and 2 such as phenylene, naphthylene, biphenylene, and polyphenylene. Valent aromatic group; and these alkyl group-substituted and aryl group-substituted products. These divalent organic groups may contain an atomic group containing an element other than carbon and hydrogen atoms, and may contain a polyether bond, a polyester bond, a polyamide bond, and a polycarbonate bond.
R ⁵ is a (k + 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. K 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.

  Specific examples of the compound represented by the formula (2) include a compound represented by the following formula (3) or the following formula (4).

[In the formulas (3) and (4), “Acryl” represents an acryloyl group. ]

  For the synthesis of the surface treating agent used in the present invention, for example, a method described in JP-A-9-100111 can be used. Preferably, mercaptopropyltrimethoxysilane and isophorone diisocyanate are mixed in the presence of dibutyltin dilaurate and reacted at 60 to 70 ° C. for several hours, then pentaerythritol triacrylate is added, and further at 60 to 70 ° C. for several hours. Produced by reacting to some extent. Typically, a mixture of the compound represented by formula (3) and the compound represented by formula (4) is obtained.

2. Compound (B) having two or more polymerizable unsaturated groups in the molecule
Component (B) used in the present invention is a compound having two or more polymerizable unsaturated groups in the molecule, and can improve the film formability and transparency of the cured film of the resulting curable composition. . By using the component (B), a cured product having excellent scratch resistance and organic solvent resistance can be obtained.

Specific examples of the component (B) include, for example, polyfunctional (meth) acrylic esters having two or more (meth) acryloyl groups in the molecule and polyfunctional vinyl compounds having two or more vinyl groups in the molecule. Can be mentioned.
Multifunctional (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 Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate, bis ((meta ) Acryloyloxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane (also referred to as “tricyclodecanediyldimethanol di (meth) acrylate”), and the starting alcohols in the preparation of these compounds. Poly (meth) acrylates of ethylene oxide or propylene oxide adducts, oligoester (meth) acrylates having two or more (meth) acryloyl groups in the molecule, oligoether (meth) acrylates, oligourethane (meth) acrylates , And oligo epoxy (Meth) acrylates and the like can be mentioned.

  Examples of the polyfunctional vinyl compounds include divinylbenzene, ethylene glycol divinyl ether, diethylene glycol divinyl ether, and triethylene glycol divinyl ether. Among them, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) ) Acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate, and tricyclodecanediyldimethanol di (meth) acrylate. These (B) components may be used individually by 1 type, and may use 2 or more types together.

Among the components (B), compounds having 6 or more polymerizable unsaturated groups in the molecule are particularly preferable.
The amount of component (B) in the composition of the present invention is preferably 74 to 98% by mass, more preferably 79 to 95% by mass, with the total solid content excluding the organic solvent being 100% by mass. When the blending amount of the component (B) is less than 74% by mass, the transparency of the obtained cured product may be lowered, and when it exceeds 98% by mass, the antistatic property may be inferior.

3. Compound containing fluorine atom in molecule (C)
The component (C) used in the present invention is a compound containing a fluorine atom in the molecule (hereinafter referred to as “fluorine-containing compound”), and is usually used to improve the coating property of the composition on a substrate. Surprisingly, the hardness at the time of making a cured film can be improved by mix | blending a component (C). Furthermore, it is possible to promote the uneven distribution of the PTO particles (A) near the interface with the base material or the interface with the air, thereby obtaining an excellent antistatic performance even if the amount of the PTO particles is small. It is done.

  The fluorine-containing compound (C) is preferably fluorine-based surfactants or fluorine-containing (meth) acrylic esters, and more preferably fluorine-based surfactants. As the fluorosurfactant, either one or both of a nonionic fluorosurfactant and an anionic fluorosurfactant can be used. From the viewpoint of solubility in a solvent, the nonionic fluorosurfactant is used. Is preferred.

  Examples of commercially available fluorosurfactants include Dainippon Ink and Chemicals, Inc., trade names: Megafac F-142D, F-144D, F-171, F-172, F-173, F- 177, F-178A, F-178K, F-179, F-179A, F-183, F-184, F-191, F-812, F-815, F-1405, F410, F-443, F- 445, F-450, F-471, F-472SF, F475, F-479, F-482, R-30, MCF-350, TF1025, manufactured by Gemco Co., Ltd. Trade names: EFTOP EF-101, EF-121 , EF-122B, EF-122C, EF-122A3, EF-121, EF-123A, EF-123B, EF-126, EF-127, EF-301, EF-302, EF- 51, EF-352, EF-601, EF-801, EF-802, manufactured by Neos Co., Ltd. Product names: Footage 250, 251, 222F, FTX-218, 212M, 245M, 290M, FTX-207S, FTX- 211S, FTX-220S, FTS-230S, FTX-209F, FTX-213F, FTX-233F, FTX-245F, FTX-208G, FTX-218G, FTX-230G, FTS-240G, FTX-204D, FTX-208D, FTX-212D, FTX-216D, FTX-218D, FTX-220D, FTX-222D, FTX-720C, FTX-740C, manufactured by Seimi Chemical Co., Ltd. Trade names: Surflon S-111, S-112, S-113, S-121, S-131, S-132, S 141, S-145, S-381, it can be mentioned S-383, S-393, S-101, KH-40, SA-100 and the like. Among these, from the viewpoint of uneven distribution of PTO particles, Megafac F-445, Footgent 222F, and the like are preferable.

  Examples of commercially available fluorine-containing (meth) acrylic esters include LINC-1001: trade name, Kyoeisha's fluorine acrylate, CN4000: trade name, Sartomer's fluorine acrylate, MegaFuck F-470: trade name, Dainippon Ink Examples include perfluoroalkyl group-containing oligomers manufactured by company, Megafac F-1405: trade names, perfluoroalkyl group-containing oligomers manufactured by Dainippon Ink and the like.

  The compounding amount of the component (C) in the composition of the present invention is preferably 0.01 to 10% by mass, preferably 0.1 to 5% by mass, with the total solid content excluding the organic solvent being 100% by mass. Further preferred. If the blending amount is less than 0.01% by mass, the uneven distribution of the PTO particles may not be sufficient, or if it exceeds 10% by mass, the hardness of the cured film may be insufficient.

4). Photopolymerization initiator (D)
Component (D) used in the present invention is a photopolymerization initiator having a molar extinction coefficient at 313 nm of 5,000 L / mol · cm or less. Here, the molar extinction coefficient at 313 nm of the photopolymerization initiator means the ratio of the absorbance and molar concentration of the solution at 313 nm to the 1 cm absorption layer. By using a photopolymerization initiator having such light absorption characteristics, the surface resistance of the cured film can be sufficiently reduced. When a photopolymerization initiator having a molar extinction coefficient at 313 nm exceeding 5,000 L / mol · cm is used, a cured film in which PTO particles are concentrated and distributed at the interface cannot be obtained. Resistance is high and sufficient antistatic performance cannot be obtained.

Although the curable composition of this invention hardens | cures only by irradiating a radiation, a component (D) can further raise a cure rate other than said function.
In the present invention, radiation means visible light, ultraviolet light, far ultraviolet light, X-rays, electron beams, α rays, β rays, γ rays, and the like.

  Examples of the photopolymerization initiator that can be used as the component (D) include 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone), 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and the like.

  The amount of component (D) in the composition of the present invention is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, with the total solid content excluding the organic solvent being 100% by mass. is there. A component (D) can be used individually by 1 type or in combination of 2 or more types. If the blending amount of component (D) is less than 0.1% by mass, curing failure may occur, and if it exceeds 15% by mass, the strength of the cured film may decrease due to an excessive amount of component.

5. Organic solvent (E)
The organic solvent (E) used in the present invention is not particularly limited, but usually a solvent having a boiling point of 200 ° C. or less at normal pressure is preferable. Specifically, water, alcohols, ketones, ethers, esters, hydrocarbons, amides and the like are used. These can be used alone or in combination of two or more. Specific examples include propylene glycol monomethyl ether (PGME), cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, methanol, and the like, and propylene glycol monomethyl ether (PGME), cyclohexanone, and methyl ethyl ketone are preferable.
In addition, when using the dispersion liquid which disperse | distributed PTO particle | grains (A) in the solvent, although the solvent which is this dispersion medium mixes in a composition, even if it uses the solvent of this dispersion as (E) component, A different solvent may be added.

  Examples of alcohols include methanol, ethanol, isopropyl alcohol, isobutanol, n-butanol, tert-butanol, ethoxyethanol, butoxyethanol, diethylene glycol monoethyl ether, benzyl alcohol, and phenethyl alcohol. Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of ethers include dibutyl ether and propylene glycol monoethyl ether acetate. Examples of the esters include ethyl acetate, butyl acetate, ethyl lactate, methyl acetoacetate, and ethyl acetoacetate. Examples of hydrocarbons include toluene and xylene. Examples of amides include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.

  The compounding amount of the organic solvent (E) in the composition of the present invention is 50 to 10,000 parts by mass, preferably 50 to 3,000 parts by mass, with the total solid content excluding the organic solvent being 100 parts by mass.

6). Other additives (F)
In the composition of the present invention, as additives other than the components (A) to (E), other compounds having a polymerizable unsaturated group, non-conductive particles, antioxidants, ultraviolet absorbers, light stabilizers Further, a thermal polymerization inhibitor, a leveling agent, a surfactant, a lubricant and the like can be blended as necessary.

(1) Compound having a polymerizable unsaturated group The compound having a polymerizable unsaturated group as an additive is a compound having one polymerizable unsaturated group in the molecule.
Specific examples of the compound having one polymerizable unsaturated group in the molecule include, for example, vinyl group-containing lactams such as N-vinylpyrrolidone and N-vinylcaprolactam, isobornyl (meth) acrylate, bornyl (meth) acrylate, Cyclodecanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, alicyclic structure-containing (meth) acrylate such as cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 4- Butylcyclohexyl (meth) acrylate, acryloylmorpholine, vinylimidazole, vinylpyridine, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (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, dodecyl (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, methoxypolypropylene glycol (meth) acrylate, diacetone (meth) acrylamide, isobutoxymethyl (Meth) acrylamide, N, N-dimethyl (meth) acrylamide, t-octyl (meth) ac Rilamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7-amino-3,7-dimethyloctyl (meth) acrylate, N, N-diethyl (meth) acrylamide, N, N-dimethylaminopropyl ( Examples include meth) acrylamide, hydroxybutyl vinyl ether, lauryl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether, and a compound represented by the following formula (5).
_{^{CH 2 = C (R 11)}} -COO (R 12 O) p -Ph-R 13 Formula (5)
(Wherein R ¹¹ represents a hydrogen atom or a methyl group, R ¹² represents an alkylene group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, and R ¹³ represents a hydrogen atom or 1 to 12 carbon atoms, preferably 1 -9 represents an alkyl group, Ph represents a phenylene group, and p represents a number of 0 to 12, preferably 1 to 8.)

  Commercially available compounds having one polymerizable unsaturated group in the molecule include Aronix M-101, M-102, M-111, M-113, M-114, M-117 (above, Toa Gosei Co., Ltd. Viscoat LA, STA, IBXA, 2-MTA, # 192, # 193 (manufactured by Osaka Organic Chemical Co., Ltd.); NK Ester AMP-10G, AMP-20G, AMP-60G (Sin Nakamura Chemical Industry) Light acrylate LA, SA, IB-XA, PO-A, PO-200A, NP-4EA, NP-8EA (above, manufactured by Kyoeisha Chemical Co., Ltd.); FA-511, FA-512A, FA-513A (manufactured by Hitachi Chemical Co., Ltd.) and the like.

  The compounding amount of the compound having one polymerizable unsaturated group in the molecule in the composition of the present invention is preferably 0 to 24% by mass, more preferably 0, based on 100% by mass of the total solid content excluding the organic solvent. -10 mass%. When the blending amount of the component (E) exceeds 30% by mass, the pencil hardness may be inferior.

(2) Non-conductive particles In the composition of the present invention, the non-conductive particles or the non-conductive particles and the alkoxysilane compound are organically mixed in such a range that the curable composition does not cause problems such as separation and gelation. You may use together the particle | grains obtained by making it react in a solvent.

By using non-conductive particles in combination with PTO particles (A) that are conductive particles, while maintaining a value of 10 ¹³ Ω / □ or less as an antistatic function, that is, a surface resistance when a cured film is used, Scratch resistance can be improved.

  Such non-conductive particles are not particularly limited as long as they are particles other than PTO particles (A). Preferably, it is oxide particles or metal particles other than PTO particles (A). Specifically, an oxide particle containing two or more elements selected from the group consisting of oxide particles such as silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, and cerium oxide, or silicon, aluminum, zirconium, titanium, and cerium. There may be mentioned physical particles.

  The primary particle diameter of the non-conductive particles is preferably 0.1 μm or less, more preferably 0.001 to 0.05 μm, as a value determined by a transmission electron microscope. When it exceeds 0.1 μm, sedimentation may occur in the composition or the smoothness of the coating film may be lowered.

  When mix | blending nonelectroconductive particle | grains with the composition of this invention, you may mix, after hydrolyzing a nonelectroconductive particle and an alkoxysilane compound in an organic solvent. This treatment improves the dispersion stability of the non-conductive particles.

As a commercial product of non-conductive particles, for example, as silicon oxide particles (for example, silica particles), colloidal silica, manufactured by Nissan Chemical Industries, Ltd. Trade names: methanol silica sol, IPA-ST, MEK-ST, NBA -ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL, etc. Can do. Further, as powder silica, product names manufactured by Nippon Aerosil Co., Ltd .: Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil OX50, Asahi Glass Co., Ltd. Product names: Sildex H31, H32, H51, H52, H121 H122, manufactured by Nippon Silica Kogyo Co., Ltd., trade names: E220A, E220, manufactured by Fuji Silysia Co., Ltd., trade name: SYLYSIA470, manufactured by Nippon Sheet Glass Co., Ltd.
Moreover, as an aqueous dispersion of aluminum oxide (alumina), product name: Alumina Sol-100, -200, -520 manufactured by Nissan Chemical Industries, Ltd .; As a dispersion of zirconium oxide, manufactured by Sumitomo Osaka Cement Co., Ltd. ( (Toluene, methyl ethyl ketone-dispersed zirconia sol); As a cerium oxide aqueous dispersion, manufactured by Taki Chemical Co., Ltd. Product name: Niedal; As a powder and solvent dispersion of alumina, zirconium oxide, titanium oxide, etc. Product name: Nanotech etc. can be mentioned.

(3) As antioxidant, Ciba Specialty Chemicals Co., Ltd. brand name: Irganox 1010, 1035, 1076, 1222 etc. are mentioned.
(4) As an ultraviolet absorber, Ciba Specialty Chemicals Co., Ltd. product name: Tinuvin P234, 320, 326, 327, 328, 213, 329, Sipro Kasei Co., Ltd. product name: Seasorb 102, 103, 501, 202, 712 and the like.
(5) As a light stabilizer, Ciba Specialty Chemicals Co., Ltd. Product name: Tinuvin 292, 144, 622LD, Sankyo Co., Ltd. Product name: Sanol LS770, LS440, Sumitomo Chemical Co., Ltd. : Sumisorb TM-061 and the like.
(6) Examples of the thermal polymerization stabilizer include paramethoxyphenol manufactured by Wako Pure Chemical Industries, Ltd.

  The compounding amount of the component (F) in the composition of the present invention is preferably 0.01 to 1% by mass, more preferably 0.01 to 0.5% by mass, with the total solid content excluding the organic solvent being 100% by mass. %. If the blending amount is less than 0.01% by mass, the storage stability of the composition may be deteriorated, or if it exceeds 0.5% by mass, the hardness of the cured film may be insufficient. is there.

  The viscosity of the composition of the present invention thus obtained is usually 1 to 20,000 mPa · s, preferably 1 to 1,000 mPa · s at 25 ° C.

8). Preparation method of composition The composition of the present invention comprises the above (A) PTO particles, (B) a compound having two or more polymerizable unsaturated groups in the molecule, (C) a compound containing a fluorine atom in the molecule, (D) A photopolymerization initiator, (E) an organic solvent, and (F) other compounds having polymerizable unsaturated groups, additives, and non-conductive particles, respectively, at room temperature or heating It can be prepared by mixing under conditions. Specifically, it can be prepared using a mixer such as a mixer, a kneader, a ball mill, or a three roll.

II. Cured film / antistatic laminate The cured film of the present invention can be obtained by applying and drying the above-mentioned curable composition and then irradiating it with radiation to cure the composition.
The surface resistance of the obtained cured film is 10 ¹³ Ω / □ or less, preferably 10 ¹¹ Ω / □ or less, more preferably 10 ⁹ Ω / □ or less. When the surface resistance exceeds 10 ¹³ Ω / □, the antistatic performance is not sufficient, and there is a possibility that dust will be easily attached or the attached dust cannot be easily removed.

  Although there is no restriction | limiting in particular as a coating method of a composition, For example, well-known methods, such as roll coating, spray coating, flow coating, dipping, screen printing, inkjet printing, are applicable.

The radiation source used for curing the composition is not particularly limited as long as it can be cured in a short time after the composition is applied.
Examples of visible ray sources include direct sunlight, lamps, fluorescent lamps, and lasers. Examples of ultraviolet ray sources include mercury lamps, halide lamps, and lasers, and electron beam sources. For example, a method using thermoelectrons generated from a commercially available tungsten filament, a cold cathode method in which metal is generated through a high voltage pulse, and a secondary electron generated by collision of ionized gaseous molecules with a metal electrode. Secondary electron system using
Examples of the source of α-rays, β-rays, and γ-rays include fission materials such as ⁶⁰ Co. For the γ-rays, a vacuum tube or the like that causes accelerated electrons to collide with the anode can be used. These radiations may be irradiated alone or in combination of two or more, or one or more kinds of radiation may be irradiated after a certain period of time.

  Since the cured film of the present invention has excellent scratch resistance and adhesion, it is useful as a hard coat. Further, since it has an excellent antistatic function, it is useful as an antistatic film by being disposed on a substrate of various shapes such as a film, a plate, or a lens.

The antistatic laminate of the present invention is an antistatic laminate having a base material and a cured resin layer containing PTO particles having an average primary particle diameter of 10 nm to 100 nm, and at least one of the PTO particles. The portion is distributed substantially concentrated on one or both of the interface on the substrate side and the interface on the opposite side of the substrate of the cured resin layer. Here, the cured resin layer refers to a layer containing a cured product obtained by curing a radiation curable resin or a thermosetting resin. Preferably, such an antistatic laminate can be produced by forming the cured film of the present invention on a substrate. In this case, the thickness of the cured film is preferably 0.1 to 20 μm. In applications where the abrasion resistance on the outermost surface such as touch panels and CRTs is important, it is relatively thick, preferably 2 to 20 μm. On the other hand, when used as an antistatic film of an optical film, the thickness is preferably 0.1 to 10 μm.
The surface resistance of the antistatic laminate of the present invention is preferably 10 ¹³ Ω / □ or less, more preferably 10 ⁹ Ω / □ or less. When the surface resistance exceeds 10 ¹³ Ω / □, the antistatic performance is not sufficient, and dust may be easily attached or the attached dust may not be easily removed.
Moreover, when using for an optical film, transparency is required and it is preferable that a total light transmittance is 85% or more.

The substrate is not particularly limited, such as metal, ceramics, glass, plastic, wood, slate, etc., but as a material capable of exhibiting high productivity and industrial usefulness such as radiation curability, for example, film, fiber-like It is preferably applied to a substrate. Particularly preferred materials are plastic film and plastic plate. Examples of such plastics include polycarbonate, polymethyl methacrylate, polystyrene / polymethyl methacrylate copolymer, polystyrene, polyester such as polyethylene terephthalate, polyolefin, triacetyl cellulose resin, diethylene glycol diallyl carbonate (CR-39), ABS, and the like. Examples thereof include resins, AS resins, polyamides, epoxy resins, melamine resins, and cyclized polyolefin resins (for example, norbornene resins).
In addition, the laminated body of this invention may have a layer which has various functions as needed other than the cured resin layer formed by hardening the base material and the radiation-curable composition of this invention. Examples of such a layer include an antireflection film layer and a ripple prevention layer.

  Examples of application of the cured film and the antistatic laminate of the present invention include, for example, a protective film for a touch panel, a transfer foil, a hard coat for an optical disk, a window film for an automobile, an antistatic protective film for a lens, a cosmetic container, and the like. The surface protective film of a designable container can be used as a hard coat mainly for the purpose of preventing scratches on the product surface and preventing dust adhesion due to static electricity.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the following, “part” and “%” respectively represent “part by mass” and “% by mass” unless otherwise specified.

Example 1
(1) Production of curable composition In a container shielded from ultraviolet rays, a PTO particle dispersion (ELCOM TL-30S manufactured by Catalyst Chemical Industry Co., Ltd., dispersion solvent: propylene glycol monomethyl ether (PGME), PTO particle concentration 28. 5 mass%, average primary particle size 20 nm, dispersant: Asahi Denka Kogyo Co., Ltd. surfactant TR701, containing 1.5 mass%. 30.70 g, DPHA (Nippon Kayaku Co., Ltd., dipentaerythritol) 155.27 g of a mixture of hexaacrylate and dipentaerythritol pentaacrylate), Megafac F445 (manufactured by Dainippon Ink & Chemicals, Inc., perfluoroalkyl group-containing polyoxyethylene ether) 5.25 g, 1-hydroxycyclohexyl phenyl ketone ( Irgacure photopolymerization initiator manufactured by Nippon Ciba-Geigy Co., Ltd. 84) 5.25 g, p-methoxyphenol 0.02 g, and was obtained methanol 278.20G, the composition 500g of a homogeneous solution by stirring for 2 hours at 50 ° C. The PGME25.31G.
After weighing 2.0 g of the obtained composition in an aluminum dish, it was dried on a hot plate at 140 ° C. for 1 hour and weighed to determine the solid content, which was 35% by mass. In addition, after weighing 2.0 g of the composition in a magnetic crucible, pre-dried on a hot plate at 80 ° C. for 30 minutes and calcined in a muffle furnace at 750 ° C. for 1 hour, the inorganic content in the solid content Was 5% by mass.

(2) Production of cured film film The composition obtained in the above (1) was coated on a PET film (film thickness 100 μm) subjected to easy adhesion treatment on one side using a wire bar coater, and in an oven. And dried at 80 ° C. for 3 minutes. Subsequently, using a high pressure mercury lamp in the atmosphere, the coating film was UV-cured under a light irradiation condition of 0.3 J / cm ² to prepare a film having a cured film (hard coat layer) having a thickness of about 1.5 μm. .

(3) Physical property evaluation of cured film film The PTO particle uneven distribution property, haze, total light transmittance, and surface resistance of the cured film film obtained in the above (2) were evaluated according to the following criteria. The results are shown in Table 1.

(A) Uneven distribution of PTO particles The cross section of the obtained cured film is observed with a transmission electron microscope, and the PTO particles are concentrated and distributed at both interfaces of the cured film or near one of the interfaces. “O”, PTO particles are concentrated and distributed at both interfaces of the cured film or near one of the interfaces, but a portion of the PTO particles remains inside the cured film. The case where it could not be said that the particles were substantially concentrated and distributed at both interfaces of the cured film or near one of the interfaces was evaluated as “x”.

(B) Haze The haze (%) of the cured film was measured according to JIS K7105 using a color haze meter (manufactured by Suga Test Instruments Co., Ltd.).

(C) Total light transmittance The total light transmittance (%) of the cured film was measured using a color haze meter (manufactured by Suga Test Instruments Co., Ltd.) in accordance with JIS K7105.
(D) Surface resistance The surface resistance (Ω / □) of the cured film film was measured using a high resistance meter (Agilent Technology Co., Ltd. Agilent 4339B) and Resistivity Cell 16008B (Agilent Technology Co., Ltd.). Used and measured under the condition of an applied voltage of 100V.

Examples 2 to 6 and Comparative Example 1
Except having used the component shown in Table 1, it carried out similarly to Example 1, and manufactured the radiation-curable composition of Examples 2-6 and the comparative example 1, produced a cured film, and performed the physical-property evaluation of the cured film. It was. The obtained results are shown in Table 1. Moreover, the transmission electron micrograph of the cured film cross section obtained in Example 2, Example 3, Example 6, and Comparative Example 1 is shown in FIGS. In FIG. 1 (Example 2), PTO particles are concentrated and distributed in the vicinity of both the base material side interface and the air side interface. In FIG. 2 (Example 3), the PTO particle is in the vicinity of the base material side interface. In FIG. 3 (Example 6), the PTO particles are concentrated and distributed at both interfaces of the cured film, but a part of the PTO particles remains inside the cured film. Distributed. In FIG. 4 (Comparative Example 1), the PTO particles are hardly concentrated near the interface, and secondary aggregates are distributed inside the cured film.

The abbreviations in Table 1 are as follows.
PTO particles: manufactured by Catalyst Kasei Co., Ltd., ELCOM TL-30S, median diameter 60 nm
Dispersant: Asahi Denka Kogyo Co., Ltd. surfactant, TR701
DPHA: Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.)
Footent 222F: Neos nonionic fluorosurfactant manufactured by Neos Co., Ltd., α-perfluorononenyloxy-ω-perfluorononenyl polyethylene oxide Megafac F445: Nonionic fluorosurfactant manufactured by Dainippon Ink & Chemicals, Inc. Agent, perfluoroalkyl group-containing polyoxyethylene ether Biscoat 4F: Fluorine-containing (meth) acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd., tetrafluoropropyl acrylate Irgacure 184: Photopolymerization initiator manufactured by Ciba Geigy Japan, 1-hydroxy Cyclohexyl phenyl ketone (Molar extinction coefficient at 313 nm: 80 L / mol · cm)

  From the results in Table 1, when the amount of PTO particles is the same (10 parts), the use of fluorine-containing compounds, particularly fluorine-based surfactants and fluorine-based acrylates, results in good uneven distribution. It can be seen that the surface resistance is good with approximately the same size. Also, by using a fluorosurfactant, even if the amount of PTO particles is reduced to 5 parts, the uneven distribution is good, and the amount of PTO particles of 5 parts is equivalent to the amount of PTO particles of 10 parts and haze, It can be seen that the surface resistance can be expressed to the same level or higher.

According to the present invention, there is provided a curable composition that is excellent in curability and can form a coating film (film) excellent in antistatic property, hardness, scratch resistance, and transparency on the surface of various substrates. Can be provided.
The cured film of the present invention mainly includes, for example, a protective film for a touch panel, a transfer foil, a hard coat for an optical disk, a window film for an automobile, an antistatic protective film for a lens, a surface protective film for a high-design container such as a cosmetic container, etc. It can be used as a hard coat for the purpose of preventing scratches on the product surface and preventing dust from adhering to static electricity.
The antistatic laminate of the present invention can be used, for example, for high-design containers such as touch panels, transfer foils, optical disk hard coats, automobile window films, cosmetic containers, and the like.

2 is a transmission electron micrograph showing a cross section of a cured film obtained in Example 2. FIG. 3 is a transmission electron micrograph showing a cross section of a cured film obtained in Example 3. FIG. 6 is a transmission electron micrograph showing a cross section of the cured film obtained in Example 6. FIG. 2 is a transmission electron micrograph showing a cross section of a cured film obtained in Comparative Example 1.

Claims (11)

The following components (A) to (C):
(A) Particles having an average primary particle diameter of 10 nm to 100 nm and containing phosphorus-containing tin oxide as a main component (B) Compound having two or more polymerizable unsaturated groups in the molecule (C) Fluorine-based surfactant Or a composition containing fluorine-containing (meth) acrylic esters ,
The curable composition which contains the said component (A) in the ratio of 1 mass% or more and less than 25 mass%, when the solid content whole quantity except the organic solvent in a composition is 100 mass%.   The curable composition according to claim 1, wherein the component (C) is a nonionic and / or anionic fluorosurfactant.   The curable composition of Claim 1 or 2 in which the said component (B) contains the compound which has a 6 or more polymerizable unsaturated group in a molecule | numerator.   Furthermore, (D) The curable composition of any one of Claims 1-3 containing the photoinitiator whose molar absorption coefficient in 313 nm is 5000 L / mol * cm or less.   The component (D) is 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone ), 2,2-dimethoxy-1,2-diphenylethane-1-one and 2-hydroxy-2-methyl-1-phenyl-propan-1-one, Item 4. The curable composition according to any one of Items 1 to 3.   Furthermore, (E) The curable composition of any one of Claims 1-5 containing the organic solvent. The cured film which is obtained by hardening | curing the curable composition of any one of Claims 1-6, and whose surface resistance value is 10 < ¹³ > ohm / square or less.   The manufacturing method of the cured film which has a process which irradiates a radiation to the curable composition of any one of Claims 1-6, and hardens this composition. An antistatic laminate comprising a substrate and a cured resin layer containing PTO particles having an average primary particle diameter of 10 nm to 100 nm, wherein at least a part of the PTO particles is a substrate of the cured resin layer Distributed substantially concentrated on one or both of the side interface and the interface opposite the substrate,
An antistatic laminate having a surface resistance value of 10 ¹³ Ω / □ or less.   The laminate for antistatics according to claim 9, wherein the cured resin layer is obtained by curing the curable composition according to any one of claims 1 to 6. An antistatic laminate comprising a substrate and a cured resin layer containing PTO particles having an average primary particle diameter of 10 nm to 100 nm, wherein at least a part of the PTO particles is a substrate of the cured resin layer A method for producing an antistatic laminate which is substantially concentrated and distributed on one or both of a side interface and a side opposite to a substrate, wherein the laminate is any one of claims 1 to 6. A method for producing an antistatic laminate, comprising: a step of applying the curable composition according to item 1; and a step of irradiating the curable composition with radiation to cure the composition.