JP6565235B2 - Curable composition, cured product and laminate - Google Patents

Description

  The present invention relates to a curable composition and a cured product and a laminate obtained by using the curable composition. In more detail, the present invention is a cured product obtained when the amount of ultraviolet irradiation such as high-speed coating is small or in the case of a thin film, the laminate is water repellency, oil repellency, antifouling property, durability, wiping property, The present invention relates to a curable composition having excellent transparency, scratch resistance, hardness, adhesion to a substrate, and the like.

  In the fields of optical articles such as touch panels and optical information media, in recent years, contaminants such as fingerprint stains have a problem not only in appearance but also in performance, which is an important problem. For this reason, a coating material (coating material) for imparting the wear resistance and antifouling property of these plastic products is required.

  For example, Patent Document 1 discloses a non-aqueous resin composition containing a fluorine-based compound having an active energy ray-curable group having antifouling properties. Patent Documents 2 and 3 disclose that a specific copolymer containing a specific perfluoroalkyl group and an epoxy group or a (meth) acrylic acid reaction product thereof has excellent wiping off of contaminants and durability thereof. It is disclosed that it is effective as an antifouling agent.

JP-A-2005-112900 JP 2010-285613 A JP 2009-102513 A

  In many cases, the hard coat material is obtained by dissolving or suspending a resin composition in a solvent, applying the resin composition on the surface of a base material to which a function is to be imparted, and then curing the resin composition to obtain a cured film. In this coating operation, since the curing conditions differ depending on the coating machine, it is preferable to obtain the same performance under any conditions. In particular, the higher the coating speed (conveying speed), the higher the productivity. Therefore, those having excellent performance with a small amount of ultraviolet irradiation are preferable.

  On the other hand, according to detailed examinations by the present inventors, the conventional techniques represented by Patent Documents 1 to 3 say that the antifouling property is reduced when the amount of ultraviolet irradiation is small, such as high-speed coating. I found out there was a problem. The present invention aims to solve such problems of the prior art. That is, the present invention provides a cured product or laminate obtained with a low UV irradiation amount, such as high-speed coating, or a thin film, which has water repellency, oil repellency, antifouling properties, durability, wiping properties, transparency, and scratch resistance. It is an object of the present invention to provide a curable composition that is excellent in adhesion, hardness, adhesion to a substrate, and the like.

  As a result of intensive studies by the present inventors in view of the above problems, a curable composition containing an ethylenically unsaturated compound and particles having a specific particle diameter and including a compound having a specific structure solves the above problems. It has been found to obtain. That is, the gist of the present invention is as follows [1] to [13].

[1] The following component (A), component (B) and component (C) are included, and component (B) is 0.01 to 50 parts by mass and component (C) is 0 with respect to 100 parts by mass of component (A). A curable composition containing 0.01 to 30 parts by mass .
Component (A): Ethylenically unsaturated compound Component (B): The average primary particle size is 1 to 100 nm, d90 measured by a laser diffraction particle size distribution meter is 200 to 2,000 nm, and d50 is 30 to 30 Oxide particle component (C) which is 1,000 nm and contains at least silica : a compound having at least one group selected from a perfluoroalkyl group, a perfluoroalkylene ether group and a polydimethylsiloxane group
[2] The curable composition according to [1 ], wherein the component (B) has a d10 measured by a laser diffraction particle size distribution meter of 10 to 500 nm.

[3] The curable composition according to [1] or [ 2], which contains a polyfunctional (meth) acrylate as the component (A).
[4] As a component (C), including at least one of a compound having a perfluoroalkyl group and a compound having a perfluoroalkylene ether group, and a compound having a polydimethylsiloxane group, [1] to [ 3 ] The curable composition according to any one of the above.
[5] The curable composition according to any one of [1] to [ 4 ], which contains an organic solvent and has a solid content concentration of 5 to 95% by mass.
[6] The curable composition according to [ 5 ], wherein the organic solvent is at least one selected from a saturated hydrocarbon solvent, an ester solvent, an ether solvent, an alcohol solvent, and a ketone solvent.
[7] The curable composition according to any one of [1] to [ 6 ], including a polymerization initiator and having a content of 0.01 to 20 parts by mass with respect to 100 parts by mass of the component (A). object.

[8] A cured product obtained by irradiating the curable composition according to any one of [1] to [ 7 ] with active energy rays.
[9] A laminate having a substrate and a hard coat layer, the hard coat layer being coated on the substrate with the curable composition according to any one of [1] to [ 7 ] A laminate formed by irradiation with active energy rays.
[10] The laminate according to [ 9 ], wherein the substrate is a plastic substrate.
[11] The laminate according to [1 0 ], wherein the plastic substrate is at least one selected from polycarbonate resin, polyethylene terephthalate resin, and polymethyl methacrylate resin.

  According to the present invention, the obtained cured product and laminate are excellent in water repellency, oil repellency, antifouling properties, durability, wiping properties, transparency, scratch resistance, hardness, adhesion to a substrate, and the like. Thus, a curable composition is provided that exhibits excellent performance even when the amount of ultraviolet irradiation is low, such as high-speed coating, or in the case of a thin film. Moreover, according to this invention, the hardened | cured material and laminated body obtained using this curable composition are provided.

Embodiments of the present invention will be described in detail below, but the following description is an example of the embodiments of the present invention, and the present invention is limited to the following description unless it exceeds the gist. is not. In addition, when using the expression “to” in the present specification, it is used as an expression including numerical values or physical property values before and after the expression. In the present invention, when the expression “(meth) acrylate” is used, it means one or both of “acrylate” and “methacrylate”, such as “(meth) acryloyl” and “(meth) acryl”. The same applies to the case of using expressions.

(Curable composition)
The curable composition of this invention contains the following component (A), component (B), and (C). Component (A): Ethylenically unsaturated compound Component (B): Particle component (C) having an average primary particle size of 1 to 100 nm and a d90 measured by a laser diffraction particle size distribution meter of 200 to 2,000 nm: Compound having at least one group selected from fluoroalkyl group, perfluoroalkylene ether group and polydimethylsiloxane group

  In the present invention, what can be understood as both the component (A) and the component (C) is not regarded as the component (A) but as the component (C).

[Component (A)]
Component (A) used in the present invention is a compound having an ethylenically unsaturated bond. The curable composition of the present invention is imparted with curability and scratch resistance by containing the component (A).

  The ethylenically unsaturated bond of the component (A) compound is not particularly limited, and examples thereof include a (meth) acryloyl group, a (meth) acrylamide group, a styryl group, and an allyl group. Among these, the component (A) preferably includes a compound having a (meth) acryloyl group. In the component (A), the number of ethylenically unsaturated bonds in one molecule is not particularly limited, but is usually 1-15.

  Among the components (A), the compound having a (meth) acryloyl group includes a monofunctional (meth) acrylate having one (meth) acryloyl group and a polyfunctional (meth) acrylate having two or more (meth) acryloyl groups. Is mentioned. These may be used alone or in combination of two or more, but preferably contain a polyfunctional (meth) acrylate.

Examples of the monofunctional (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth). Acrylate, t-butyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acryloylmorpholine, tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate , Isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, phosphoric acid (meth) acrylate, ethylene oxide modified phosphoric acid (meth) acrylate, phenoxy (meth) acrylate , Ethylene oxide modified phenoxy (meth) acrylate, propylene oxide modified phenoxy (meth) acrylate, nonylphenol (meth) acrylate, ethylene oxide modified nonylphenol (meth) acrylate, propylene oxide modified nonylphenol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, Methoxypolyethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, 2- (meth Acryloyloxyethyl-2-hydroxypropyl phthalate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl hydrogen phthalate, 2- (meth) acryloyloxypropyl hydrogen phthalate, 2- (meth) Acryloyloxypropyl hexahydrohydrogen phthalate, 2- (meth) acryloyloxypropyl tetrahydro phthalate, dimethylaminoethyl (meth) acrylate, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoropropyl (meth) Acrylate, octafluoropropyl (meth) acrylate, octafluoropropyl (meth) acrylate, 2-adamantane And adamantane derivative mono (meth) acrylate such as adamantyl (meth) acrylate having a monovalent mono (meth) acrylate derived from adamantanediol. These may use only 1 type and may use it in combination of 2 or more type.

Examples of the polyfunctional (meth) acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, nonanediol di (meth) acrylate, Ethoxylated hexanediol di (meth) acrylate, propoxylated hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) Acrylate, neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, tripropylene glycol di (me ) Acrylate, bifunctional (meth) acrylate such as hydroxypivalate neopentyl glycol di (meth) acrylate; trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri ( (Meth) acrylate, tris 2-hydroxyethyl isocyanurate tri (meth) acrylate, glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) a Trifunctional or more polyfunctional (meth) acrylates such as relate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane hexa (meth) acrylate; Modified products of polyfunctional (meth) acrylate compounds in which a part of these (meth) acrylates are substituted with alkyl groups or ε-caprolactone; nitrogen atom-containing heterocyclic structures such as polyfunctional (meth) acrylates having an isocyanurate structure Polyfunctional (meth) acrylate having polybranched dendritic structure such as polyfunctional (meth) acrylate having dendrimer structure, polyfunctional (meth) acrylate having hyperbranched polymer structure, etc .; Urethane (meth) acrylate in which (meth) acrylate having hydroxyl group is added to anate or triisocyanate, (meth) acrylate having hydroxyl group in the reaction product having isocyanate group at the terminal obtained by reacting isocyanate compound and diol compound And urethane (meth) acrylates such as urethane (meth) acrylate to which is added. These can be used alone or in combination of two or more.
Among them, (meth) acrylates having 2 or more and 10 or less functions, and further (meth) acrylates having 3 or more and 8 or less functions are preferable because they can achieve both high hardness and low curing shrinkage, and are all ethylenically unsaturated compounds. The ratio of the polyfunctional (meth) acrylate to is preferably 50% by mass or more, and more preferably 70% by mass or more from the viewpoint that both high hardness and low curing shrinkage can be achieved.

The molecular weight of the compound having an ethylenically unsaturated bond is usually 50 or more. On the other hand, as described above, the compound having an ethylenically unsaturated bond can be used alone or in combination of two or more, but when it contains a plurality of components (A), it is curable. From the viewpoint of improving the handleability and coating properties of the composition, the component (A) as a whole preferably has a mass average molecular weight (Mw) of 2,100 or less, and a mass average molecular weight of 1,600 or less. Is preferable, and it is more preferable that it is 1,100 or less. The mass average molecular weight (Mw) of the component (A) can be measured by a gel permeation chromatography method (GPC method) as shown in the Examples below.

[Component (B)]
Component (B) used in the present invention has an average primary particle diameter of 1 to 100 nm and d90 measured by a laser diffraction particle size distribution meter (accumulated value is 90% in the result measured by a laser analysis particle size distribution meter). Particles having a particle diameter value of 200 to 2,000 nm. Here, d90 being in a predetermined range different from the value of the average primary particle diameter indicates that the component (B) is an aggregate. That is, the component (B) used in the present invention is one in which particles having an average primary particle diameter in a specific range are present in a specific aggregation state. In the curable composition of the present invention, when the curable composition of the present invention contains the component (B), irregularities are formed on the surface of the cured product when cured, and the contact area between the cured product surface and the soil component is increased. Can be small.

As described above, the component (B) has an average primary particle size of 1 to 100 nm and d90 measured by a laser analysis particle size distribution meter of 200 to 2,000 nm. Since the concavo-convex structure is formed, both the magic wiping property and transparency of the cured product formed using the curable composition containing the component (B) can be improved. The average primary particle diameter of the component (B) is 1 nm or more from the viewpoint of the magic wiping property, preferably 5 nm or more, more preferably 10 nm or more, still more preferably 15 nm or more, and most preferably On the other hand, from the viewpoint of transparency, it is 10 nm or more.
Although it is 0 nm or less, More preferably, it is 75 nm or less, More preferably, it is 50 nm or less. In addition, d90 of the component (B) is 200 nm or more from the viewpoint of magic wiping properties, but is preferably 250 nm or more, more preferably 300 nm or more. On the other hand, from the viewpoint of transparency, 2,000 nm or less. However, it is preferably 1,500 nm or less, more preferably 1,000 nm or less, still more preferably 800 nm or less, and particularly preferably 600 nm or less.

  Moreover, in the result measured by the laser analysis type particle size distribution meter, the particle diameter value (d10) at which the cumulative value becomes 10% and the particle diameter value (d50) at which the cumulative value becomes 50% are in the following ranges. It is more preferable from the viewpoint of achieving both magic wiping and transparency. That is, d10 of the component (B) is preferably 10 nm or more, more preferably 20 nm or more, further preferably 30 nm or more, particularly preferably 40 nm or more, and 50 nm or more. On the other hand, it is preferably 500 nm or less, more preferably 300 nm or less, still more preferably 200 nm or less, and particularly preferably 150 nm or less. Further, d50 of the component (B) is preferably 30 nm or more, more preferably 50 nm or more, further preferably 70 nm or more, particularly preferably 90 nm or more, while 1,000 nm. Is preferably 750 nm or less, more preferably 500 nm or less.

  The average primary particle diameter of the component (B) is a value measured using a scanning electron microscope or a transmission electron microscope. When the primary particles of the component (B) are other than spherical, the average primary particle diameter is The particle diameter is obtained as an average of the major axis diameter and the minor axis diameter. The particle diameter measured by a laser diffraction particle size distribution meter is specifically a value determined using [Microtrac UPA: Nikkiso Co., Ltd.].

  The component (B) may have an average primary particle diameter and d90 within the above ranges, respectively, and the aggregated particles may be adjusted by crushing the aggregated particles or by using the sol-gel method or the like. The particle diameter may be adjusted by aggregating dispersed particles using an aggregating agent.

  The type of the component (B) is not particularly limited as long as the average primary particle diameter and d90 satisfy the above range, and any of inorganic particles, organic particles, and organic-inorganic composite particles may be used. Moreover, only one of these may be used, or two or more may be used in combination. When the component (B) particles are inorganic particles, the heat resistance and hardness of the hard coat tend to increase, which is preferable.

  Examples of inorganic particles include silica, alumina, titania, zirconia, zeolite, mica, synthetic mica, calcium oxide, zirconium oxide, zinc oxide, magnesium fluoride, smectite, synthetic smectite, vermiculite, ITO (indium oxide / tin oxide). , Oxide particles such as ATO (antimony oxide / tin oxide), tin oxide, indium oxide, and antimony oxide. Among these, at least one oxide particle selected from the group consisting of silica, alumina, titania, zirconia, zinc oxide, ITO, tin oxide, and antimony oxide is preferable, and oxide particles containing at least silica. Is more preferable.

  Oxide particles containing silica can be obtained as a commercial product. Examples of applicable commercial products are CIR Nanotech's SIRMIBK15WT% -H58, SIRMIBK15WT% -M18, SIRMIBK15WT% -E83, SIRMIBK15WT% -M05, SIRMIBK15WT% -H84, SIRMIBK15WTM-B15, TIR -M06, SIRMIBK15WT% -M44, SIRMIBK15WT% -M46, SIRMIBK15WT% -M42, SIRMIBK15WT% -M47, SIRMIBK15WT% -M61, SIRMIBK15WT% -M62 and the like.

  Specific examples of the organic particles include organic crosslinked polymer particles. For example, (meth) acrylic crosslinked polymer particles, styrene-based crosslinked polymer particles, urethane-based crosslinked polymer particles, polyester-based crosslinked polymer particles, Examples include silicone-based crosslinked polymer particles, polyimide-based crosslinked polymer particles, and fluorine-based crosslinked polymer particles. Acrylic crosslinked polymer particles are particularly preferred. Specifically, (meth) acrylic monofunctional monomers such as methyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate (here, “(meth “) Acrylic monofunctional monomer” is a general term for (meth) acrylic acid monomers, (meth) acrylate monomers having one unsaturated double bond, and (meth) acrylamide monomers having one unsaturated double bond.) And (meth) acrylic polyfunctional monomers such as trimethylolpropane tri (meth) acrylate, allyl (meth) acrylate, and ethylene glycol di (meth) acrylate (where, “(meth) acrylic polyfunctional monomer” Is a (meth) acrylate monomer having two or more unsaturated double bonds and two unsaturated double bonds (Met) acrylic crosslinks obtained by polymerization methods such as suspension polymerization, emulsion polymerization, soap-free emulsion polymerization, miniemulsion polymerization, dispersion polymerization, seed polymerization, etc. Examples thereof include polymer particles. The (meth) acrylic crosslinked particles are styrene- (meth) acrylic crosslinked by copolymerizing styrene monofunctional monomers such as styrene and α-methylstyrene and styrene polyfunctional monomers such as divinylbenzene at the time of polymerization. Polymer particles may be used.

  Examples of the organic-inorganic composite particles include particles having an organic polymer skeleton and a polysiloxane skeleton having an organic silicon in which a silicon atom is directly chemically bonded to at least one carbon atom in the skeleton, and (meth) acryloxy groups Examples thereof include particles in which a vinyl polymer is contained in the structure of the polysiloxane particles having the following.

As long as the component (B) has an average primary particle diameter and d90 satisfying the above ranges, the shape of the aggregated state is not particularly limited, and is spherical, chain-like, needle-like, plate-like, scaly, crushed, The shape may be any shape such as a shape, a bowl shape, and a confetti shape. The shape of component (B) is preferably spherical or chain-like, and particularly preferably spherical. When the shape of the component (B) is spherical or chain-like, the uniformity of unevenness on the surface of the obtained cured product tends to be better.

  The curable composition of this invention may contain only 1 type of the above particles as a component (B), and may contain 2 or more types.

[Component (C)]
Component (C) used in the present invention is a compound having at least one group selected from a perfluoroalkyl group, a perfluoroalkylene ether group and a polydimethylsiloxane group. In the curable composition of the present invention, when the component (C) includes a component having at least one of a perfluoroalkyl group and a perfluoroalkylene ether group, water repellency and oil repellency are imparted.
In particular, a compound having a perfluoroalkylene ether group is preferable because of good water and oil repellency, that is, good antifouling property. In addition, when the component (C) contains a polydimethylsiloxane group in particular, the surface when the curable composition is cured is given slipperiness, and the wiping durability is reduced by reducing the frictional resistance during wiping. It will be good.
Furthermore, the curable composition of the present invention comprises at least one of a compound having a perfluoroalkyl group and a compound having a perfluoroalkylene ether group (the total mass thereof is represented as [CF]), and a polydimethylsiloxane group. It is particularly preferable to contain a compound having the above (this mass is expressed as [CSi]) because both excellent antifouling property and wiping durability can be achieved. The ratio (mass ratio) of [CF] / [CSi] is preferably 1/9 to 9.5 / 0.5, and [CF] / [CSi] is 2/8 to 9/1. More preferably, [CF] / [CSi] = 3/7 to 9/1 is still more preferable, and [CF] / [CSi] is most preferably 5/5 to 9/1.

<C-1: Compound having a perfluoroalkyl group>
The compound having a perfluoroalkyl group as component (C) is not particularly limited as long as it has a perfluoroalkyl group, but is preferably a (meth) acrylic polymer having a perfluoroalkyl group. Although the manufacturing method in particular is not restrict | limited, For example, it can obtain by superposing | polymerizing the (meth) acrylate which has a perfluoroalkyl group as a raw material. In this polymerization reaction, a raw material other than the perfluoroalkyl group-containing compound may be used for copolymerization.

  Examples of the (meth) acrylate having a perfluoroalkyl group include perfluorobutylethyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, perfluorohexylethyl (meth) acrylate, and (meth) perfluorohexyl glycidyl ether. Acrylic acid adduct, (meth) acrylic acid adduct of perfluoroheptylglycidyl ether, 1H, 1H, 7H-dodecafluoroheptyl (meth) acrylate, 1H, 1H, 9H-hexadecafluorononyl (meth) acrylate, 2- (Perfluoro-7-methyloctyl) ethyl (meth) acrylate, heptadecafluorononenyl (meth) acrylate, perfluorohexylethyl (meth) acrylate, perfluorohexyl glycidylate And the like of (meth) acrylic acid adduct. These (meth) acrylates having a perfluoroalkyl group may be used singly or in combination of two or more.

The perfluoroalkyl group of the (meth) acrylate having a perfluoroalkyl group is preferably a perfluoroalkyl group having 4 to 12 carbon atoms. When the carbon number of the perfluoroalkyl group is 4 or more, it is preferable from the viewpoint of antifouling properties. On the other hand, when the carbon number is 12 or less, the solubility is good, and the resulting cured product has good transparency and appearance. It is preferable because of its tendency.
The (meth) acrylate having a perfluoroalkyl group preferably contains 20% by mass or more, more preferably 30% by mass or more of a monomer having a perfluoroalkyl group in the polymer composition. The content is more preferably at least 50% by mass, and most preferably at least 50% by mass.

  Examples of raw materials that can be copolymerized with a (meth) acrylate having a perfluoroalkyl group include (meth) acrylic acid, glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and 3,4- Epoxy cyclohexyl methyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) Acrylate, sec-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-decyl (meth) acrylate, lauryl (meth) acrylate, n- G Decyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ethoxyethyl (meth) acrylate, ethyl carbitol (meth) ) Acrylate, butoxyethyl (meth) acrylate, cyanoethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (Meth) acrylates, (meth) acrylates such as 2-acryloyloxyethyl-2-hydroxyethylphthalate; N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-ethyl (meth) acrylamide, N, N-ethylmethyl (meth) acrylamide, N-methoxy (meth) acrylamide, N, N-dimethoxy (meth) acrylamide, N-ethoxy (meth) acrylamide, N, N-diethoxy (meth) acrylamide, diacetone (meth) acrylamide N-methylol (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N, N-dimethylaminomethyl (meth) acrylamide, N- (2-dimethylamino) ethyl (meth) acrylamide, N, N-methylenebis And (meth) acrylic monomers such as (meth) acrylamide and N, N-ethylenebis (meth) acrylamide. These may be used alone or in combination of two or more. Among these, it is preferable to use a (meth) acryl monomer having an epoxy group such as glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, or 3,4-epoxycyclohexylmethyl (meth) acrylate.

  The reaction of copolymerizing a (meth) acrylate having a perfluoroalkyl group and other monomers used as necessary is usually a radical polymerization reaction, specifically, the presence of a radical polymerization initiator in an organic solvent. Can be done below. The reaction time of this reaction is usually 1 to 50 hours, preferably 3 to 12 hours. The organic solvents and radical polymerization initiators that can be used here are as follows.

Examples of the organic solvent include ketone solvents such as acetone and methyl ethyl ketone (MEK); alcohol solvents such as ethanol, methanol, isopropyl alcohol (IPA), and isobutanol; ether solvents such as ethylene glycol dimethyl ether and propylene glycol monomethyl ether. Ester solvents such as ethyl acetate, propylene glycol monomethyl ether acetate and 2-ethoxyethyl acetate; aromatic hydrocarbon solvents such as toluene and the like. These organic solvents may be used alone or in combination of two or more.

  As the radical polymerization initiator, for example, known initiators generally used for radical polymerization can be used. Organic peroxides such as benzoyl peroxide and di-t-butyl peroxide; 2,2′-azobisbutyl Examples include azo compounds such as nitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), and 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile). These radical polymerization initiators may be used alone or in combination of two or more.

When synthesizing a (meth) acrylic polymer having a perfluoroalkyl group, a chain transfer agent is preferably used from the viewpoint of molecular weight control and the like. Examples of the chain transfer agent include α, ω-dimercaptopolydimethylsiloxane, α, ω-dimercaptopolydiethylsiloxane, α, ω-dimercaptopolymethylethylsiloxane, α, ω-dimercaptopolydihydroxymethylsiloxane, Examples include α, ω-dimercaptopolydimethoxymethylsiloxane. These may be used alone or in combination of two or more.
The (meth) acrylic polymer having a perfluoroalkyl group preferably has an unsaturated double bond, and particularly preferably has a (meth) acryloyl group. A (meth) acrylic polymer having a perfluoroalkyl group and an unsaturated double bond, particularly a (meth) acrylic polymer having a perfluoroalkyl group and a (meth) acryloyl group, has a perfluoroalkyl group as described above. The polymer obtained by copolymerizing the (meth) acrylate having an epoxy group, the (meth) acrylate having an epoxy group, and other monomers used as necessary further has a carboxyl group and a (meth) acryloyl group. It is obtained by reacting a compound. The reaction temperature is preferably 50 to 110 ° C, more preferably 55 to 100 ° C. Moreover, reaction time becomes like this. Preferably it is 3 to 50 hours, More preferably, it is 4 to 30 hours. This reaction is usually an addition reaction between the epoxy group in the copolymer and a compound having a carboxyl group and an acryloyl group.

  Examples of the compound having a carboxyl group and an acryloyl group that can be used in this reaction include (meth) acrylic acid, carboxyethyl (meth) acrylate, an adduct of glycerin di (meth) acrylate and succinic anhydride, pentaerythritol tri ( Examples include adducts of meth) acrylate and succinic anhydride, adducts of pentaerythritol tri (meth) acrylate and phthalic anhydride, and the like. Among these, (meth) acrylic acid or an adduct of pentaerythritol tri (meth) acrylate and succinic anhydride is preferable. In addition, the compound which has a carboxyl group and an acryloyl group may be used individually by 1 type, or may be used in combination of 2 or more type.

  The compound having a carboxyl group and an acryloyl group is preferably 10 to 150 mol%, more preferably 30 to 130 mol%, particularly preferably 50 to 110, as the mol% of the carboxyl group with respect to the epoxy group in the copolymer. It is preferable to use it in the proportion of mol% from the viewpoint of allowing the reaction to proceed without excess and deficiency and reducing the amount of raw material residues.

Moreover, in order to promote the reaction which adds the compound which has a carboxyl group and an acryloyl group to the said copolymer, it can be made to react using a catalyst. Examples of the catalyst include triethylamine, tributylamine, triethylenediamine, N, N-dimethylbenzylamine, benzyltrimethylammonium chloride, triphenylphosphine, and the like. The amount of the catalyst used is preferably 0.01 to 2% by mass and more preferably 0.05 to 1% by mass with respect to the total amount of raw materials. In addition, in this reaction, you may make it react using the organic solvent used for reaction in manufacture of the said copolymer as it is, and you may make it react by adding an organic solvent suitably. The organic solvents that can be used for this reaction are the same as those listed above.

  When the (meth) acrylic polymer having a perfluoroalkyl group has an unsaturated double bond, the amount of the unsaturated double bond is 1.0 mmol / g from the viewpoint of wiping resistance and scratch resistance. Preferably, it is 1.3 mmol / g or more, more preferably 1.6 mmol / g or more, and 4.2 mmol / g from the viewpoint of antifouling properties and oil repellency. Is preferably 3.9 mmol / g or less, more preferably 3.6 mmol / g or less.

  The weight average molecular weight (Mw) of the (meth) acrylic polymer having a perfluoroalkyl group as the component (C) is such that the viscosity of the curable resin composition is within an appropriate range from the viewpoint of antifouling properties of the resulting cured product. From the viewpoint of good compatibility with other components in the curable resin composition and the tendency to segregate on the coating surface, it is preferably 2,100 or more, more preferably 3,000. Or more, more preferably 4,000 or more, and particularly preferably 5,000 or more. In addition, the mass average molecular weight (Mw) of the (meth) acrylic polymer having a perfluoroalkyl group as the component (C) is such that the viscosity of the curable resin composition is in an appropriate range, and the other in the curable resin composition. From the viewpoint of improving the compatibility with the components, it is preferably 100,000 or less, more preferably 50,000 or less, still more preferably 30,000 or less, and particularly preferably 20,000 or less. It is. In addition, the mass average molecular weight of a component (C) can be calculated | required by gel permeation chromatography. More specific measuring methods are shown in the examples given later.

<C-2: Compound having a perfluoroalkylene ether group>
The compound having the perfluoroalkylene ether group as the component (C) is not particularly limited as long as it has a perfluoroalkylene ether group, but is preferably a (meth) acrylic polymer having a perfluoroalkylene ether group. The (meth) acrylic polymer having a perfluoroalkylene ether group can be obtained by polymerizing a (meth) acrylate having a perfluoroalkylene ether group as a raw material. In this polymerization reaction, raw materials other than (meth) acrylate having a perfluoroalkylene ether group may be used for copolymerization.

  The perfluoroalkylene ether group in the (meth) acrylate having a perfluoroalkylene ether group is preferably a perfluoroalkylene ether group having 4 to 12 carbon atoms. When the carbon number of the perfluoroalkylene ether group is 4 or more, it is preferable from the viewpoint of antifouling properties. On the other hand, when the carbon number of the perfluoroalkylene ether group is 12 or less, the solubility of the curable resin composition becomes good. This is preferable because the resulting cured product tends to have good transparency and appearance.

Examples of raw materials that can be copolymerized with a (meth) acrylate having a perfluoroalkylene ether group include (meth) acrylic acid, glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and 3,4. -Epoxycyclohexylmethyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meta ) Acrylate, sec-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-decyl (meth) acrylate, lauryl (meth) acrylate , N-tridecyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ethoxyethyl (meth) acrylate, ethyl carb Tall (meth) acrylate,
Butoxyethyl (meth) acrylate, cyanoethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy (Meth) acrylates such as butyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-acryloyloxyethyl-2-hydroxyethyl phthalate; N-methyl ( (Meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-ethyl (meth) acrylamide, N, N-ethylmethyl (meth) acrylamide, N-methoxy (meth) a Rilamide, N, N-dimethoxy (meth) acrylamide, N-ethoxy (meth) acrylamide, N, N-diethoxy (meth) acrylamide, diacetone (meth) acrylamide, N-methylol (meth) acrylamide, N- (2-hydroxy Ethyl) (meth) acrylamide, N, N-dimethylaminomethyl (meth) acrylamide, N- (2-dimethylamino) ethyl (meth) acrylamide, N, N-methylenebis (meth) acrylamide, and N, N-ethylenebis Examples include (meth) acrylic monomers such as (meth) acrylamide. These may be used alone or in combination of two or more. Among these, it is preferable to use a (meth) acryl monomer having an epoxy group such as glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, or 3,4-epoxycyclohexylmethyl (meth) acrylate.

  The reaction of copolymerizing the (meth) acrylate having a perfluoroalkylene ether group and other monomers used as required is usually a radical polymerization reaction, specifically, a radical polymerization initiator in an organic solvent. Can be done in the presence. The reaction time of this reaction is usually 1 to 50 hours, preferably 3 to 12 hours. The organic solvents and radical polymerization initiators that can be used here are as follows.

Examples of the organic solvent and the radical polymerization initiator include those described in the above-mentioned <C-1: compound having a perfluoroalkyl group>.
When synthesizing a (meth) acrylic polymer having a perfluoroalkylene ether group, it is preferable to use a chain transfer agent from the viewpoint of molecular weight control and the like. As the chain transfer agent, the aforementioned <C-1: perfluoro Examples thereof include those similar to those described in the compound having an alkyl group.

  The (meth) acrylic polymer having a perfluoroalkylene ether group preferably has an unsaturated double bond, and particularly preferably has a (meth) acryloyl group. A (meth) acrylic polymer having a perfluoroalkyl group and an unsaturated double bond, in particular, a (meth) acrylic polymer having a perfluoroalkyl group and a (meth) acryloyl group is a perfluoroalkylene ether group as described above. A copolymer obtained by copolymerizing a (meth) acrylate having an epoxy group, a (meth) acrylate having an epoxy group, and other monomers used as necessary, and further, a carboxyl group and a (meth) acryloyl group It is obtained by reacting a compound having The reaction temperature is preferably 50 to 110 ° C, more preferably 55 to 100 ° C. Moreover, reaction time becomes like this. Preferably it is 3 to 50 hours, More preferably, it is 4 to 30 hours. This reaction is usually an addition reaction between the epoxy group in the copolymer and a compound having a carboxyl group and an acryloyl group.

Examples of the compound having a carboxyl group and an acryloyl group that can be used in this reaction include the same compounds as those described above in <C-1: Compound having a perfluoroalkyl group>.
The compound having a carboxyl group and an acryloyl group is preferably 10 to 150 mol%, more preferably 30 to 130 mol%, particularly preferably 50 to 110, as the mol% of the carboxyl group with respect to the epoxy group in the copolymer. It is preferable to use it in the proportion of mol% from the viewpoint of allowing the reaction to proceed without excess and deficiency and reducing the amount of raw material residues.

  Moreover, in order to promote the reaction which adds the compound which has a carboxyl group and an acryloyl group to the said copolymer, it can be made to react using a catalyst. Examples of the catalyst are the same as those described in the above-mentioned <C-1: Compound having a perfluoroalkyl group>. The amount of the catalyst used is preferably 0.01 to 2% by mass and more preferably 0.05 to 1% by mass with respect to the total amount of raw materials. In addition, in this reaction, you may make it react using the organic solvent used for reaction in manufacture of the said copolymer as it is, and you may make it react by adding an organic solvent suitably. The organic solvents that can be used for this reaction are the same as those listed above.

When the (meth) acrylic polymer having a perfluoroalkylene ether group has an unsaturated double bond, the amount of the unsaturated double bond is 1.0 mmol /% from the viewpoint of wiping resistance and scratch resistance. g or more, more preferably 1.3 mmol / g or more, still more preferably 1.6 mmol / g or more. On the other hand, from the viewpoint of antifouling properties and oil repellency, 4.2 mmol / g It is preferably g or less, more preferably 3.9 mmol / g or less, still more preferably 3.6 mmol / g or less.
Furthermore, as the (meth) acrylic polymer having a perfluoroalkylene ether group, for example, a polymer described in JP 2010-285613 A, that is, a radical generating ability at both ends of a poly (perfluoroalkylene ether) chain. A polymerizable unsaturated monomer having at least one reactive group selected from the group consisting of a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide and an acid anhydride at both ends of the compound having a functional group. A hydroxyl group, an isocyanate group, or an epoxy group that reacts with the reactive group to form a bond with respect to a part or all of the reactive group of a polymer obtained by polymerizing a monomer component that has an essential body. At least one functional group selected from the group consisting of a carboxyl group, a carboxylic acid halide, and an acid anhydride, and polymerization Fluorine-containing polymerizable polymer obtained by reacting a compound having an unsaturated group can also be mentioned as preferable. In addition, such a (meth) acrylic polymer having a perfluoroalkylene ether group can also be obtained as a commercial product, for example, DIC's MegaFace (registered trademark) RS-76-E To do.

<C-3: Compound having a polydimethylsiloxane group>
The compound in which component (C) has a polydimethylsiloxane group is not particularly limited as long as it has a polydimethylsiloxane group, but is a (meth) acrylic polymer having a polydimethylsiloxane group or a polyether-modified polydimethylsiloxane. preferable.

  Examples of the (meth) acrylic polymer having a polydimethylsiloxane group include polydimethylsiloxane having an acryloyl group at one end (for example, commercially available Silaplane (registered trademark) FM0711, FM0721, FM0725, etc., manufactured by JNC), both Polydimethylsiloxane having an acryloyl group at the end (for example, X-22-164A manufactured by Shin-Etsu Chemical Co., Ltd. as a commercial product), polydimethylsiloxane having an epoxy group at both ends and an acryloyl group in the side chain, Examples thereof include a copolymer having polydimethylsiloxane in the chain and / or side chain and having 1 to 2 acryloyl groups in the side chain and / or terminal. Among these, polydimethylsiloxane having an acryloyl group at one end and / or both ends is preferable. In particular, a silicone-containing (meth) acrylate represented by the following formula (1) and a (meth) acrylate having an epoxy group are used. A (meth) acrylic copolymer obtained by reacting a copolymer obtained by copolymerization with a compound having a carboxyl group and a (meth) acryloyl group is preferred.

(In the above formula (1), R ¹ is a hydrogen atom or a methyl group, R ² is an alkylene group having 1 to 12 carbon atoms, R ³ and R ⁴ are each independently a methyl group, R ⁵ Is an alkyl group having 1 to 12 carbon atoms, n is an average value, and is a number of 5 to 1000.)

In formula (1), R ¹ represents a hydrogen atom or a methyl group, but the glass transition temperature (Tg) of the component (C-3-1) obtained is high, and the surface when the layer (A) is cured In order to increase the hardness, it is preferably a methyl group.

In Formula (1), R ² is an alkylene group having 1 to 12 carbon atoms. However, in order to easily obtain the raw material and easy to produce, the number of carbon atoms is preferably 2 or more, and 3 or more. On the other hand, it is preferably 10 or less, and more preferably 8 or less.

In formula (1), R ⁵ is an alkyl group having 1 to 12 carbon atoms. The number of carbon atoms in R ⁵ is preferably 2 or more, more preferably 3 or more. On the other hand, the number of carbon atoms in R ⁵ is preferably 10 or less, and more preferably 8 or less. It is preferable for the carbon number of R ⁵ to be in the above range because the raw materials are easily available and are easy to produce.

  In formula (1), n is an average value and is a number of 5 to 1000. When n is 5 or more, the surface slipperiness of the cured film obtained by curing the curable composition (α) is sufficiently expressed and the slipperiness is improved. From the viewpoint of making this effect better, n is preferably 25 or more, and more preferably 50 or more. On the other hand, when n is 1000 or less, the solubility in a solvent is good. From the viewpoint of making this effect better, n is preferably 9500 or less, and more preferably 8100 or less. The value of n can be obtained by calculation from the number average molecular weight (Mn).

  The number average molecular weight (Mn) of the silicone-containing (meth) acrylate represented by the formula (1) is sufficient to exhibit the slipperiness of the surface of the cured film obtained by curing the curable composition and to have good slipping property. In view of the above, preferably 500 or more, more preferably 1,000 or more, still more preferably 2,000 or more, most preferably 3,000 or more, while preferably 50,000 or less. More preferably, it is 20,000 or less, More preferably, it is 10,000 or less. When the number average molecular weight of this compound is not less than the above lower limit value, it is preferable from the viewpoint of antifouling properties and slipperiness, and when it is not more than the above upper limit value, it is preferable from the viewpoint of maintaining compatibility with other components. .

Among the silicone-containing (meth) acrylates represented by the formula (1), polydimethylsiloxane having a methacryloyl group at one end (as a specific example of a commercially available product, “Silaplane (registered trademark) FM0711” manufactured by JNC, “ Such as “Silaplane (registered trademark) FM0721”, “Silaplane (registered trademark) FM0725”, and the like. The silicone-containing (meth) acrylate represented by the formula (1) may be used alone or in combination of two or more.
Examples of the (meth) acrylate having an epoxy group to be copolymerized with the silicone-containing (meth) acrylate represented by the formula (1) include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 3,4- An epoxy cyclohexyl methyl (meth) acrylate etc. are mentioned.

  Other monomers that can be copolymerized with the silicone-containing (meth) acrylate represented by the formula (1) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and iso-propyl. (Meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, sec-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) ) Acrylate, n-decyl (meth) acrylate, lauryl (meth) acrylate, n-tridecyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate , Tetrahydrofurfuryl (meth) acrylate, ethoxyethyl (meth) acrylate, ethyl carbitol (meth) acrylate, butoxyethyl (meth) acrylate, cyanoethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol ( (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) ) (Meth) acrylates such as acrylate and 2-acryloyloxyethyl-2-hydroxyethyl phthalate; N-methyl (meth) acrylamide, N, N-dimethyl (Meth) acrylamide, N-ethyl (meth) acrylamide, N, N-ethylmethyl (meth) acrylamide, N-methoxy (meth) acrylamide, N, N-dimethoxy (meth) acrylamide, N-ethoxy (meth) acrylamide, N, N-diethoxy (meth) acrylamide, diacetone (meth) acrylamide, N-methylol (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N, N-dimethylaminomethyl (meth) acrylamide, N -(2-Dimethylamino) ethyl (meth) acrylamide, N, N-methylenebis (meth) acrylamide, N, N-ethylenebis (meth) acrylamide may be mentioned.

  Each of the silicone-containing (meth) acrylate represented by the formula (1), the (meth) acrylate having an epoxy group, and other monomers used as necessary are copolymerized to produce an acrylic copolymer. Although there is no restriction | limiting in particular in the usage-amount of a monomer, Preferably the silicone containing (meth) acrylate represented by Formula (1) 5-90 mass%, (meth) acrylate 10-95 mass% which has an epoxy group, and necessity 0 to 80% by mass of other monomers used depending on (however, the silicone-containing (meth) acrylate represented by the formula (1), the (meth) acrylate having an epoxy group, and other monomers used as necessary The total amount is 100% by mass.), And particularly preferably, the silicone-containing (meth) acrylate 10 to 75 represented by the formula (1) %, Having an epoxy group (meth) acrylate 20 to 85% by weight, and other monomers 5-60 wt% scratch resistance is used in an amount of optionally used, from the viewpoint of antifouling property.

  The reaction of copolymerizing the silicone-containing (meth) acrylate represented by the formula (1), the (meth) acrylate having an epoxy group, and other monomers used as necessary is usually a radical polymerization reaction. Can be carried out in an organic solvent in the presence of a radical polymerization initiator. The reaction time of this reaction is usually 1 to 50 hours, preferably 3 to 12 hours. The organic solvents and radical polymerization initiators that can be used here are as follows.

Examples of the organic solvent and the radical polymerization initiator include those described in the above-mentioned <C-1: compound having a perfluoroalkyl group>.

  Furthermore, an acrylic copolymer obtained by copolymerizing the silicone-containing (meth) acrylate represented by the formula (1), the (meth) acrylate having an epoxy group and other monomers used as necessary is not used. Those having a saturated double bond are preferred, and those having a (meth) acryloyl group are more preferred. In particular, the amount of unsaturated double bonds is preferably 0.5 mmol / g or more, more preferably 0.8 mmol / g or more, from the viewpoint of wiping resistance and scratch resistance, and 1.1 mmol / g. On the other hand, it is preferably 4.2 mmol / g or less, more preferably 3.9 mmol / g or less, more preferably 3.6 mmol / g from the viewpoint of wiping property (sliding property). More preferably, it is g or less.

  Unsaturated double in acrylic copolymer obtained by copolymerizing silicone-containing (meth) acrylate represented by formula (1), (meth) acrylate having epoxy group and other monomers used as required Examples of the method for introducing a bond include a method in which a compound having a (meth) acryloyl group and a carboxyl group is reacted with this acrylic group copolymer.

  Obtained by copolymerizing at least the silicone-containing (meth) acrylate represented by formula (1), the (meth) acrylate having an epoxy group, and other monomers used as necessary. What is obtained by further reacting the copolymer with a compound having a carboxyl group and an acryloyl group is preferred. The reaction temperature is preferably 50 to 110 ° C, more preferably 55 to 100 ° C. Moreover, reaction time becomes like this. Preferably it is 3 to 50 hours, More preferably, it is 4 to 30 hours. This reaction is usually an addition reaction between the epoxy group in the copolymer and a compound having a carboxyl group and an acryloyl group.

Examples of the compound having a carboxyl group and an acryloyl group that can be used in this reaction include the same compounds as those described above in <C-1: Compound having a perfluoroalkyl group>.
The compound having a carboxyl group and an acryloyl group is preferably 10 to 150 mol%, more preferably 30 to 130 mol%, particularly preferably 50 to 110, as the mol% of the carboxyl group with respect to the epoxy group in the copolymer. It is preferable to use at a mol% ratio from the viewpoint of allowing the reaction to proceed without excess and deficiency and reducing the amount of raw material residues.

Moreover, in order to promote the reaction which adds the compound which has a carboxyl group and an acryloyl group to the said copolymer, it can be made to react using a catalyst. Examples of the catalyst are the same as those described in the above-mentioned <C-1: Compound having a perfluoroalkyl group>. The amount of the catalyst used is preferably 0.01 to 2% by mass and more preferably 0.05 to 1% by mass with respect to the total amount of raw materials. In addition, in this reaction, you may make it react using the organic solvent used for reaction in manufacture of the said copolymer as it is, and you may make it react by adding an organic solvent suitably. The organic solvents that can be used for this reaction are the same as those listed above.
In addition, as a compound in which a component (C) has a polydimethylsiloxane group, the thing as described in the polyether silicone oil as described in WO2013 / 147151 can also be used.

The number average molecular weight (Mn) of the compound having a siloxane structure and one or more acryloylpolydimethylsiloxane groups is preferably 500 or more, more preferably 1,000 or more, and further preferably 2,000 or more. , Most preferably 3,000 or more,
On the other hand, it is preferably 50,000 or less, more preferably 20,000 or less, and still more preferably 10,000 or less. When the number average molecular weight of this compound is not less than the above lower limit value, it is preferable from the viewpoint of antifouling properties and slipperiness, and when it is not more than the above upper limit value, it is preferable from the viewpoint of maintaining compatibility with other components. .

  Of the compounds having a polydimethylsiloxane group, polyether-modified polydimethylsiloxane is preferable because it exhibits good slip properties and good compatibility with ethylenically unsaturated compounds. The polyether-modified polydimethylsiloxane can be obtained as a commercial product. An organic group may be further introduced into the polyether-modified polydimethylsiloxane, and examples thereof include an alkyl group, an aralkyl group, a hydroxyl group, an acryloyl group, a carboxyl group, a carbonyl group, a fluoro group, an amino group, and an epoxy group. Examples of commercially available products corresponding to the polyether-modified polydimethylsiloxane include BYK-300, BYK-302, BYK-306, BYK-307, BYK-320, BYK-325, and BYK-330 which are polyether-modified polydimethylsiloxanes. BYK-331, BYK-333, BYK-337, BYK-342, BYK-345, BYK-347, BYK-348, BYK-349, BYK-375, BYK-377, BYK-378, BYK-3455, BYK -3500, BYK-3510, BYK-3530, Silface SAG001, Silface SAG005 (Nisshin Chemical Industry Co., Ltd.), which is a polyether-modified polydimethylsiloxane.

[Blending amount]
The curable composition of the present invention preferably contains 0.01 part by mass or more of component (B) with respect to 100 parts by mass of component (A) from the viewpoint of forming irregularities on the surface of the cured product when cured. More preferably, it is 0.1 part by mass or more, more preferably 1 part by mass or more, and particularly preferably 2 parts by mass or more. On the other hand, the curable composition preferably contains 50 parts by mass or less, and 45 parts by mass or less of component (B) with respect to 100 parts by mass of component (A) from the viewpoint of scratch resistance and transparency of the cured product surface. More preferably, it is more preferably 40 parts by mass or less, and particularly preferably 30 parts by mass or less.

  In addition, the curable composition of the present invention contains 0.01 to 30 parts by mass of the component (C) with respect to 100 parts by mass of the component (A), and the water repellency, oil repellency, slipperiness, wiping durability, and scratch resistance. It is preferable from the viewpoint of improving the attachment. In particular, the content of the component (C) with respect to 100 parts by mass of the component (A) is preferably 0.1 parts by mass or more from the viewpoint of water repellency, oil repellency, slipperiness, wiping durability, and the like. On the other hand, the content of the component (C) with respect to 100 parts by mass of the component (A) is more preferably 25 parts by mass or less and 20 parts by mass or less from the viewpoint of scratch resistance. More preferred is 10 parts by mass or less.

[Organic solvent]
The curable composition of the present invention preferably contains an organic solvent. Moreover, when the curable composition of this invention contains the organic solvent, it is preferable that solid content concentration is 5-95 mass%. A solid content concentration of 5% by mass or more is preferable from the viewpoint of transparency because the dispersibility of the component (B) is good, and an unintended curing reaction (such as gelation) of the curable composition. Also preferred to prevent. Moreover, it is preferable from a viewpoint of coating property and storage stability that solid content concentration is 95 mass% or less. From these viewpoints, the solid content concentration is more preferably 10% by mass or more, further preferably 15% by mass or more, more preferably 90% by mass or less, and further preferably 85% by mass or less. Especially preferably, it is 80 mass% or less. In the present invention, “solid content” means a component excluding the solvent, and includes not only a solid component but also a semi-solid or viscous liquid material.

  It does not specifically limit as an organic solvent, The kind of base material used when forming the kind of a component (A), a component (B), a component (C), and a hard-coat layer, The coating method to a base material It can be appropriately selected in consideration of the above. Specific examples of the organic solvent include, for example, n-hexane, n-heptane, n-octane, n-decane, n-dodecane, 2,3-dimethylhexane, 2-methylheptane, 2-methylhexane, and 3-methyl. Saturated hydrocarbon solvents such as hexane and cyclohexane; aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone (MEK), acetone, methyl isobutyl ketone (MIBK), and cyclohexanone; diethyl ether, isopropyl ether, tetrahydrofuran, Dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether (PGM), anisole, phenetole Ether solvents such as ethyl acetate, butyl acetate, isopropyl acetate, ethylene glycol diacetate, propylene glycol monomethyl ether acetate and other ester solvents; dimethylformamide, diethylformamide, N-methylpyrrolidone and other amide solvents; methyl cellosolve, ethyl Examples include cellosolve solvents such as cellosolve and butylcellosolve; alcohol solvents such as methanol, ethanol, propanol, isopropanol, and butanol; halogen solvents such as dichloromethane and chloroform.

  These organic solvents may be used individually by 1 type, and may be used in combination of 2 or more type. Among these, it is preferable to include at least one selected from saturated hydrocarbon solvents, ester solvents, ether solvents, alcohol solvents, and ketone solvents.

[Polymerization initiator]
The curable composition of the present invention preferably contains a polymerization initiator in order to improve curability.
As the polymerization initiator, a photopolymerization initiator is preferable. For example, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-1- [4 -(Methylthio) phenyl] -2-morpholinopropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholino Phenyl) -butanone-1,2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, 2,4, Examples include 6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like. It is. These polymerization initiators may be used alone or in combination of two or more.

  In the curable composition of the present invention, the content of the polymerization initiator is preferably 0.01 parts by mass or more, more preferably 0. 05 parts by mass or more, more preferably 0.1 parts by mass or more. Further, the content of the polymerization initiator is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, with respect to 100 parts by mass of the component (A), from the viewpoint of the stability of the curable composition. More preferably, it is 8 mass parts or less.

[Other ingredients]
The curable composition of this invention may contain other components other than a component (A), a component (B), a component (C), an organic solvent, and a polymerization initiator in the range which does not inhibit the effect of this invention. . Other components include UV absorbers, hindered amine light stabilizers, fillers (excluding those that fall under component (B)), silane coupling agents (but those that fall under component (B)) ), Reactive diluent (excluding those corresponding to component (A)), antistatic agent, organic pigment, slip agent (excluding those corresponding to component (C)), dispersion Agents, thixotropic imparting agents (thickeners), antifoaming agents, antioxidants, thermoplastic resins and the like.

[Method for producing curable composition]
The production method of the curable composition of the present invention is not particularly limited. For example, the component (A), the component (B), the component (C) and, if necessary, an organic solvent, a polymerization initiator, other components, and the like are mixed. Can be obtained. When mixing each component, it is preferable to mix uniformly with a disperser, a stirrer, or the like.

[Hardened product and laminate]
A cured product (sometimes referred to as “cured product of the present invention”) can be obtained by curing the curable composition of the present invention by irradiating active energy rays or the like. Moreover, it can be set as a laminated body by apply | coating the curable composition of this invention on a base material, and irradiating an active energy ray to this and forming a hard-coat layer. In particular, a hard coat film can be obtained by applying the curable composition of the present invention on a substrate and curing it in a film form. In the present invention, “application” is used as a concept including what is generally called “coating”.

  As a base material used for said laminated body, inorganic materials, such as organic materials, such as a plastic base material; a metal base material, a glass base material, are mentioned. Examples of plastic substrates include various synthetic resins such as acrylonitrile-butadiene-styrene copolymer (ABS) resin, polycarbonate (PC) resin, polyethylene terephthalate (PET) resin, polybutylene terephthalate (PBT) resin, polymethyl methacrylate (PMMA). ) Resin, polystyrene (PS) resin, polyimide (PI) resin, polyolefin (PO) resin and the like. The metal substrate is not particularly limited. For example, a steel plate such as a hot-rolled plate or a cold-rolled plate, a hot-dip galvanized steel plate, an electrogalvanized steel plate, tinplate, tin-free steel, various other types of plating, or an alloy-plated steel plate And metal plates such as stainless steel plates and aluminum plates. Furthermore, these may be subjected to various surface treatments such as phosphate treatment, chromate treatment, organic phosphate treatment, organic chromate treatment, heavy metal substitution treatment such as nickel. As a glass substrate, in addition to normal glass, glass subjected to various chemical treatments (for example, Corning Gorilla Glass (registered trademark), Asahi Glass Dragon Trail (registered trademark), etc.) and multicomponent glass. May be used. The curable composition of the present invention is suitable for plastic substrates and glass substrates, particularly suitable for plastic substrates, and particularly suitable for polycarbonate resins, polyethylene terephthalate resins and polymethyl methacrylate resins among plastic substrates. . In addition, the base material mentioned above may use only 1 type, or may be used in combination of 2 or more type.

  Examples of the method for coating (coating) the curable composition of the present invention on a substrate include, for example, a reverse coating method, a gravure coating method, a rod coating method, a bar coating method, a Mayer bar coating method, a die coating method, and a spray coating. Law. In addition, the form of the cured product of the present invention is not particularly limited. However, in the case of a cured product obtained by irradiating an active energy ray on a substrate and curing it, a cured coating is formed on at least a part of one side of the substrate. It can be obtained as a (cured film) state.

  The humidity at the time of applying (coating) the curable composition of the present invention on a substrate is not particularly limited, and is usually 1 to 100%, preferably 5 to 95%. Moreover, when obtaining the hardened | cured material of this invention, it is preferable to dry beforehand before irradiating an active energy ray, and the drying temperature at this time is 40-160 degreeC normally, Preferably it is 45-150 degreeC.

  Active energy rays that can be used in curing the curable composition of the present invention include ultraviolet rays, electron beams, X-rays, infrared rays, and visible rays. Among these active energy rays, ultraviolet rays and electron beams are preferable from the viewpoints of curability and prevention of resin deterioration.

When the curable composition of the present invention is cured by ultraviolet irradiation, various ultraviolet irradiation apparatuses can be used, and a xenon lamp, a high-pressure mercury lamp, a metal halide lamp, an LED-UV lamp, or the like is used as the light source. Can do. The amount of ultraviolet irradiation is usually 10 to 10,000 mJ / cm ² , and preferably 30 to 5,000 mJ / from the viewpoints of curability of the curable composition of the present invention, flexibility of a cured product (cured film), and the like. cm ² , more preferably 50 to 3,000 mJ / cm ² . Moreover, ultraviolet illuminance is 50-1,000 mW / cm < ² > normally, Preferably it is 70-800 mW / cm < ² >.

  Moreover, when hardening the curable composition of this invention by electron beam irradiation, various electron beam irradiation apparatuses can be used. The irradiation amount (Mrad) of the electron beam is usually 0.5 to 20 Mrad, and preferably 1 from the viewpoints of curability of the curable composition of the present invention, flexibility of the cured product, prevention of damage to the substrate, and the like. ~ 15 Mrad.

[Use]
The curable composition of the present invention has a cured product and laminate that are water-repellent, oil-repellent, antifouling, durable, wiping, It is excellent in transparency, scratch resistance, hardness and the like. For this reason, the curable composition of the present invention is suitable as a stain resistance imparting agent for the display panel surface of a flat display (liquid crystal display, plasma display, rear projection display, front projector screen, inorganic EL display, organic EL display, etc.). Among them, among them, a car navigation system, a mobile phone, a mobile information terminal (PDA, etc.), a personal computer (PC) monomer, etc., a display having a touch panel input function, a household flat-screen television (TV) It can be suitably used as an antifouling imparting agent for the surface. The curable composition of the present invention can also be suitably used as a stain-resistant hard coat layer for optical recording media.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited at all by the following example. In addition, the value of various manufacturing conditions and evaluation results in the following examples has a meaning as a preferable value of the upper limit or the lower limit in the embodiment of the present invention, and the preferable range is the above-described upper limit or lower limit value. A range defined by a combination of values of the following examples or values of the examples may be used.

[Evaluation method]
The evaluation method of the cured film (laminated body) manufactured by the following examples and comparative examples is as follows.

<Transparency (haze)>
Transparency after a laminate having a cured film formed on a PET film was left in a temperature-controlled room at 23 ° C. and a relative humidity of 60% for 12 hours was evaluated with a haze value (H%) according to JIS K-7136 (2000). The evaluation was made according to the following criteria.
○: Haze value of cured film is less than 0.6% Δ: Haze value of cured film is 0.6% or more and less than 1.0% ×: Haze value of cured film is 1.0% or more

<Hardness (pencil hardness)>
Using a JIS-compliant pencil hardness tester (manufactured by Dazai Equipment Co., Ltd.), measurement was performed based on the conditions of JIS K-5400, and the hardness was indicated by the hardest pencil count without scratches.

<Adhesion>
According to the grid pattern method described in JIS K5400, 100 grids were placed in the cured film at intervals of 1 mm, and the test was performed using cellophane tape (Cello Tape (registered trademark) manufactured by Nichiban Co., Ltd.). This operation was repeated 5 times (a new cellophane tape was always used), and the adhesion was evaluated according to the following criteria.
○: No scratches or peeling occurred. Δ: Less than 10% scratched or peeled. ×: Over 10% scratched or peeled.

<Water and oil repellency>
After adjusting the state of the laminate having a cured film formed on a PET film in a constant temperature room at a temperature of 23 ° C. and a humidity of 60% RH for 24 hours, a contact angle meter (“DropMaster DM500” manufactured by Kyowa Interface Science Co., Ltd.) ), 0.002 mL of pure water or hexadecane was dropped onto the cured film, and after 1 minute, the contact angle for water and the contact angle for hexadecane were measured using a contact angle meter (DropMaster 500 manufactured by Kyowa Interface Science Co., Ltd.). Each was measured, and the former was water repellency and the latter was oil repellency (unit: degree).

<Magic resistance>
A line was drawn on the cured film with an oil-based magic marker (Zebra Mackey Care extra fine (black) fine), and evaluation was performed based on the presence or absence of line repelling after 30 seconds.
○: Repels the line ×: Does not repel the line

<Magic wiping durability>
Draw a line on the cured film with an oily magic marker (Zebra's Mackey Care extra fine (black) fine). After 10 seconds, wipe the surface with tissue paper (Crecia) and repeat this process until you cannot wipe it. The greater the number of times, the better.
◎: Exceeding 10 times ○: 5-10 times △: 2-4 times ×: 1 time

<Wipeability (sliding property)>
Draw a line on the cured film with an oily magic marker (Zebra's Mackey Care extra fine (black) fine). After 10 seconds, wipe the surface with tissue paper (Crecia). It was evaluated with.
◯: Can be wiped off with almost no force applied and △: Can be wiped off when wiped off: Cannot be wiped off unless a strong force is applied

(Measurement method of mass average molecular weight (Mw) of component (A) and component (C))
For C-1 to C-4, the mass average molecular weight was measured by the GPC method under the following conditions.
Equipment: “HLC-8120GPC” manufactured by Tosoh Corporation
Column: “TSKgel Super H1000 + H2000 + H3000” manufactured by Tosoh Corporation
Detector: Differential refractive index detector (RI detector / built-in)
Solvent: Tetrahydrofuran Temperature: 40 ° C
Flow rate: 0.5 mL / min Injection volume: 10 μL
Concentration: 0.2% by mass
Calibration sample: Monodisperse polystyrene Calibration method: Polystyrene conversion

[material]
The raw materials used in the following examples and comparative examples are as follows.

<Component (A)>
A-1:
Nippon Kayaku Kayrad DPHA
Mixed substance amount average molecular weight (Mw) of dipentaerythritol tetraacrylate and dipentaerythritol hexaacrylate: 700

<Component (B)>
B-1:
Silica particles (solvent: PGM) manufactured by CIK Nanotech
B-2:
Silica particles (solvent: MIBK) manufactured by CIK Nanotech
b-1 (for comparative example):
MEK-ST silica particles (solvent: MEK) manufactured by Nissan Chemical Co., Ltd.
b-2 (for comparative example):
In a flask equipped with a thermometer, a stirrer and a reflux condenser, 3.89 g (solid content: 30% by mass) of a silane coupling agent (“KBM5103” (trimethoxysilyl compound having an acryloyl group) manufactured by Shin-Etsu Chemical Co., Ltd.) , “MEK-ST” (b-1) 95.60 g manufactured by Nissan Chemical Co., Ltd., 0.16 g of acetylacetone aluminum, 0.33 g of water and 0.02 g of p-methoxyphenol were added, and silane coupling reaction was performed at 70 ° C. for 4 hours. And silica particles surface-modified with acryloyl groups were obtained.
b-3:
MEK-ST-L silica particles manufactured by Nissan Chemical Co., Ltd. (solvent: MEK)

  The average primary particle of each raw material used as the component (B) and the particle size distribution measured by a laser diffraction particle size distribution analyzer are as shown in Table 1 below.

<Component (C)>
C-1: Acrylic copolymer having a perfluoroalkyl structure and a polydimethylsiloxane structure (obtained by the following method) perfluorohexylethyl methacrylate 50 g, lauryl methacrylate 10 g, α, ω-dimercaptopropyl poly 10 g of dimethylsiloxane (Shin-Etsu Chemical Co., Ltd. X-22-167B, number average molecular weight 1600), 30 g of glycidyl methacrylate, 0.9 g of dodecyl mercaptan, 200 g of 1-methoxy-1-propanol (PGM) were added, and the internal temperature was reduced under a nitrogen stream. The temperature was raised to 55 ° C. Thereafter, 2,2′-azobis (2,4-dimethylvaleronitrile) (V65) was divided into 2 portions, a total of 0.6 g was added, and stirring was continued at 65 ° C. for 6 hours. Thereafter, the internal temperature was raised to 80 ° C., V65 was completely deactivated, and then returned to room temperature. The solid content concentration was 35% by mass.
Next, after heating to 90 ° C. in an air atmosphere, 0.5 g of p-methoxyphenol and 4.6 g of triphenylphosphine were added. After 5 minutes, 127.2 g of pentaerythritol triacrylate modified with succinic anhydride (Toagosei Co., Ltd. “Aronix M510”) was dissolved in 201.9 g of PGMAc and added dropwise over 30 minutes. Thereafter, the liquid temperature was raised to 110 ° C., maintained at this temperature for 14 hours, and then returned to room temperature, and the solid content was 35% by mass.

C-2: DIC Corporation Megafuck (registered trademark) RS-76-E
(Compound having perfluoroalkylene polyether and acryloyl group)

C-3: Acrylic copolymer having a polydimethylsiloxane structure (obtained by the following method)
To a reactor equipped with a stirrer, a reflux condenser and a thermometer, a one-terminal methacryloyl group-substituted polydimethylsiloxane having a number average molecular weight of 5,000 (“Sylaplane FM0721” manufactured by JNC, represented by the above formula (1)) 20 parts by mass of a compound containing a silicone-containing (meth) acrylate, 60 parts by mass of glycidyl methacrylate (“Acryester G” manufactured by Mitsubishi Rayon Co., Ltd.), 10 parts by mass of methyl methacrylate (“Acryester M” manufactured by Mitsubishi Rayon Co., Ltd.), stearyl Charge 10 parts by weight of methacrylate (“Acryester S” manufactured by Mitsubishi Rayon Co., Ltd.) and 151 parts by weight of methyl isobutyl ketone (MIBK). After starting stirring, the system was purged with nitrogen, and the temperature was raised to 55 ° C. '-Azobis (2,4-dimethylvaleronitrile) (“V-65” manufactured by Wako Pure Chemical Industries, Ltd. ) After adding 1.2 parts by mass and 0.9 parts by mass of 1-dodecanethiol (manufactured by Wako Pure Chemical Industries, Ltd.), the system was heated to 65 ° C. and stirred for 3 hours, and then V-65 was further reduced to 0. .6 parts by mass was added and stirred at 65 ° C. for 3 hours. The system was heated to 100 ° C. and stirred for 30 minutes, and then 163 parts by mass of MIBK was added. After adding 0.5 parts by mass of p-methoxyphenol (manufactured by Wako Pure Chemical Industries, Ltd.) and 2.6 parts by mass of triphenylphosphine (manufactured by Wako Pure Chemical Industries, Ltd.), acrylic acid (manufactured by Mitsubishi Chemical Corporation) 31.0 parts by mass was added, the temperature was raised to 110 ° C., and the mixture was stirred for 6 hours. After cooling, 4.8 parts by mass of MIBK was added to obtain a MIBK solution of a copolymer having a number average molecular weight of 6,500 (acrylic copolymer having a polydimethylsiloxane group in the side chain). The composition of the copolymer MIBK solution was 30% by mass of the copolymer and 70% by mass of MIBK (solid content 30% by mass).
C-4: BYK306 (polyether-modified polydimethylsiloxane) manufactured by BYK

[Example 1]
After mixing each component shown in Table-2 (but using BASF Irgacure (registered trademark) 184 as a polymerization initiator) in a four-necked flask, the solid content is 40% by mass. A curable composition was obtained by diluting with a 1: 7: 2 (mass ratio) mixed solvent of PGM, ethyl acetate, and MIBK. The curable composition was applied to a PET film (188 μm) using a bar coater so that the coating thickness after drying was 2 to 3 μm, and dried by heating at 80 ° C. for 30 seconds to form a coating film. The PET film on which the coating film of the curable composition is formed is a EYE manufactured by Eye Graphic Co., Ltd. at a position of 15 cm under the light source using a high-pressure mercury lamp with an output density of 90 W / cm ² as a light source.
Using UV METER UVPF-A1 and PD365, a cured film was obtained by irradiating ultraviolet rays so as to obtain an integrated light amount of 90 mJ / cm ² .

About the prepared curable composition and the formed cured film (hard coat film), transparency, water repellency, oil repellency, adhesion, magic adhesion resistance, magic wiping durability, scratch resistance, and hardness are as described above. The results are shown in Table 2.

<Examples 2 to 11 and Comparative Examples 1 to 8>
A curable composition was obtained in the same manner as in Example 1 except that the composition of the curable composition was changed as shown in Table-2 or Table-3. Each of the obtained curable compositions was subjected to a coating process and a curing process in the same manner as in Example 1 to obtain a cured film (laminate). Using the obtained cured film (laminated body), transparency, water repellency, oil repellency, adhesion, magic adhesion resistance, magic wiping durability, scratch resistance, hardness were evaluated, and the results are shown in Table-2 or It is shown in Table-3.

As is clear from the results of Tables 2 and 3, Comparative Examples 1 to 8 that do not contain the component (B) in the present invention have poor magic wiping durability, whereas the component (A) in the present invention. It can be seen that Examples 1 to 5 containing ~ (C) have markedly improved magic wiping durability.
In particular, each of Example 4 using “B-1” and Example 5 using “B-2” as component (B), and Comparative Example 1 using “b-1” instead of these. When Comparative Example 2 using “b-2” and Comparative Example 3 using no component (B) were compared, it was found that Examples 4 and 5 were all excellent in magic wiping durability.

  Further, Example 8 using “B-1” as the component (B) and “C-2” as the component (C), and “C-2” as the component (C) without using the component (B). When comparing with Comparative Example 4 using “”, it can be seen that Example 8 is excellent in magic wiping durability. Further, Example 9 using “B-1” as the component (B) and “C-3” as the component (C), and “C-3” as the component (C) without using the component (B). When compared with Comparative Example 5 using “”, it can be seen that Example 9 is excellent in magic wiping durability. Further, Example 10 using “B-1” as the component (B) and “C-4” as the component (C), and “C-4” as the component (C) without using the component (B). When compared with Comparative Example 4 using "", it can be seen that Example 10 is excellent in the magic wiping durability.

Claims (11)

The following component (A), component (B) and component (C) are included, and component (B) is 0.01 to 50 parts by mass and component (C) is 0.01 to 100 parts by mass of component (A). A curable composition containing 30 parts by mass .
Component (A): Ethylenically unsaturated compound Component (B): The average primary particle size is 1 to 100 nm, d90 measured by a laser diffraction particle size distribution meter is 200 to 2,000 nm, and d50 is 30 to 30 Oxide particle component (C) which is 1,000 nm and contains at least silica : a compound having at least one group selected from a perfluoroalkyl group, a perfluoroalkylene ether group and a polydimethylsiloxane group The curable composition according to claim 1, wherein component (B) has a d10 of 10 to 500 nm measured by a laser diffraction particle size distribution meter. The curable composition of Claim 1 or 2 containing a polyfunctional (meth) acrylate as a component (A). As component (C), and at least one of compounds having the compound and perfluoroalkylene ether group having a perfluoroalkyl group, and a compound having a polydimethylsiloxane group, any one of claims 1 to 3 The curable composition according to 1. The curable composition according to any one of claims 1 to 4 , comprising an organic solvent and having a solid content concentration of 5 to 95 mass%. The curable composition according to claim 5 , wherein the organic solvent is at least one selected from a saturated hydrocarbon solvent, an ester solvent, an ether solvent, an alcohol solvent, and a ketone solvent. The curable composition according to any one of claims 1 to 6, comprising a polymerization initiator and having a content of 0.01 to 20 parts by mass with respect to 100 parts by mass of the component (A). Hardened | cured material formed by irradiating an active energy ray to the curable composition of any one of Claims 1 thru | or 7 . It is a laminated body which has a base material and a hard-coat layer, and this hard-coat layer apply | coats the curable composition of any one of Claims 1 thru | or 7 on this base material, and this is an active energy ray. A laminate that is formed by irradiating. The laminate according to claim 9 , wherein the substrate is a plastic substrate. Wherein the plastic substrate is a polycarbonate resin, polyethylene terephthalate resin, is at least one selected from polymethyl methacrylate resin laminate of claim 1 0.