JP2019196428A - Curable composition - Google Patents

Abstract

To provide a curable composition that has an effectively reduced surface resistance value of a cured film for the carbon nanotube content.SOLUTION: The curable composition including (A) carbon nanotube, (B) a polyfunctional (meth)acrylate compound, (C) a cationic polymerizable compound, (D) a radical polymerization initiator and (E) an acid generator can form a cured film having a remarkably reduced surface resistance value of the cured film for the carbon nanotube content and therefore, the cured film can be obtained as one excellent in antistatic properties and transparency.SELECTED DRAWING: None

Description

  The present invention relates to a curable composition. More specifically, the present invention relates to a curable composition in which the surface resistance value of a cured film is significantly reduced for the content of carbon nanotubes.

  Carbon nanotubes are a kind of fullerene in which a carbon six-membered ring network (graphene sheet) is formed into a single-layer or multi-layer tube shape. Single-wall carbon nanotubes (SWCNT) are single-wall carbon nanotubes and multi-walls are multi-wall ones. It is called a carbon nanotube (MWCNT). One of the characteristics of this carbon nanotube is that it has a high dielectric constant (low electrical resistance). In terms of its application, the negative electrode agent of a fuel cell, a Li ion secondary battery, an electron emission source for a flat panel display, or Transparent conductive materials are being studied. For curable compositions containing carbon nanotubes, due to the ease of patterning and high coating film properties after curing, attempts to expand into various applications utilizing the characteristics of carbon nanotubes as described above Has been made.

As an example of such an attempt, it has been studied to provide an antistatic ability by adding carbon nanotubes to a curable composition for hard coating. For example, in Patent Document 1, by using a polyfunctional urethane (meth) acrylate having a carbon nanotube and an isocyanurate structure, the dispersion stability of the carbon nanotube in the antistatic hard coat composition is improved. There has been disclosed an antistatic hard coat coating film which can provide sufficient antistatic performance only by using a small amount and is excellent in transparency. In Patent Document 1, specifically, in a cured coating film having a thickness of 1 to 2 μm of a resin composition containing 0.9 to 7.4% of carbon nanotubes, the total light transmittance is 70 to 90%, and the surface resistance value is 2. It is described that × 10 ⁷ to 8 × 10 ¹⁰ Ω / □ and pencil hardness H to 2H were obtained.

In addition, for example, Patent Document 2 fully exhibits the characteristics of carbon nanotubes, siloxane compounds, and conductive polymers themselves, is not dependent on humidity, has excellent conductivity and film formability, water resistance, weather resistance, mechanical properties. A carbon nanotube-containing curable composition excellent in strength, scratch resistance and hardness is disclosed. Specifically, Patent Document 2 discloses an antistatic composition containing carbon nanotubes, a siloxane compound, and a cationic polymerization initiator. From the antistatic resin composition containing 0.25% of carbon nanotubes, a surface resistance value is disclosed. It is described that a cured film of 6.7 × 10 ⁸ Ω / □ was obtained.

JP 2012-62357 A JP 2007-56125 A

  In both Patent Documents 1 and 2, the amount of carbon nanotubes added to obtain the desired antistatic property is still large. For this reason, there is a problem in that the transparency is insufficient in applications requiring high transparency, and the antistatic ability is insufficient in applications where high transparency is not required. These problems are caused by the fact that the conventional antistatic curable composition cannot effectively reduce the surface resistance of the cured film for the amount of carbon nanotubes added.

  Therefore, an object of the present invention is to effectively reduce the surface resistance value of the cured film relative to the content of the carbon nanotubes. It may be described as resistance reduction.) To provide a curable composition.

  As a result of intensive studies, the present inventor made a curable composition containing carbon nanotubes coexist with a polyfunctional (meth) acrylate compound and a polymerization initiator thereof together with a cationic polymerizable compound and a polymerization initiator thereof. It has been found that excellent surface resistance reduction can be obtained. The present invention has been completed by further studies based on this finding.

That is, this invention provides the invention of the aspect hung up below.
Item 1. A curable composition comprising (A) a carbon nanotube, (B) a polyfunctional (meth) acrylate compound, (C) a cationic polymerizable compound, (D) a radical polymerization initiator, and (E) an acid generator. object.
Item 2. Item 2. The curable composition according to Item 1, wherein the component (B) contains a tri- or higher functional (meth) acrylate compound.
Item 3. Item 3. The curable composition according to Item 1 or 2, wherein the component (B) contains a polyfunctional (meth) acrylate compound having an SP value of 10.8 or more.
Item 4. The component (B) is selected from the group consisting of a polyfunctional (meth) acrylate compound having an acidic group, a polyfunctional (meth) acrylate compound having an alkylene oxide group, and a polyfunctional (meth) acrylate compound having a polyglycerin structure. Item 4. The curable composition according to any one of Items 1 to 3.
Item 5. Item 5. The curable composition according to any one of Items 1 to 4, wherein the component (C) is a polyfunctional cationically polymerizable compound.
Item 6. Item 6. The curable composition according to any one of Items 1 to 5, wherein the component (C) is a non-aromatic cationic polymerizable compound.
Item 7. Item 7. The curable composition according to any one of Items 1 to 6, wherein the component (C) is a non-aromatic epoxy compound.
Item 8. Item (F) The curable composition according to any one of Items 1 to 7, further comprising a heteropolymerizable compound having a cationic polymerizable group and a radical polymerizable group in one molecule.
Item 9. Item 9. The curable composition according to Item 8, wherein the component (F) is a vinyl ether group-containing (meth) acrylic acid ester.
Item 10. Item 1-9, wherein the content of the component (A) with respect to 100 parts by mass of the components other than the organic solvent among the components constituting the curable composition is 0.01 to 0.15 parts by mass. The curable composition as described.
Item 11. Item 11. The curable composition according to any one of Items 1 to 10, wherein the content of the component (C) with respect to 100 parts by mass of the total amount of the component (B) and the component (C) is 35 to 80 parts by mass. object.
Item 12. Item 12. The curable composition according to any one of Items 1 to 11, which is an antistatic curable composition.
Item 13. Item 13. A cured film of the curable composition according to any one of Items 1 to 12.
Item 14. Item 14. A laminate having the cured film according to Item 13 on a substrate.

  ADVANTAGE OF THE INVENTION According to this invention, the curable composition in which the surface resistance value of the cured film was effectively reduced is provided for the content of carbon nanotubes.

About each curable composition obtained in Comparative Example 1 and Examples 1 to 5 and Comparative Example 3 and Examples 7 to 12, the ratio of cationically polymerizable compounds (total of (B) and (C) The relationship between the value of (C) parts by mass per 100 parts by mass) and the surface resistance value is shown.

<Curable composition>
The curable composition of the present invention comprises (A) carbon nanotubes (hereinafter sometimes simply referred to as component (A)) and (B) a polyfunctional (meth) acrylate compound (hereinafter simply referred to as component (B). ), (C) a cationic polymerizable compound (hereinafter sometimes simply referred to as component (C)), and (D) a radical polymerization initiator (hereinafter simply referred to as component (D)). And (E) an acid generator (hereinafter sometimes simply referred to as component (E)). The curable composition of the present invention further includes a heteropolymerizable compound (F) having a cationic polymerizable group and a radical polymerizable group in one molecule (hereinafter sometimes simply referred to as the component (F)). be able to.

  In the curable composition of the present invention, the component (A), the component (B) having a fast curing reaction rate, and the component (C) having a slow reaction rate are allowed to coexist. And the difference in the curing reaction rate of the component (B) is utilized. Specifically, as the curing reaction proceeds, the component (A) dispersed in the curable composition is taken into the component (C), which has a slow curing reaction, and the components (A) gather together in the cured film. Take advantage of the nature. Thereby, the conductive network of (A) components can be formed very simply and efficiently. The conductive network of the components (A) thus formed can reduce the surface resistance of the cured film and obtain a good antistatic ability.

<(A) Carbon nanotube>
The curable composition of this invention contains a carbon nanotube as (A) component. The carbon nanotube is not particularly limited, and examples thereof include a substance in which a six-membered ring network (graphene sheet) made of carbon has a single-layer or multilayer coaxial tube. Specifically, examples of the carbon nanotube include a single-wall single-wall carbon nanotube (SWCNT) and a multi-wall multi-wall carbon nanotube (MWCNT).

  The carbon nanotube may be produced by any method. The carbon nanotube production method preferably includes a method in which a bundle of a plurality of carbon nanotubes is formed on a substrate and vertically aligned. Specifically, a method of generating an arc discharge between carbon electrodes and growing it on the cathode surface of the discharge electrode (arc discharge method), a method of heating and sublimating silicon carbide with a laser beam (laser evaporation method) And a method of carbonizing hydrocarbons in a gas phase under a reducing atmosphere using a transition metal catalyst (chemical vapor deposition method: CVD method), a thermal decomposition method, a method using plasma discharge, and the like. The carbon nanotubes are preferably obtained by a process in which the carbon nanotube bundles are loosened in strong dispersion after the carbon nanotube bundles are formed. Since carbon nanotubes are easily cut by this step, a chemical vapor deposition method (CVD method) in which long carbon nanotubes are easily obtained is more preferable as a method for producing carbon nanotubes.

As more specific examples of carbon nanotubes, TUBALL ^™ MATRIX 301 (manufactured by OCSiAl); CNF-T (manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd.); SN2301, SN7689, SN2302, SN9847 and SN4908 (manufactured by SUN INNOVATIONS); VGCF-X (made by Showa Denko KK) etc. are mentioned.

  As a diameter of a carbon nanotube, 0.4 nm or more and 30 nm or less are mentioned from a viewpoint of addition amount suppression and transparency, for example. Examples of the length of the carbon nanotube include 0.1 μm or more and 50 μm or less from the viewpoint of conductivity, dispersibility, and transparency.

The content of the component (A) in the curable composition of the present invention is not particularly limited, but the curable composition of the present invention significantly reduces the surface resistance value of the cured film relative to the content of carbon nanotubes. Therefore, the content can be made very low. Reducing the content of carbon nanotubes is extremely advantageous in that high transparency can be obtained. Specifically, the content of the component (A) in the curable composition is other than the organic solvent among the components constituting the curable composition from the viewpoint of achieving both reduced surface resistance and transparency of the cured film. 100 parts by mass of the component (100 parts by mass refers to the amount of the entire curable composition when the curable composition does not contain an organic solvent, and in the curable composition when the curable composition contains an organic solvent. The total amount of components other than the organic solvent is 0.01 to 0.15 parts by mass, preferably 0.03 to 0.15 parts by mass, more preferably 0.05 parts by mass. -0.10 mass part is mentioned.

High transparency means that the total light transmittance of a cured film having a thickness of 10 μm obtained from the curable composition of the present invention is measured when the total light transmittance is measured by performing the transparency test described in the Examples below. For example, it means 80% or more, preferably 84% or more. In the case where such high transparency is not required, the content of the component (A) in the curable composition constitutes the curable composition from the viewpoint of more preferably reducing the surface resistance of the cured film. It does not matter even if it exceeds 0.15 parts by mass with respect to 100 parts by mass of the components other than the organic solvent.

<(B) Polyfunctional (meth) acrylate compound>
The curable composition of this invention contains a polyfunctional (meth) acrylate compound as (B) component. The polyfunctional (meth) acrylate compound refers to a (meth) acrylate compound having two or more (meth) acryloyl groups in one molecule (that is, bifunctional or more). (Meth) acrylate means either one or both of acrylate and methacrylate.

  The polyfunctional (meth) acrylate compound quickly polymerizes and cures starting from the radical generated from the component (D). By using a polyfunctional (meth) acrylate compound, a cured film having a high crosslinking density and excellent scratch resistance can be obtained. In addition, the polyfunctional (meth) acrylate compound is considered to be easily separated from other components (for example, the (A) component and the (C) component) in the cured composition because of particularly shrinkage due to curing. A) It is considered that a conductive network between components can be formed very simply and efficiently.

  As the bifunctional (meth) acrylate compound, an ester compound of a dihydric alcohol and (meth) acrylic acid [for example, di (meth) acrylate of ethylene glycol, di (meth) acrylate of diethylene glycol, di (meth) acrylate of propylene glycol, Di (meth) acrylate of dipropylene glycol, di (meth) acrylate of neopentyl glycol]; ester compound of trihydric or higher polyhydric alcohol and (meth) acrylic acid [for example, di (meth) acrylate of glycerin, trimethylol Di (meth) acrylate of propane, di (meth) acrylate of pentaerythritol, di (meth) acrylate of ditrimethylolpropane and di (meth) acrylate of dipentaerythritol]; linear aliphatic diol and (meth Ester compound of acrylic acid [e.g., 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10- Di (meth) acrylate of decanediol]; ester compound of aliphatic diol having side chain and (meth) acrylic acid [for example, di (meth) acrylate of 3-methyl-1,5-pentanediol, 2-butyl-2 -Di (meth) acrylate of ethyl-1,3-propanediol]; ester compound of alicyclic hydrocarbon diol and (meth) acrylic acid [eg di (meth) acrylate of dimethylol-tricyclodecane]; aromatic Hydrocarbon diol and (meth) acrylic acid ester compounds [eg di (meth) a of bisphenol A Relate]; ester compound of polyhydric alcohol and (meth) acrylic acid [for example, di (meth) acrylate of ethylene oxide adduct of bisphenol A, di (meth) acrylate of propylene oxide adduct of bisphenol A, ethylene oxide of pentaerythritol Di (meth) acrylate of adduct]; ester compound of polyhydric alcohol, (meth) acrylic acid and hydroxycarboxylic acid [for example, neopentyl glycol di (meth) acrylate of hydroxypivalate]; terminal having hydroxyl group in side chain is epoxy And an ester compound of an epoxy compound of a group and acrylic acid.

  Examples of the trifunctional (meth) acrylate compound include glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, and pentaerythritol tri (meth) acrylate.

  As tetrafunctional or higher (for example, tetrafunctional to hexafunctional) (meth) acrylate compounds, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate (Shin Nakamura Chemical Co., Ltd.) Company-made A-DPH etc.) etc. are mentioned.

  As the polyfunctional (meth) acrylate compound, in addition to the above polyfunctional (meth) acrylate compound, a compound containing one or more urethane bonds with two or more (meth) acryloyl groups in one molecule (polyfunctional urethane) (Meth) acrylate compounds).

  As the polyfunctional urethane (meth) acrylate compound, a urethane (meth) acrylate compound which is a reaction product of a diol, a polyisocyanate and a (meth) acrylate having a hydroxyl group, a polyfunctional (meta) having active hydrogen (hydroxyl group, amine, etc.) ) A polyfunctional urethane (meth) acrylate compound that is a reaction product of an acrylate and a polyisocyanate compound. These can be used individually or in mixture of 2 or more types.

  Examples of the polyfunctional (meth) acrylate having active hydrogen (hydroxyl group, amine, etc.) include pentaerythritols, methylols, and epoxy (meth) acrylates. Pentaerythritols include pentaerythritol poly (meth) acrylates such as pentaerythritol di (meth) acrylate and pentaerythritol tri (meth) acrylate; dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, di Examples thereof include dipentaerythritol poly (meth) acrylates such as pentaerythritol tetra (meth) acrylate and dipentaerythritol penta (meth) acrylate. Examples of methylols include trimethylolpropane di (meth) acrylate. Examples of the epoxy (meth) acrylates include bisphenol A diepoxy (meth) acrylate. Among these, pentaerythritols are preferable, dipentaerythritol poly (meth) acrylate is more preferable, and dipentaerythritol penta (meth) acrylate is more preferable. These polyfunctional (meth) acrylates having active hydrogen can be used alone or in combination of two kinds.

  As said polyisocyanate, the polyisocyanate comprised by a chain | strand-shaped saturated hydrocarbon, cyclic saturated hydrocarbon (alicyclic), and aromatic hydrocarbon can be used. Examples of such polyisocyanates include isocyanurates and other polyisocyanates, for example, chain saturated hydrocarbon polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate; Cyclic saturated hydrocarbon (alicyclic) polyisocyanates such as isophorone diisocyanate, dicyclohexylmethane diisocyanate, methylenebis (4-cyclohexylisocyanate), hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, hydrogenated toluene diisocyanate; 2,4-tolylene diisocyanate 1,3-xylylene diisocyanate, p-phenylene diisocyanate, 3,3′-dimethyl-4,4′-diisocyanate Sulfonates, 6-isopropyl-1,3-phenyl diisocyanate, aromatic polyisocyanates such as 1,5-naphthalene diisocyanate. Among these, chain saturated hydrocarbon polyisocyanate is preferable, and isocyanurate of hexamethylene diisocyanate is more preferable. These polyisocyanates can be used alone or in combination of two kinds.

  From the viewpoint of scratch resistance of the cured film, the polyfunctional urethane (meth) acrylate compound is preferably trifunctional or more, more preferably 6 or more, still more preferably 12 or more, and even more preferably 15 or more. Examples include urethane (meth) acrylate compounds.

  Among the polyfunctional urethane (meth) acrylates described above, a reaction product of dipentaerythritol poly (meth) acrylate and isocyanurate of hexamethylene diisocyanate is preferable, and dipentaerythritol penta (meth) acrylate and isocyanurate of hexamethylene diisocyanate The reaction product is more preferable.

  From another point of view, the component (B) preferably contains a highly polar polyfunctional (meth) acrylate compound for the purpose of more preferably obtaining reduced surface resistance of the cured film. The highly polar polyfunctional (meth) acrylate compound becomes more hydrophilic depending on its polarity, so that it can be easily separated from the hydrophobic (A). Thereby, the conductive network of (A) components can be formed more simply and efficiently.

  Examples of the highly polar polyfunctional (meth) acrylate compound include a polyfunctional (meth) acrylate compound having an SP value of 10.8 or more from the viewpoint of the SP value. The SP value of the highly polar polyfunctional (meth) acrylate compound is a value calculated from the measurement results of solubility in tetrahydrofuran (THF), heptane and water as follows. Specifically, it is derived by the method described in the examples.

  Moreover, as a highly polar polyfunctional (meth) acrylate compound, from the viewpoint of molecular structure, a polyfunctional (meth) acrylate compound having an acidic group, a polyfunctional (meth) acrylate compound having an alkylene oxide group, and a polyglycerin structure And polyfunctional (meth) acrylate compounds having These highly polar polyfunctional (meth) acrylate compounds can be used alone or in combination of two or more.

  In the polyfunctional (meth) acrylate compound having an acidic group, examples of the acidic group include a carboxyl group, a sulfo group, and a phosphate ester group, and a carboxyl group is preferable. These acidic groups can be used alone or in combination.

  Examples of the polyfunctional (meth) acrylate compound having a carboxyl group include a succinic acid adduct of pentaerythritol tri (meth) acrylate, a succinic acid adduct of dipentaerythritol penta (meth) acrylate, and a pentaerythritol tri (meth) acrylate. Maleic acid adduct, maleic acid adduct of dipentaerythritol penta (meth) acrylate, dicarboxylic acid adduct of dipentaerythritol tetra (meth) acrylate, maleic acid adduct of EO 6 mol addition pentaerythritol tri (meth) acrylate, EO10 Examples thereof include cyclohexenyl carboxylic acid adducts of molar addition dipentaerythritol penta (meth) acrylate. The carboxyl group content is indicated by an acid value. The acid value of the polyfunctional (meth) acrylate having a carboxyl group is, for example, 10 to 200 mgKOH / g, preferably 20 to 120 mgKOH / g, and more preferably 80 to 120 mgKOH / g. More specifically, Aronix M510 (manufactured by Toagosei Co., Ltd.), Aronix M520 (manufactured by Toagosei Co., Ltd.) and the like can be mentioned.

  Examples of the polyfunctional (meth) acrylate compound having a sulfo group include sulfonate esters of pentaerythritol tri (meth) acrylate, sulfonate esters of dipentaerythritol penta (meth) acrylate, and the like.

  Examples of the polyfunctional (meth) acrylate compound having a phosphate ester group include phosphate ester of pentaerythritol tri (meth) acrylate, phosphate ester of dipentaerythritol penta (meth) acrylate, and the like.

In the polyfunctional (meth) acrylate compound having an alkylene oxide group, the alkylene oxide group is — (OR) _n — (R represents a linear or branched alkylene group, and n represents an integer of 2 to 30). expressed.

  Examples of the polyfunctional (meth) acrylate compound having an alkylene oxide group include esterified product of polyalkylene oxide of dihydric alcohol and (meth) acrylic acid [for example, di (meth) acrylate of polyethylene glycol, di (meth) acrylate of polypropylene glycol ] Tri (meth) acrylate of ethylene oxide adduct of trimethylolpropane; Poly (meth) acrylate of alkylene oxide adduct of above-mentioned tetrafunctional or higher (for example, tetrafunctional to hexafunctional) (meth) acrylate.

  Examples of polyfunctional (meth) acrylate compounds having a polyglycerin structure include polyglycerin-modified (meth) acrylate compounds, polyglycerin ethylene oxide-modified (meth) acrylate compounds, and hyperbranched polyglycerin-modified (meth) acrylate compounds. .

  The polyglycerol-modified (meth) acrylate compound is a compound in which polyglycerol is added to (meth) acrylate. As an average degree of polymerization obtained by the hydroxyl equivalent of polyglycerol, 2-20 are mentioned, Preferably 2-10 are mentioned. (Meth) acrylic acid, (meth) acrylic acid ester of lower alcohol, (meth) acrylic acid halide, isocyanate compound having (meth) acryloyl group (for example, 2-isocyanatoethyl methacrylate (Showa Denko Karenz AOI)), It can be obtained by reacting an epoxy compound having a (meth) acryloyl group. The polyglycerol-modified (meth) acrylated product has a molecular structure in which a (meth) acryloyl group is added to all or a part of the hydroxyl groups of polyglycerol.

  The polyglycerol ethylene oxide-modified (meth) acrylate compound is a (meth) acrylate compound obtained by modifying ethylene glycol with polyglycerol. As an average degree of polymerization obtained by the hydroxyl equivalent of polyglycerol, 2-20 are mentioned, Preferably 2-10 are mentioned. As a total of the addition unit number of ethylene oxide added to polyglycerol, 1-40 mol is mentioned with respect to 1 mol of polyglycerol, Preferably 4-40 mol is mentioned. Polyglycerin ethylene oxide modified (meth) acrylate compound is obtained by reacting polyglycerin with ethylene oxide to obtain polyglycerin alkylene oxide, then (meth) acrylic acid, (meth) acrylic acid ester of lower alcohol, (meth) acrylic It can be obtained by reacting an acid halide, an isocyanate compound having a (meth) acryloyl group, an epoxy compound having a (meth) acryloyl group, and the like. The polyglycerol ethylene oxide-modified (meth) acrylate compound has a molecular structure in which ethylene oxide is added to all of the hydroxyl groups of polyglycerol and (meth) acryloyl groups are added to all or part of the ends of the molecular branches.

  More specifically, as the polyglycerin ethylene oxide modified (meth) acrylate compound, NK ECONOMER series (A-PG5009E, A-PG5027E, A-PG5054E; manufactured by Shin-Nakamura Chemical Co., Ltd.), M-460 (Dongguan) Synthetic Co., Ltd.) and the like.

  The hyperbranched polyglycerin-modified (meth) acrylate compound has a configuration in which a hydrogen atom of at least one hydroxyl group of the hyperbranched polyglycerin is substituted with a (meth) acryloyl group. The hyperbranched polyglycerin has a degree of polymerization (the number of monomer units derived from glycerin) of, for example, 3 or more, preferably 3 to 40, more preferably 10 to 20, and 50% or more of all hydroxyl groups, preferably 50 to 100. %, More preferably 70 to 100%, and still more preferably 75 to 100% is a primary hydroxyl group. The number of (meth) acryloyloxy groups in polyglycerin (meth) acrylate [addition ratio of (meth) acryloyl group] is (meth) relative to the sum of hydroxyl groups and (meth) acryloyloxy groups of polyglycerin (meth) acrylate. As a ratio of an acryloyloxy group, 2 to 100%, for example, Preferably 10 to 50% is mentioned.

  The component (B) preferably contains a trifunctional or higher functional (meth) acrylate compound from the viewpoint of scratch resistance and hardness of the cured film. (B) As a quantity of the tri- or more functional (meth) acrylate compound per 100 parts by mass of the component, from the viewpoint of scratch resistance and hardness of the cured film, for example, 40 to 100 parts by mass, preferably 50 to 100 parts by mass, More preferably, it is 70-100 mass parts, More preferably, 90-100 mass parts or 100 mass parts is mentioned.

  When the (B) component contains a highly polar polyfunctional (meth) acrylate compound, the amount of the highly polar polyfunctional (meth) acrylate compound per 100 parts by mass of the component (B) is the surface resistance reducing property of the cured film. From the viewpoint of being more preferable, for example, 40 to 100 parts by mass, preferably 50 to 100 parts by mass, more preferably 70 to 100 parts by mass, and still more preferably 90 to 100 parts by mass, or 100 parts by mass.

  The content of the component (B) per 100 parts by mass of the total amount of the component (B) and the component (C) is, for example, 10 to 90 parts by mass, preferably 20 to 80 from the viewpoint of reducing the surface resistance of the cured film. A mass part, More preferably, it is 70-20 mass part, More preferably, it is 20-65 mass part, More preferably, it is 25-55 mass part, Most preferably, 35-55 mass part is mentioned.

  As the component (B) in the curable composition of the present invention, the component (D) contained in the curable composition (in an amount matching the ratio to the component (B) in the curable composition) is used (B). A component having a cured product having a hardness of B or higher, preferably H or higher, more preferably 2H or higher, and particularly preferably 3H or higher when the component is cured alone can be used. In the curable composition of the present invention, particularly when a curable composition for hard coat is used, at least one of the (B) component and the (C) component may contain a component having a cured product hardness of 3H or more. preferable. Although it does not specifically limit as an upper limit of hardness, For example, 6H is mentioned. In addition, hardness is the value measured based on the mechanical property-scratch hardness (pencil method) of a JISK5600-5-4 (1999) coating film as described in an Example.

  As content of (B) component in the curable composition of this invention, the total amount of (B) component and (C) component is components 100 other than the organic solvent among the components which comprise a curable composition. For example, 70 mass parts-99 mass parts with respect to a mass part, Preferably 80 mass parts-98 mass parts are mentioned. Moreover, as content of (B) component in the curable composition of this invention, 100 mass parts of components other than the organic solvent among the components which comprise a curable composition from a viewpoint of the surface resistance reduction property of a cured film. For example, 10 mass parts-90 mass parts, Preferably 15 mass parts-80 mass parts are mentioned.

<(C) Cationic polymerizable compound>
The cationically polymerizable compound is not particularly limited, and is not particularly limited as long as it is a compound that starts a polymerization reaction with an acid generated from the component (E) and cures. Specifically, as a cationic polymerizable compound, a compound having an oxetane ring (hereinafter also referred to as an oxetane compound), a compound having an oxirane ring (epoxy ring) (hereinafter also referred to as an epoxy compound), a vinyl ether compound, and the like. Is mentioned. These cationically polymerizable compounds can be used alone or in combination of two or more.

  Among these cationic polymerizable compounds, the cationic polymerizable compound is preferably a compound having a cyclic ether structure such as an oxetane compound and an epoxy compound from the viewpoint of reducing the surface resistance of the cured film.

As another aspect, the cationic polymerizable compound may be an aromatic cationic polymerizable compound having an aryl group or a non-aromatic cationic polymerizable compound not containing an aryl group. From the viewpoint of more preferably reducing the surface resistance, it is preferably a non-aromatic cation polymerizable compound. Specific examples of the non-aromatic cationic polymerizable compound include alicyclic cationic polymerizable compounds and aliphatic cationic polymerizable compounds.

From the viewpoint of the number of functional groups, the cationic polymerizable compound may be a monofunctional cationic polymerizable compound or a polyfunctional cationic polymerizable compound. From the viewpoint of further preferably reducing the surface resistance of the cured film, it is preferably a polyfunctional cation polymerizable compound.

  The oxetane compound is not particularly limited as long as it is a compound having an oxetane ring in the molecule, and a known oxetane compound can be arbitrarily selected and used. In the present invention, examples of the oxetane compound include a compound having one oxetane ring in the molecule (monofunctional oxetane compound) and a compound having two or more oxetane rings in the molecule (polyfunctional oxetane compound).

  Examples of the compound having one oxetane ring in the molecule include compounds represented by the following formula (1).

R ^a1 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, an allyl group, an aryl group, a furyl group, or a thienyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. Preferred examples of the fluoroalkyl group include those in which any hydrogen of these alkyl groups is substituted with a fluorine atom.

R ^a2 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, an alkylcarbonyl group having 2 to 6 carbon atoms, or an alkyl group having 2 to 6 carbon atoms. An alkoxycarbonyl group, an N-alkylcarbamoyl group having 2 to 6 carbon atoms, preferably a non-aromatic hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms Group, an alkylcarbonyl group having 2 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, and an N-alkylcarbamoyl group having 2 to 6 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the alkenyl group include a 1-propenyl group, a 2-propenyl group, a 2-methyl-1-propenyl group, and 2-methyl-2. -Propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, and the like. Examples of the group having an aryl group include phenyl group, benzyl group, fluorobenzyl group, methoxybenzyl group, phenoxyethyl group and the like. Can be mentioned. As the alkylcarbonyl group, an ethylcarbonyl group, a propylcarbonyl group, a butylcarbonyl group, etc., as an alkoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, etc., as an N-alkylcarbamoyl group, Examples thereof include an ethylcarbamoyl group, a propylcarbamoyl group, a butylcarbamoyl group, and a pentylcarbamoyl group. R ^a2 may have a substituent, and examples of the substituent include 1 to 6 alkyl groups and fluorine atoms.

  As a commercial item of the compound represented by the formula (1), OXT-101 (3-ethyl-3-hydroxymethyloxetane: manufactured by Toagosei Co., Ltd.), OXT-212 (3-ethyl-3-[(2-ethyl) Hexyloxy) methyl] oxetane: manufactured by Toagosei Co., Ltd.).

  From the viewpoint of further preferably reducing the surface resistance of the cured film, the oxetane compound preferably includes at least a compound having two or more oxetane rings (polyfunctional oxetane compound). In the oxetane compound having two or more oxetane rings, the number of oxetane rings in the molecule is preferably 2 to 4, more preferably 2 to 3, and still more preferably 2.

  Examples of the compound having two oxetane rings in the molecule include compounds represented by the following formulas (2) and (3). Among these, a compound represented by the following formula (3) is preferable from the viewpoint of further preferably improving the surface resistance reduction of the cured film.

R ^a1 has the same ^meaning as in formula (1). Two R ^a1 may be the same as or different from each other.

R ^a3 represents a linear or branched alkylene group, a linear or branched poly (alkyleneoxy) group, a linear or branched unsaturated hydrocarbon group, a carbonyl group or an alkylene group containing a carbonyl group, a carboxyl group Represents an alkylene group containing a carbamoyl group. Examples of the alkylene group include an ethylene group, a propylene group, and a butylene group. Examples of the poly (alkyleneoxy) group include a poly (ethyleneoxy) group and a poly (propyleneoxy) group. Examples of the unsaturated hydrocarbon group include a propenylene group, a methylpropenylene group, and a butenylene group. R ^a3 may be a polyvalent group represented by (1A) to (1C) below.

When R ^a3 is the above polyvalent group (1A) to (1C), R ^a4 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, or a nitro group. , A cyano group, a mercapto group, a lower alkyl carboxyl group, a carboxyl group, or a carbamoyl group. R ^a5 represents an oxygen atom, a sulfur atom, a methylene group, NH, SO, SO ₂ , C (CF ₃ ) ₂ , or C (CH ₃ ) ₂ . R ^a6 represents an alkyl group having 1 to 4 carbon atoms or an aryl group. R ^a6 is preferably a non-aromatic alkyl group having 1 to 4 carbon atoms. N represents an integer of 0 to 2,000. R ^a7 represents an alkyl group having 1 to 4 carbon atoms or an aryl group. R ^a7 is preferably a non-aromatic alkyl group having 1 to 4 carbon atoms or a monovalent group having a structure of the following formula (1C-A). In the following formula (1C-A), R ^a8 represents an alkyl group having 1 to 4 carbon atoms or an aryl group. R ^a8 is preferably a non-aromatic alkyl group having 1 to 4 carbon atoms. m represents an integer of 0 to 100.

  As a commercial item of the compound represented by the formula (2), OXT-121 (1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene: manufactured by Toagosei Co., Ltd.) and the like can be mentioned. Moreover, as a commercial item of the compound represented by Formula (3), OXT-221 (3-ethyl-3 {[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane: manufactured by Toagosei Co., Ltd.) Is mentioned.

  Examples of the compound having 3 to 4 oxetane rings in the molecule include compounds represented by the following formula (4).

In the formula (4), R ^a1 has the same ^{meaning as} that in the formula (1). Moreover, as R ^a9 which is a polyvalent linking group, for example, a branched alkylene group having 1 to 12 carbon atoms such as groups represented by the following (4A) to (4C), a group represented by the following (4D) and the like: A branched poly (alkyleneoxy) group, or a branched polysiloxy group such as a group represented by E below. j (repeat unit) is 3 or 4.

In the above (4A), R ^a10 represents a methyl group, an ethyl group or a propyl group. In the above (4D), p (repeating unit) is an integer of 1 to 10.

  Moreover, as an oxetane compound, the compound shown by following formula (5) which has an oxetane ring in a side chain is also mentioned.

In the formula (5), R ^a1 and R ^a8 have the same ^{meaning as} in the above formula. R ^a11 is an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group, or a trialkylsilyl group, and r (repeating unit) is 1 to 4.

  Examples of polyfunctional and non-aromatic oxetane compounds that are particularly preferably used in the present invention are listed in (2-1) to (2-3) and (3-1) to (3-2) below.

  The epoxy compound is not particularly limited as long as it is a compound having an oxirane ring in the molecule, and a known epoxy compound can be arbitrarily selected and used. Specifically, examples of the epoxy compound include aromatic epoxides that are aromatic epoxy compounds, and alicyclic epoxides and aliphatic epoxides that are non-aromatic epoxy compounds. Non-aromatic epoxy compounds, specifically alicyclic epoxides and aliphatic epoxides, can be mentioned from the viewpoint of more preferably reducing the surface resistance of the cured film, and the viewpoint of further improving the scratch resistance of the cured film. To alicyclic epoxides.

  Aromatic epoxides include polyphenols having at least one aromatic nucleus or di- or polyglycidyl ethers produced by reaction of an alkylene oxide adduct with epichlorohydrin, such as bisphenol A or Examples thereof include di- or polyglycidyl ether of the alkylene oxide adduct, hydrogenated bisphenol A or di- or polyglycidyl ether of the alkylene oxide adduct, and a novolac type epoxy resin. Here, examples of the alkylene oxide include ethylene oxide and propylene oxide.

  As the alicyclic epoxide, cyclohexene obtained by epoxidizing a compound having at least one cycloalkane ring such as cyclohexene ring or cyclopentene ring with a suitable oxidizing agent such as hydrogen peroxide or peracid. Preference is given to oxide or cyclopentene oxide-containing compounds.

  Examples of aliphatic epoxides include dihydric polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, and typical examples thereof include diglycidyl ether of ethylene glycol, diglycidyl ether of propylene glycol, or 1,6. -Diglycidyl ether of alkylene glycol such as diglycidyl ether of hexanediol, polyglycidyl ether of polyhydric alcohol such as di- or triglycidyl ether of glycerin or its alkylene oxide adduct, diglycidyl of polyethylene glycol or its alkylene oxide adduct Diglycidyl of polyalkylene glycol typified by diglycidyl ether of ether, polypropylene glycol or its alkylene oxide adduct Ether and the like. Here, examples of the alkylene oxide include ethylene oxide and propylene oxide.

  Examples of the epoxy compound include a compound having one oxirane ring in the molecule (monofunctional epoxy compound) and a compound having two or more oxirane rings in the molecule (polyfunctional epoxy compound).

  As an epoxy compound which has one oxirane ring in a molecule | numerator, phenyl glycidyl ether, p-tert- butylphenyl glycidyl ether, etc. are mentioned as an aromatic epoxy compound. ; Non-aromatic epoxy compounds such as butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, 1,3-butadiene monooxide, 1,2-epoxydodecane, epichlorohydrin 1,2-epoxydecane, styrene oxide, cyclohexene oxide, 3-methacryloyloxymethylcyclohexene oxide, 3- (meth) acryloyloxymethylcyclohexene oxide, 3-vinylcyclohexene oxide, 4-vinylcyclohexene oxide, and the like. The epoxy compound having one oxirane ring in the molecule is preferably a non-aromatic epoxy compound.

  From the viewpoint of more preferably reducing the surface resistance of the cured film, the epoxy compound is preferably a compound having two or more oxirane rings (polyfunctional epoxy compound). In the epoxy compound having two or more oxirane rings, the number of oxirane rings in the molecule is preferably two.

  Epoxy compounds having two or more oxirane rings in the molecule include aromatic epoxy compounds such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, bromine Bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, epoxy novolac resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, and the like. As non-aromatic epoxy compounds, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) Cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ′, 4 ′ -Epoxy-6'-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di (3,4-epoxycyclohexylmethyl) ether, ethylene bis (3,4-epoxy Cyclohexane Boxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, (4R) -1,2-epoxy-4- (2-methyloxiranyl) -1-methylcyclohexane (limonene dioxide) ), 1,2,5,6-diepoxycyclooctane, 1,4-butanediol diglycidyl ether, butyl diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl Ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ethers, 1,13-tetradecadiene dioxide, 1,2,7,8-diepoxyoct Emissions, and the like. The epoxy compound having two or more oxirane rings in the molecule is preferably a non-aromatic epoxy compound.

  Examples of commercially available epoxy compounds include monofunctional epoxy compounds such as YED series (YED111N, YED111AN, YED122, YED188, etc .: manufactured by Mitsubishi Chemical Corporation), Celoxide series (Celoxide 2000: manufactured by Daicel Corporation), and the like. As polyfunctional epoxy compounds, YED series (YED216M, YED216D, etc .: manufactured by Mitsubishi Chemical Corporation), Denacol series (EX-211, EX-212: manufactured by Nagase ChemteX Corporation), Celoxide series (Celoxide 2021P, Celoxide 2081: manufactured by Daicel Corporation), LDO (produced by ARKEMA Corporation), and the like.

  Examples of polyfunctional and non-aromatic epoxy compounds that are particularly preferably used in the present invention are shown in the following (6-1) to (6-3).

  Examples of vinyl ether compounds include monofunctional vinyl ether compounds and polyfunctional vinyl ether compounds. Examples of the monofunctional vinyl ether compound include aromatic vinyl ether compounds such as benzyl vinyl ether, phenylethyl vinyl ether, and phenoxy polyethylene glycol vinyl ether. Non-aromatic vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, 4-methylcyclohexyl methyl vinyl ether, Dicyclopentenyl vinyl ether, 2-dicyclopentenoxyethyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, butoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, ethoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether, tetrahydrofurfuryl vinyl ether, 2-hydroxy Echi Vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxymethyl-cyclohexylmethyl vinyl ether, diethylene glycol monovinyl ether, polyethylene glycol vinyl ether, chloroethyl vinyl ether, chlorobutyl vinyl ether, chloroethyl ethoxyethyl vinyl ether. The monofunctional vinyl ether compound is preferably a non-aromatic vinyl ether compound.

  The vinyl ether compound is preferably a polyfunctional vinyl ether compound from the viewpoint of more preferably reducing the surface resistance of the cured film. Examples of the polyfunctional vinyl ether compound include bisphenol A alkylene oxide divinyl ether and bisphenol F alkylene oxide divinyl ether as aromatic vinyl ether compounds, preferably ethylene glycol dialkyl ether as non-aromatic vinyl ether compounds. Examples thereof include vinyl ethers, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, and the like. Examples of the bifunctional or more non-aromatic vinyl ether compounds include trimethylolethane trivinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol. Hexavinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, propylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, propylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether Ether, propylene oxide adduct of pentaerythritol tetravinyl ether, ethylene oxide adduct of dipentaerythritol hexavinyl ether, and propylene oxide adduct of dipentaerythritol hexavinyl ether. The polyfunctional vinyl ether compound is preferably a non-aromatic vinyl ether compound.

  A silane coupling agent is also mentioned as a cationically polymerizable compound. By including the silane coupling agent, the scratch resistance of the cured film can also be improved. (C) In a component, a silane coupling agent can be used individually or in combination with cationically polymerizable compounds other than the above-mentioned silane coupling agent.

  A silane coupling agent includes a hydrolyzable group having affinity or reactivity with an inorganic material and a cationically polymerizable group (specifically, a group containing an oxirane ring, an oxetane ring, or a vinyl group that chemically bonds to an organic material). The compound represented by the following general formula (7) is preferable.

  R represents a methyl group or an ethyl group, s represents 0, 1 or 2, and L is a group represented by the following general formula (8), (9), (10) or (11). L preferably has an oxirane ring, an oxetane ring, or a vinyl group, and more preferably has an oxirane ring.

  Y represents an alkylene group having 1 to 3 carbon atoms, Z represents an oxygen atom or a divalent organic group having an organopolysiloxane represented by the following general formula (12), V represents a vinyl group, an allyl group, ( It represents a (meth) acryloyl group, a glycidyl group, a 3,4-epoxycyclohexyl group, or a (3-ethyloxetanyl) methyl group.

  Q represents a C1-C4 alkoxy group or a C1-C4 alkyl group each independently, and t represents the integer of 1-10.

  Specific examples of the silane coupling agent include glycidoxyoctyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, and 3-glycidyloxypropyl. Examples include ethyldiethoxysilane, epoxycyclohexylethyltrimethoxysilane, and 3-ethyl-3-[[3- (triethoxysilyl) propoxy] methyl] oxetane. These silane coupling agents can be used alone or in combination.

  The content of the component (C) per 100 parts by mass of the total amount of the component (B) and the component (C) is, for example, 10 to 90 parts by mass, preferably 20 to 80 from the viewpoint of reducing the surface resistance of the cured film. A mass part, More preferably, it is 30-80 mass parts, More preferably, it is 35-80 mass parts, More preferably, it is 45-75 mass parts, Most preferably, 45-65 mass parts is mentioned.

  As the component (C) in the curable composition of the present invention, the component (E) contained in the curable composition (in an amount that matches the ratio to the component (C) in the curable composition) is used (C). A component having a cured product having a hardness of B or higher, preferably H or higher, more preferably 2H or higher, and particularly preferably 3H or higher when the component is cured alone can be used. In the curable composition of the present invention, particularly when a curable composition for hard coat is used, at least one of the (B) component and the (C) component may contain a component having a cured product hardness of 3H or more. preferable. Here, in the cured product hardness of the component (B), the cured product hardness is the amount that matches the ratio of the component (D) contained in the curable composition to the ratio of the component (B) in the curable composition. ) Used to mean the hardness of the cured product when the component (B) is cured alone. In the cured product hardness of the component (C), the component (E) contained in the curable composition is (curable). The hardness of the cured product when the component (C) is cured alone using an amount that matches the ratio to the component (C) in the composition. Although the upper limit of these hardness is not specifically limited, For example, 6H is mentioned. In addition, hardness is the value measured based on the mechanical property-scratch hardness (pencil method) of a JISK5600-5-4 (1999) coating film as described in an Example.

  As content of (C) component in the curable composition of this invention, the total amount of (B) component and (C) component is components 100 other than the organic solvent among the components which comprise a curable composition. The amount of the above-mentioned amount per part by mass (that is, for example, 70 to 99 parts by mass, preferably 80 to 98 parts by mass) is mentioned. Moreover, as content of (C) component in the curable composition of this invention, 100 mass parts of components other than the organic solvent among the components which comprise a curable composition from a viewpoint of the surface resistance reduction property of a cured film. For example, 10 to 90 parts by mass, preferably 20 to 85 parts by mass is mentioned.

<(D) Radical polymerization initiator>
The curable composition of this invention contains a radical polymerization initiator as (D) component. Any radical polymerization initiator may be used as long as it becomes a polymerization initiator for the component (B), which generates radicals as active species upon irradiation with active energy rays such as visible light, ultraviolet rays, heat rays, and electron beams. A radical polymerization initiator can be used without any limitation.

  Specific examples of the radical polymerization initiator include alkylphenone compounds, benzoin compounds, benzophenone compounds, thioxanthone compounds, and acyl phosphine oxide compounds.

Examples of the alkylphenone compounds include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy- 2-Methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one Α-hydroxyalkylphenone compounds such as diethoxyacetophenone, benzyldimethyl ketal, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- ( 4-morpholinophenyl) butanone, 2-hydroxy-2-methyl-1- [4- (1-methylvini) ) Phenyl] propanone oligomer, and the like.
Examples of benzoin compounds include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl). Oxime esters such as -9H-carbazol-3-yl]-, 1- (O-acetyloxime); benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and the like. Examples of the benzophenone compounds include benzophenone, methyl ortho-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl). ) Benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethananium bromide, (4-benzoylbenzyl) ) Trimethylammonium chloride and the like. Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy ) -3,4-dimethyl-9H-thioxanthone-9-one mesochloride. Examples of the acyl phosphine oxide compound include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, bis (2, 4,6-trimethylbenzoyl) -phenylphosphine oxide and the like. These radical polymerization initiators can be used alone or in combination.

  Among the above radical polymerization initiators, alkylphenone compounds are preferable, and α-hydroxyalkylphenone compounds are more preferable. More specifically, as radical polymerization initiators, IRGACURE184 (1-hydroxy-cyclohexyl-phenyl-ketone: manufactured by BASF Japan Ltd.), IRGACURE1173 (2-hydroxy-2-methyl-1-phenylpropan-1-one) : BASF Japan Ltd.), IRGACURE 2959 (1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one: produced by BASF Japan Ltd.), IRGACURE 127 ( 2-Hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one: manufactured by BASF Japan Ltd.) it can.

  Further, as an auxiliary for the radical polymerization initiator, triethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone (Michler ketone), 4,4'-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, 4-dimethyl Ethyl aminobenzoate, ethyl 4-dimethylaminobenzoate (n-butoxy), isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, etc. May be used in combination. These adjuvants for radical polymerization initiators can be used alone or in combination.

  The content of the component (D) may be appropriately adjusted within a range in which the polymerization reaction (radical polymerization) of the component (B) proceeds favorably, and is not particularly limited. For example, as for content of (D) component, 1-10 mass parts is mentioned per 100 mass parts of (B) component.

<(E) Acid generator>
The curable composition of this invention contains an acid generator as (E) component. The acid generator may be an active energy ray such as visible light, ultraviolet ray, heat ray, electron beam, or any initiator that can generate Lewis acid or Bronsted acid as an active species by heat. A thermal acid generator can be used without particular limitation. Any one of the active energy ray acid generator and the thermal acid generator can be used alone or in combination. Preferably, an active energy ray acid generator is mentioned as (E) component.

Examples of the active energy ray acid generator include onium salt acid generators. Examples of the cation portion of the onium salt include complex ions such as sulfonium salt, diazonium salt, ammonium salt, iodonium salt, thioxanthonium salt, selenonium salt, thianthrhenium salt, iron complex salt, preferably sulfonium salt. It is done. The onium salt preferably has an aryl group, and more preferably a triarylsulfonium salt. The anion moiety includes trifluoromethanesulfonate (CF ₃ SO ₃ ⁻ ), chlorine ion (Cl ⁻ ), bromine ion (Br ⁻ ), tetrafluoroborate (BF ₄ ⁻ ), hexafluorophosphate (PF ₆ ⁻ ), hexafluoro Examples include antimonate (SbF ₆ ⁻ ), hexafluoroarsenate (AsF ₆ ⁻ ), hexachloroantimonate (SbCl ₆ ⁻ ), and preferably trifluoromethanesulfonate and hexafluorophosphate.

  As more specific examples of the active energy ray acid generator, CD1010 (manufactured by Sartomer); WPAG-281, WPAG-336, WPAG-367, WPI-113 (manufactured by Wako Pure Chemical Industries, Ltd.); IPTX, CI- 5102, CI-2855 (manufactured by Nippon Soda Co., Ltd.); UVI-6970, UVI-6974 (manufactured by Union Carbide); RHODROSIL Photoinitiator 2074 (manufactured by Rhone-Poulenc); 150, SP-151, SP-152, SP-170, SP-171, SP-172 (made by ADEKA Corporation); CPI-100P, CPI-101A, CPI-210S, CPI-300PG (made by San Apro Corporation) Can be mentioned.

Examples of the thermal acid generator include onium salt acid generators. Examples of the cation portion of the onium salt include complex ions such as sulfonium salts, diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfoxonium salts, and the like, and preferably sulfonium salts. The onium salt preferably has an aryl group. Examples of the anionic portion, chlorine ions (Cl @ -), bromine ion (Br @ -), hexafluorophosphate (PF ₆ ^-), hexafluoroantimonate (SbF ₆ ^-) and the like, preferably, hexafluorophosphate (PF ₆ ^-), hexafluoroantimonate (SbF ₆ ^-) and the like.

  More specific examples of the thermal acid generator include CI-2624, CI-2855 (manufactured by Nippon Soda Co., Ltd.); SI-60, SI-60L, SI-80, SI-80L, SI-100, SI- 100L, SI-145, SI-150, SI-160, SI-180, SI-180L (manufactured by Sanshin Chemical Co., Ltd.); TA-90, TA-100, TA-120, TA-160, IK-1, IK-2 (manufactured by San Apro Co., Ltd.); Adeka Opton CP-66, Adeka Opton CP-77 (manufactured by ADEKA Co., Ltd.) and the like can be mentioned.

  The content of the component (E) is not particularly limited, and may be appropriately adjusted within a range in which the polymerization reaction (cationic polymerization) of the component (C) proceeds favorably. For example, as for content of (E) component, 1-10 mass parts is mentioned per 100 mass parts of (C) component.

<(F) Heterogeneous polymerizable compound>
The curable composition of the present invention may contain a heteropolymerizable compound having a cationic polymerizable group and a radical polymerizable group in one molecule as the component (F). By including the component (F) in the present invention, the scratch resistance of the cured film can be improved. Examples of the cationic polymerizable group include an oxirane ring, an oxetane ring, or a group containing a vinyl group, preferably a group containing a vinyl group, and preferably a vinyl ether group from the viewpoint of scratch resistance of a cured film. It is done. Examples of the radical polymerizable group include a (meth) acryloyl group.

  As the heteropolymeric compound, a vinyl ether group-containing (meth) acrylic acid ester is preferable. Specific examples of the vinyl ether group-containing (meth) acrylic acid ester are not particularly limited. For example, 2- (vinyloxyethoxy) ethyl (meth) acrylate (commercially available products such as VEEA, VEEM (Nippon Shokubai) Etc.), 2- (vinyloxyisopropoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxy) propyl (meth) acrylate, 2- (vinyloxyethoxy) isopropyl (meth) acrylate, (Meth) acrylic acid 2- (vinyloxyisopropoxy) propyl, (meth) acrylic acid 2- (vinyloxyisopropoxy) isopropyl, (meth) acrylic acid 2- (vinyloxyethoxyethoxy) ethyl, (meth) acrylic acid 2- (vinyloxyethoxyisopropoxy) ethyl, (meth) acrylic acid 2- (vinyl Xylisopropoxyethoxy) ethyl, 2- (vinyloxyisopropoxyisopropoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxyethoxy) propyl (meth) acrylate, 2- (vinyloxyethoxy) (meth) acrylate Isopropoxy) propyl, 2- (vinyloxyisopropoxyethoxy) propyl (meth) acrylate, 2- (vinyloxyisopropoxyisopropoxy) propyl (meth) acrylate, 2- (vinyloxyethoxyethoxy) (meth) acrylate ) Isopropyl, (meth) acrylic acid 2- (vinyloxyethoxyisopropoxy) isopropyl, (meth) acrylic acid 2- (vinyloxyisopropoxyethoxy) isopropyl, (meth) acrylic acid 2- (vinyloxyisopropoxyisopropoxy) Isopropyl 2- (vinyloxyethoxyethoxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxyethoxyethoxyethoxy) ethyl (meth) acrylate, 2- (isopropoxyethoxy) ethyl (meth) acrylate, (meta ) 2- (isopropoxyethoxyethoxyethoxy) ethyl acrylate, 2- (isopropoxyethoxyethoxyethoxy) ethyl (meth) acrylate, 2- (isopropoxyethoxyethoxyethoxyethoxy) ethyl (meth) acrylate, (meth) acrylic Polyethylene glycol monovinyl ether, (meth) acrylic acid polypropylene glycol monovinyl ether, etc., preferably 2- (vinyloxyethoxy) ethyl (meth) acrylate (commercially available products such as VEEA, VEEM (Nippon Shokubai Co., Ltd.) Etc.). These vinyl ether group-containing (meth) acrylic acid esters can be used alone or in combination.

  The content of the component (F) may be appropriately adjusted according to the content of the component (B) and the component (C). For example, the content of the component (B) and the component (C) is 5 per 100 parts by mass. -20 mass parts, Preferably 10-15 mass parts is mentioned.

<Other ingredients>
In addition to the component (A), the component (B), the component (C), the component (D) and the component (E), and the component (F) contained as necessary, the curable composition of the present invention includes: Components such as an organic solvent and additives such as a dispersant, a leveling agent, an ultraviolet absorber, an antifouling agent, a surface conditioner, and a polymerization inhibitor can be further included.

  When the curable composition of this invention contains the organic solvent, the organic solvent can be used 1 type or in mixture of 2 or more types by arbitrary ratios. Examples of the organic solvent include those used for dispersion of the component (A), those used as a solvent for each component such as the component (D) and the component (E), and the purpose and curing for ensuring the coating suitability of the curable composition. What is used for the purpose etc. which improve the adhesiveness of a membrane | film | coat and a base material is mentioned. Specific examples include alcohols such as methanol, ethanol, propanol, n-butanol and i-butanol; ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone and cyclohexanone; cellosolves such as ethyl cellosolve; and aromatics such as toluene and xylene Glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate; Acetic esters such as methyl acetate, ethyl acetate, butyl acetate; Cyclic carbonate solvents such as ethylene carbonate and propylene carbonate; Examples include diacetone alcohol.

  The amount of the organic solvent in the curable composition of the present invention can be appropriately adjusted in consideration of ensuring applicability and the like. Specifically, 0-90 mass% in a curable composition, Preferably it is 0-80 mass%, More preferably, 20-80 mass% is mentioned.

  Examples of the dispersant include poly (oxyethylene) alkyl ethers such as alcohol ethoxylates.

  Examples of the ultraviolet absorber include compounds derived from a benzophenone series, a benzotriazole series, a phenyl salicylate series, a phenyl benzoate series, and an ultraviolet absorbent having a maximum absorption wavelength in the range of 240 to 380 nm. Preferably, a benzophenone-based or benzotriazole-based UV absorber is preferable.

Specific examples of the ultraviolet absorber include 2-hydroxybenzophenone, 5-chloro-2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2-hydroxy-4-octyloxybenzophenone. 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octatesiloxybenzophenone, 2,2′-dihydroquin-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone phenyl salicylate, p-tert-butylphenyl salicylate, p- (1,1,3,3-tetramethylbutyl) phenyl salicylate, 3-hydroxyphenylbenzoate, phenylene-1,3-dibenzoate, 2- (2-hydroxy-5 ′ − Methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-tert-butylphenyl) benzotriazole, 2- (2 -Hydroxy-5-tert-butylphenyl) benzotriazole, 2- (2-hydroxy-4-octylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methacryloxyethylphenyl) -2H-benzotriazole, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -2H-benzotriazole, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4 - dimethylphenyl) -1,3,5-triazine and glycidyl alkyl (C ₁₂ -C ₁₃₎ ether And the like are reaction products. These ultraviolet absorbers can be used alone or in combination.

  The leveling agent can be used for the purpose of reducing the surface tension by acting on the coating surface after coating in order to obtain the coating suitability of the curable composition. Examples of the leveling agent include a fluorine leveling agent, a siloxane leveling agent, a (meth) acrylic leveling agent, and an acetylene glycol leveling agent. These leveling agents can be used alone or in combination.

  More specifically, examples of the fluorine-based leveling agent include Fluorad FC-430, Fluorard FC170 (Sumitomo 3M Co., Ltd.), MegaFuck F177, and MegaFac F471 (manufactured by DIC Corporation), and siloxane-based leveling agents include BYK. -300, BYK-077 (manufactured by Big Chemie Japan Co., Ltd.) and BYK-380 (manufactured by Big Chemie Japan Co., Ltd.) and Disparon L-1984-50, Disparon L-1970 (Enomoto Kasei) And acetylene glycol leveling agents include Dynol 604, Surfynol 104 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.

<Manufacture of curable composition>
The curable composition of the present invention comprises the above component (A), component (B), component (C), component (D) and component (E), and component (F) and other components contained as necessary. Can be prepared by mixing and dispersing. Each component may be added and mixed and dispersed all at once. For example, when a solvent is used, the component (A) is dispersed in part or all of the solvent, and the obtained component (A) The remaining components may be added to the dispersion and mixed and dispersed. In mixing and dispersing, stirring or kneading devices such as ultrasonic waves, homogenizers, spiral mixers, planetary mixers, dispersers (preferably high-pressure dispersers), and hybrid mixers can be used.

<Use of curable composition>
Since the curable composition of this invention can reduce the surface resistance of a cured film effectively, it can obtain favorable antistatic ability. For this reason, the curable composition of this invention becomes useful as a curable composition for antistatic which gives an antistatic hardened | cured material. For the same reason, the curable composition of the present invention is useful as an antistatic curable composition that gives an antistatic and highly transparent cured product. Furthermore, the curable composition of the present invention includes at least one of the component (B) and the component (C), for example, a component having a cured product hardness of 3H or more, so that the curable composition for a hard coat is used. It is useful as a curable composition for an antistatic hard coat. In addition, as said hardened | cured material hardness is in hardened | cured material hardness of (B) component as above-mentioned, (D) component contained in a curable composition is set to the ratio with respect to (B) component in a curable composition. This is the hardness of the cured product when the component (B) is cured alone using the same amount). In the cured product hardness of the component (C), the component (E) contained in the curable composition (In an amount that matches the ratio to the component (C) in the curable composition) and the hardness of the cured product when the component (C) is cured alone.

<Hardened film>
The cured film of the present invention is a cured product of the above-described curable composition. Since the above-mentioned curable composition is useful as an antistatic curable composition that gives an antistatic cured product, the cured film is also useful as an antistatic film. Moreover, since the above-mentioned curable composition is useful as an antistatic curable composition that gives an antistatic and highly transparent cured product, the cured film is also useful as an antistatic highly transparent film. Here, the high transparency in the antistatic high transparency film is obtained by performing the transparency test described in the examples below on the cured film having a thickness of 10 μm obtained from the curable composition of the present invention to obtain the total light transmittance. When measured, the total light transmittance is, for example, 80% or more, preferably 84% or more. Further, the curable composition described above is used for hard coating, preferably when at least one of the component (B) and the component (C) includes a component having a cured product hardness of 3H or more, preferably an antistatic hard coat. Therefore, the cured film is also useful as a hard coat film, preferably as an antistatic hard coat film. Here, the hardness of the antistatic hard coat film is, for example, 2H or more, preferably 3H or more, when the pencil hardness is measured by performing a pencil hardness test described in Examples below.

  The cured film can be obtained, for example, by forming a coating film of the curable composition directly on the surface of the substrate described later or via an intermediate layer, drying the coating film, and then curing. It is not particularly limited as a method of forming a coating film, gravure coater, roll coater, curtain flow coater, spin coater, bar coater, reverse coater, kiss coater, phanten coater, rod coater, air doctor coater, knife coater, blade coater, Application methods such as cast coater and screen coater; spraying methods such as spray coating such as air spray and airless spray; and dipping methods such as dip are used.

  The curable composition of the present invention is a cured film in which the network of the component (A) is effectively formed by simply curing the coating film, and the surface resistance is remarkably reduced for the amount of the component (A). Therefore, a complicated coating process is not required for forming a cured film, and it is not necessary to form a multilayered structure of the carbon nanotube-containing layer and the hard coat layer. That is, the curable composition of the present invention may have only one coating film formed in the coating process, and a cured film can be obtained very simply.

  Although it does not specifically limit as a hardening method, Irradiation and heating of active energy rays, such as visible light, an ultraviolet-ray, a heat ray, an electron beam, are suitably used according to the kind etc. of the acid generator of (E) component. A high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, or the like is used as a light source when performing ultraviolet irradiation. The irradiation time varies depending on the type of the light source, the distance between the light source and the coating surface, and other conditions, but may be several tens of seconds at most, usually several seconds. Preferably, an irradiation source having a lamp output of about 80 to 300 W / cm is used. In the case of electron beam irradiation, an electron beam having an energy in the range of 50 to 1000 KeV can be used and cured with an irradiation amount of 2 to 5 Mrad. Heating can be performed as necessary after irradiation with active energy rays.

  The thickness of the cured film of the present invention is not particularly limited. In the cured film of the present invention, since the surface resistance value of the cured film is remarkably reduced for the amount of the component (A), good transparency can be obtained even with a relatively large thickness. Is acceptable in a wide range. Therefore, the thickness can be appropriately determined according to the use of the cured film. For example, the thickness of the cured film is, for example, 0.1 to 50 μm, preferably 0.3 to 20 μm, more preferably 0.5 to 15 μm, and can be appropriately adjusted according to the use of the cured film.

<Laminate>
The laminated body of this invention has the above-mentioned cured film on a base material. As a structure of a laminated body, the cured film may be directly laminated | stacked on the base material, and may be laminated | stacked through the intermediate | middle layer arrange | positioned suitably for the purpose of improving interlayer adhesiveness. A laminated body can be manufactured by performing the manufacturing method of the above-mentioned cured film on a base material.

  As the substrate, it can be appropriately selected depending on the use of the laminate, but the cured film of the present invention can exhibit excellent transparency due to excellent surface resistance reduction, preferably translucency, More preferably, a transparent substrate is used. Specifically, examples of the base material include glass and plastic. Examples of the plastic include polyester, polyethylene, polypropylene, polyethylene terephthalate, cellophane, diacetyl cellulose, triacetyl cellulose, acetyl cellulose butyrate, polyvinyl chloride, and polychlorinated chloride. Examples include vinylidene, polyvinyl alcohol, ethylene vinyl alcohol, polystyrene, polycarbonate, polymethylpenter, polysulfone, polyether ketone, polyether sulfone, polyether imide, polyimide, fluororesin, nylon, (meth) acrylic resin, and the like. More specifically, a triacetyl cellulose plastic substrate film used as a polarizing plate member in a liquid crystal television or the like, a polyethylene terephthalate plastic substrate film in a touch panel, or the like can be given.

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these. The reagents used in Examples and Comparative Examples are shown below.

(A) Carbon nanotubes / TUBALL ^™ MATRIX 301 (manufactured by OCSiAl): SWCNT carbon nanotubes (B) polyfunctional (meth) acrylate compounds / A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.): dipentaerythritol hexaacrylate / HDI nurate 15 acrylate: reaction product of hexamethylene diisocyanate trimer (Asahi Kasei Co., Ltd.) and dipentaerythritol polyacrylate (A-9550 manufactured by Shin-Nakamura Chemical Co., Ltd.) (up to 15 functions)
Aronics M510 (manufactured by Toagosei Co., Ltd.): polybasic acid-modified acrylic oligomer, acid value 80-12 mg / g KOH
Light acrylate 14EGA (manufactured by Kyoeisha Chemical Co., Ltd.): polyethylene glycol (14EG) diacrylate (C) cationically polymerizable compound Celoxide 2021P (manufactured by Daicel Corporation): 3 ′, 4′-epoxycyclohexylmethyl-3,4- Epoxycyclohexanecarboxylate (bifunctional)
OXT221 (manufactured by Toagosei Co., Ltd.): 3-ethyl-3 {[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane (bifunctional)
EPICLON850S (DIC Corporation): Bisphenol A type epoxy resin (bifunctional)
KBM-4803 (manufactured by Shin-Etsu Chemical Co., Ltd.): 3-glycidoxyoctyltrimethoxysilane (monofunctional)
(F) Heterogeneous polymerizable compound / VEEA (manufactured by Nippon Shokubai Co., Ltd.): 2- (2-vinyloxyethoxy) ethyl acrylate (D) radical polymerization initiator / Irg184 (manufactured by BASF Corporation): 1-benzoyl- 1-cyclohexanol (E) acid generator, WPAG336 (manufactured by Wako Pure Chemical Industries, Ltd.): diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate, CPI-100P (manufactured by San Apro Co., Ltd.): triarylsulfonium, PF ₆ salt 50 mass% propylene carbonate solution / SI-60 (manufactured by Sanshin Chemical Industries, Ltd., Sun-Aid): arylsulfonium / SbF ₆ salt

[Measurement of SP value]
The SP value of component (B) was calculated from the measurement results of solubility in tetrahydrofuran (THF), heptane and water as follows.

(1) 2 g of the polyfunctional (meth) acrylate compound to be measured was weighed, and 18 g of tetrahydrofuran (THF) was added thereto to prepare a 10 mass% polyfunctional (meth) acrylate compound solution.
(2) A predetermined amount of the 10 mass% polyfunctional (meth) acrylate compound solution was taken under conditions of 25 ° C. and 1 atmosphere, and this volume (ml) was defined as V _THF .
(3) n-Heptane or ion-exchanged water is added dropwise to the solution separated in (2) above. The point at which the solution became cloudy and the cloudiness state was maintained for 10 seconds or more was taken as the titration end point. The drop amount (ml) of n-heptane up to the end of titration was V _Heptane , and the _titer (ml) of ion-exchanged water up to the end of titration was V _Water .
(4) V _Heptane and V _Water were substituted into the following (Formula a) and (Formula b) to calculate SPa and SPb. Then, the calculated SPa and SPb were substituted into (Formula c) to obtain SPA. In addition, log in (Formula c) is a common logarithm (base is 10).
Here, as the SP value of _THF (SP _THF ), the SP value of heptane (SP _Heptane ), and the SP value of ion-exchanged water (SP _Water ), values obtained from the chemical structural formula by the Fedors method described later were used ( SP _THF = 8.28, SP _Heptane = 7.43, SP _Water = 26.7).

The SP value of THF (SP _THF ), the SP value of heptane (SP _Heptane ) and the SP value of ion-exchanged water (SP _Water ) by the Fedors method were calculated as follows. Specifically, “POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1974, Vol. 14, No. 2, ROBERT F. FEDORS. (Pp. 147-154)” “Solubility Parameter Application Cases, Information Organization Issue, March 2007 Calculation is performed by the method described in “First printing on 15th, pages 12-14”. Specifically, it was calculated using the following mathematical formula d.

[Preparation of carbon nanotube dispersion]
SWCNT carbon nanotubes (TUBALL ^™ MATRIX 301 (carbon nanotube content 10 mass%, alcohol ethoxylate dispersion) manufactured by OCSiAl Co., Ltd.) is propylene glycol monomethyl ether acetate under conditions of 100 MPa with a high pressure disperser (starburst made by Sugino Machine). A carbon nanotube dispersion liquid having a carbon nanotube content of 0.1% by mass was obtained.

[Preparation of curable composition]
Using the carbon nanotube dispersion liquid obtained as described above, curable compositions (Examples 1 to 29 and Comparative Examples 1 to 8) having the compositions described in Tables 1 to 6 were prepared. . In the curable composition, propylene glycol monomethyl ether acetate was used as the organic solvent, and the total amount of components other than the organic solvent in the curable composition was adjusted to 25% by mass. In addition, the unit of the numerical value which shows the quantity of each component of Table 1-Table 6 is a mass part. The amount of each component is shown as the amount of components other than the organic solvent. For example, CPI-100P which is a 50% by mass solution of the polymerization initiator is described in terms of the amount of the polymerization initiator in the reagent, not the amount of the CPI-100P reagent. The obtained curable composition was used for the following evaluation tests. The results are shown in Tables 1-6. In Tables 1 to 6, “-” and “not contained” are synonymous. Further, for Comparative Example 1 and Examples 1 to 5 and Comparative Example 3 and Examples 7 to 12, (C) per 100 parts by mass in total of the ratios (B) and (C) of the cationic polymerizable compound The graph which shows the relationship between the value of a mass part and a surface resistance value is shown in FIG.

[Create test plate]
A PET film (Toyobo Cosmo Shine A4300 thickness 188 μm) was used as a base material, and the curable composition was bar coater no. 18 was applied to evaporate the solvent. Thereafter, the obtained coating film was dried at 80 ° C. for 5 minutes to remove the solvent, and further irradiated with ultraviolet rays under a condition of an integrated light quantity of 300 mJ / cm ² using a high-pressure mercury lamp (manufactured by Eye Graphics Co., Ltd.). Then, it was cured at 100 ° C. for 1 hour, and a laminate having a 10 μm cured film on the substrate was obtained as a test plate.

[transparency]
The test plate was subjected to measurement of total light transmittance Tt and HAZE by a measuring method based on JISK7105 using a haze meter (TC-H III DPK manufactured by Tokyo Denshoku Technical Center).

[Surface resistance value]
The test plate was subjected to measurement of the surface resistance value in accordance with ASTM-D257 using a resistance measuring instrument (Electrometer 6517 manufactured by KEITHLEY and low efficiency chamber MODL8009).

[Abrasion resistance]
The surface of the test plate was rubbed 10 times with # 0000 steel wool at a pressure of 9.8 × 10 ⁴ Pa, and the HAZE of the test plate after rubbing the surface was measured in the same manner as described above, before rubbing the surface. The amount of change HAZE from HAZE was evaluated.

[Pencil hardness]
Using a surface property measuring instrument (manufactured by Shinto Kagaku Co., Ltd., Tribogear 14FW) and a pencil for measuring pencil hardness (Mitsubishi Uni manufactured by Mitsubishi Pencil Co., Ltd.), The test was conducted in accordance with “Mechanical Properties—Scratch Hardness (Pencil Method)”. The measurement load was 750 g, the measurement speed was 30 mm / min, and the measurement distance was 5 mm. The measurement was performed 5 times, and the pencil hardness at which the number of passes exceeded 4/5 times was taken as the evaluation result.

  In Comparative Examples 1 to 4 containing only the (B) polyfunctional acrylate compound as the polymerizable compound, a cured film having high scratch resistance can be obtained if the component (B) is trifunctional or higher as in Comparative Examples 1 to 3. However, in any of Comparative Examples 1 to 4, the surface resistance value of the cured film was not sufficiently lowered. (When the component (B) is bifunctional as in Comparative Example 4, the surface resistance value of the cured film itself appears to be lower than that of Comparative Examples 1 to 3, but when the bifunctional (B) component is used, Compared with Examples 16, 17, 19, 23 to 29, the reduction of the surface resistance was also poor.) This is because the polyfunctional acrylate compound has a high curing rate, and (A) the conductive network of carbon nanotubes It is thought that it was difficult to form.

  In Comparative Examples 5 to 8 containing only the (C) cationic polymerizable compound as the polymerizable compound, the surface resistance value of the cured film tended to be low on average. On the other hand, in Comparative Examples 5 to 8 containing only the (C) cationic polymerizable compound as a polymerization component, a tendency to be inferior in scratch resistance was observed.

  On the other hand, in Examples 1 to 29 in which (B) a polyfunctional (meth) acrylate compound was combined with (C) a cationic polymerizable compound, the surface resistance was insufficient for the component (B) alone. The value was reduced well. Specifically, in the case of Examples 1 and 6, the surface resistance value is reduced to a level close to that of the component (C) alone (Comparative Example 5); in the case of Examples 4, 5, 7, 12, and 13 The surface resistance is reduced to the same extent as in the case of component (C) alone (Comparative Example 5), and in the case of Example 22 to the same extent as in the case of Component (C) alone (Comparative Example 8); In the case of 2, 3, 8-11, 14, 15-19, 23-29, to a lower level than in the case of component (C) alone (Comparative Example 5), in the case of Example 20, component (C) alone (comparison) The surface resistance value was reduced to a lower level than in Example 6), and in Example 21 to a level lower than that in the case of Component (C) alone (Comparative Example 7). This is because (B) polyfunctional (meth) acrylate compound reacts quickly and cures slowly (C) cationically polymerizable compound and cures (A) carbon nanotubes (C This is considered to be because (A) a network of carbon nanotubes was effectively formed by localizing in the cationically polymerizable compound and then slowly curing the (C) cationically polymerizable compound.

  Furthermore, as shown in FIG. 1, in the case where a highly polar polyfunctional (meth) acrylate compound is included as the component (B) (the same tendency is expected in Examples 7 to 12 and Example 6), (B ) It was found that the degree of reduction in the surface resistance of the cured film was greater than when the polyfunctional (meth) acrylate compound containing no high polarity was included as the component (Examples 1 to 5). This is because the (B) component highly polar polyfunctional (meth) acrylate compound becomes more hydrophilic due to its polarity, and (B) the hydrophobic ( (A) Since the carbon nanotubes are more highly localized in the (C) cationic polymerizable compound, (A) the network of carbon nanotubes is more effectively formed. It is thought that it was because it was done.

Claims (14)

  A curable composition comprising (A) a carbon nanotube, (B) a polyfunctional (meth) acrylate compound, (C) a cationic polymerizable compound, (D) a radical polymerization initiator, and (E) an acid generator. object.   The curable composition according to claim 1, wherein the component (B) contains a trifunctional or higher functional (meth) acrylate compound.   The curable composition according to claim 1 or 2, wherein the component (B) contains a polyfunctional (meth) acrylate compound having an SP value of 10.8 or more.   The component (B) is selected from the group consisting of a polyfunctional (meth) acrylate compound having an acidic group, a polyfunctional (meth) acrylate compound having an alkylene oxide group, and a polyfunctional acrylate compound having a polyglycerin structure. Item 4. The curable composition according to any one of Items 1 to 3.   The curable composition as described in any one of Claims 1-4 whose said (C) component is a polyfunctional cation polymeric compound.   The curable composition according to any one of claims 1 to 5, wherein the component (C) is a non-aromatic cationic polymerizable compound.   The curable composition according to any one of claims 1 to 6, wherein the component (C) is a non-aromatic epoxy compound.   (F) The curable composition as described in any one of Claims 1-7 which further contains the different polymeric compound which has a cationically polymerizable group and a radically polymerizable group in 1 molecule.   The curable composition according to claim 8, wherein the component (F) is a vinyl ether group-containing (meth) acrylic acid ester.   The content of the said (A) component with respect to 100 mass parts of components other than the organic solvent among the components which comprise the said curable composition is any one of Claims 1-9 which are 0.01-0.15 mass parts. The curable composition according to one item.   The content of the (C) component with respect to 100 parts by mass of the total amount of the (B) component and the (C) component is 35 to 80 parts by mass, according to any one of claims 1 to 10. Curable composition.   The curable composition according to any one of claims 1 to 11, which is an antistatic curable composition.   The cured film of the curable composition as described in any one of Claims 1-12.   A laminate having the cured film according to claim 13 on a substrate.

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