TW201522470A - Active energy ray-curable composition, cured product thereof, and article having cured coating film thereof - Google Patents

Abstract

The present invention provides an active energy ray-curable composition characterized by containing: an active energy ray curable compound (A); a fluorine compound (B) having a structure in which a cyclo polysiloxane structure is bonded to both terminals of a poly(perfluoroalkylene ether) chain via a divalent coupling group, and in which a (meth) acryloyl group is bonded to the cyclo polysiloxane structure via a divalent coupling group; a reactive silica (C1); and a non-reactive silica (C2). The active energy ray-curable composition can provide a cured coating film exhibiting high lead hardness and superior scratch resistance, antifouling properties, and lubricity.

Description

Active energy ray hardening type composition and cured product thereof and article having the same

The present invention relates to an active energy ray-curable composition which imparts high pencil hardness to the surface energy of various articles, and which can impart excellent scratch resistance, antifouling property, and slidability, and a cured product thereof and a hardened coating film thereof. article.

Since the active energy ray-curable composition has a long heat history to the coated substrate and is excellent in coating film hardness and scratch resistance, it can be used as a scratch resistant surface for a plastic molded article having a soft surface scratch resistance. A hard coating agent is used. Further, in order to impart antifouling properties to the cured coating film of the active energy ray-curable composition, a fluorine compound having a perfluoropolyether group and a polymerizable group has been proposed as a material to be added to the active energy ray-curable composition (for example, Patent Document 1.).

However, the cured coating film of the active energy ray-curable composition containing the fluorine compound described in Patent Document 1 has excellent antifouling properties, but has problems of scratch resistance, pencil hardness, and sliding property. Therefore, there is a need for an active energy ray-curable composition which can obtain a cured coating film which is excellent in antifouling property and excellent in scratch resistance, pencil hardness, and slidability. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 3963169

[The subject to be solved by the invention]

An object of the present invention is to provide an active energy ray-curable composition capable of obtaining a hardened coating film having high pencil hardness and excellent scratch resistance, antifouling property, and slidability; a cured product thereof; The article of the hardened coating film. [Means for solving the problem]

In order to solve the above problems, the inventors of the present invention have found that an active energy ray-curable type is obtained by adding a fluorine compound having a specific structure, a reactive cerium oxide, and a non-reactive cerium oxide to an active energy ray-curable compound. The surface of the hardened coating film of the composition has high pencil hardness, and also has excellent scratch resistance, antifouling property, and slidability, and the present invention has been completed.

That is, the present invention relates to an active energy ray-curable composition and a cured product thereof and an article having the same; the active energy ray-curable composition contains: an active energy ray-curable compound (A) having a cyclopolymerization The oxoxane structure is bonded to both ends of the poly(perfluoroalkylene ether) chain via a divalent linking group and the (meth)acryloyl group is bonded to the cyclopyroxyne structure via a divalent linking group. A fluorine compound (B) having a structure, a reactive cerium oxide (C1), and a non-reactive cerium oxide (C2). Furthermore, the present invention relates to a hard coat film obtained by using a cured product of the active energy ray-curable composition as a hard coat layer, and a protective film obtained by providing an adhesive layer on the hard coat film. [Effects of the Invention]

The active energy ray-curable composition of the present invention has a high pencil hardness on the surface of the cured coating film, and also has excellent scratch resistance, antifouling property, and slidability, and thus is a hard coating agent for protecting the surface of various articles. Very useful.

The active energy ray-curable composition of the present invention comprises: an active energy ray-curable compound (A) having a cyclic polyoxyalkylene structure and a divalent linking group bonded to a poly(perfluoroalkyl ether) chain. a fluorine compound (B) having a structure in which a (meth)acrylonyl group is bonded to a cyclopentasiloxane via a divalent linking group, a reactive cerium oxide (C1), and a non-reactive two Cerium oxide (C2).

Further, in the present invention, "(meth) acrylate" means one or both of acrylate and methacrylate; "(meth) propylene sulfhydryl" means propylene fluorenyl and methacryl One or both of the bases.

The active energy ray-curable compound (A) may, for example, be an amine ester (meth) acrylate or a polyfunctional acrylate.

As the amine ester (meth) acrylate, (A1) has four or more molecules in one molecule obtained by reacting an aliphatic polyisocyanate (a1) with a hydroxyl group-containing (meth) acrylate (a2). Base) acrylonitrile base.

The aliphatic polyisocyanate (a1) is a compound composed of an aliphatic hydrocarbon other than the isocyanate group. Specific examples of the aliphatic polyisocyanate (a1) include aliphatic polyisocyanates (a1-1) such as hexamethylene diisocyanate, diazonic acid diisocyanate, and isocyanuric acid triisocyanate; norbornane diisocyanate; Isophorone diisocyanate, methylene bis(4-cyclohexyl isocyanate), 1,3-bis(isocyanatomethyl)cyclohexane, 2-methyl-1,3-diisocyanato group An alicyclic polyisocyanate (a1-2) such as cyclohexane or 2-methyl-1,5-diisocyanatocyclohexane. Further, a terpolymer obtained by polymerizing the aliphatic polyisocyanate (a1-1) or the alicyclic polyisocyanate (a1-2) 3 can also be used as the aliphatic polyisocyanate (a1). Among the aliphatic polyisocyanates (a1), hexamethylene diisocyanate which is a diisocyanate of a linear aliphatic hydrocarbon, norbornane diisocyanate of a alicyclic diisocyanate, and isophorone diisocyanate can be improved. The active energy ray-curable composition of the present invention is preferred because it has a pencil hardness and a scratch resistance on the surface of the cured coating film.

The (meth) acrylate (a2) is a compound having a hydroxyl group and a (meth) acrylonitrile group, but the amine ester (meth) acrylate (A1) has four or more molecules in one molecule (A) The base of the acrylonitrile group preferably has two or more (meth) acrylonitrile groups. Examples of such a (meth) acrylate (a2) include trimethylolpropane di(meth) acrylate, ethylene oxide modified trimethylolpropane di(meth) acrylate, and epoxy. Propane modified trimethylolpropane di(meth)acrylate, glycerol di(meth)acrylate, bis(2-(methyl)acryloxyethyl)hydroxyethyl isocyanurate, new Pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and the like. One type of the (meth) acrylate (a2) may be used alone or two or more types may be used in combination with one type of the above-mentioned aliphatic polyisocyanate (a1). Further, among the (meth) acrylates (a2), pentaerythritol tri(meth) acrylate or dipentaerythritol penta (meth) acrylate can further enhance the active energy ray hardening of the present invention. The pencil hardness and scratch resistance of the surface of the cured coating film of the type composition are preferred.

The reaction of the above aliphatic polyisocyanate (a1) with the above (meth) acrylate (a2) can be carried out by a conventional amine esterification reaction. Further, in order to promote the progress of the amine esterification reaction, it is preferred to carry out the amine esterification reaction in the presence of an amine esterification catalyst. The amine esterification catalyst may, for example, be an amine compound such as pyridine, pyrrole, triethylamine, diethylamine or dibutylamine; a phosphide such as triphenylphosphine or triethylphosphine; dibutyltin dilaurate or the like. An organic tin compound such as octyltin laurate, octyltin diacetate, dibutyltin diacetate or tin octylate, or an organic zinc compound such as zinc octylate.

The above-mentioned amine ester (meth) acrylate (A1) obtained by the above-mentioned amine esterification reaction may be used singly or in combination of two or more kinds. Further, when two or more kinds are used, an amine ester acrylate obtained by using hexamethylene diisocyanate as the aliphatic polyisocyanate (a1) and a trimer using hexamethylene diisocyanate as the aforementioned aliphatic polycondensation are used. The combination of the isocyanate (a1) and the amine ester acrylate can further improve the pencil hardness and the scratch resistance of the surface of the cured coating film of the active energy ray-curable composition of the present invention, which is preferable.

The polyfunctional (meth) acrylate (A2) is a compound having three or more (meth) acrylonitrile groups in one molecule. Specific examples of the polyfunctional (meth) acrylate (A2) include trimethylolpropane tri(meth) acrylate and ethylene oxide modified trimethylolpropane tri(meth) acrylate. , propylene oxide modified trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ginseng (2 -(Meth)acryloxyethyl)isocyanurate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tris(A) Acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and the like. These polyfunctional (meth) acrylates (A2) may be used alone or in combination of two or more. Further, among the polyfunctional (meth) acrylates (A2), from the viewpoint of further improving the pencil hardness and the scratch resistance of the surface of the cured coating film of the active energy ray-curable composition of the present invention, The methyl group propylene oxime equivalent is preferably in the range of 50 to 200 g/eq., preferably in the range of 70 to 150 g/eq., more preferably in the range of 80 to 120 g/eq. Specific examples of the polyfunctional (meth) acrylate (A2) in the range of (meth) acrylonitrile equivalent of 80 to 200 g/eq., for example, neopentyl alcohol tetraacrylate (acrylonitrile equivalent: 88 g/ Eq.), dipentaerythritol hexaacrylate (acrylonitrile equivalent: 118 g/eq.), and the like.

The mass ratio [(A1)/(A2)] of the above-mentioned amine ester (meth) acrylate (A1) to the aforementioned polyfunctional (meth) acrylate (A2) is 90/ from the viewpoint of improving scratch resistance. The range of 10~10/90 is suitable, and the range of 80/20~20/80 is better, and the range of 75/25~25/75 is better.

Further, in the active energy ray-curable composition of the present invention, in addition to the amine ester (meth) acrylate (A1) and the polyfunctional (meth) acrylate (A2), the present invention may be omitted. The range of effects is blended with a mono(meth)acrylate having one (meth)acrylinyl group in one molecule, a di(meth)acrylate having two (meth)acrylonyl groups in one molecule, and the like. (Meth) acrylate. When other (meth) acrylate is blended in the active energy ray-curable composition of the present invention, the blending amount thereof is relative to the aforementioned amine ester (meth) acrylate (A1) and the aforementioned polyfunctional (methyl) The total amount of the acrylate (A2) is preferably 40 parts by mass or less, preferably 20 parts by mass or less.

The fluorine compound (B) has a cyclic polyoxyalkylene structure and is bonded to both ends of the poly(perfluoroalkylene ether) chain via a divalent linking group, and the (meth)acryloyl group is separated by a divalent linking group. A compound bonded to the structure of the aforementioned cyclopolyoxyalkylene structure. Further, in the present invention, "poly(perfluoroalkylene ether)" may also be referred to as "perfluoropolyether".

The poly(perfluoroalkylene ether) chain of the fluorine compound (B) is exemplified by a structure in which a divalent fluorinated carbon group having 1 to 3 carbon atoms and an oxygen atom are bonded to each other. The divalent fluorinated carbon group having 1 to 3 carbon atoms may be one type or a combination of two or more types. Specifically, the following structural formula (1) can be exemplified.

(In the above formula (1), X is a formula (1-1) to (1-5), and X may be any one of the following formulas (1-1) to (1-5), and Two or more types of the following formulas (1-1) to (1-5) may exist in a random form or in a block form. Further, n is an integer of 2 to 200 representing a repeating unit.

Among the poly(perfluoroalkylene ether) chains, the perfluorochemical represented by the above formula (1-1) is added from the viewpoint of improving the antifouling property of the cured coating film of the active energy ray-curable composition of the present invention. The methylene group and the poly(perfluoroalkylene ether) chain formed by the perfluoroethyl group represented by the above formula (1-2) are preferred. Here, the ratio of the perfluoromethylene group represented by the above formula (1-1) to the perfluoroethyl group represented by the above formula (1-2) [(1-1)/(1-2)] It should be in the range of 1/10~10/1. Further, the value of n in the above formula (1) is preferably in the range of 2 to 200, preferably in the range of 10 to 100, more preferably in the range of 20 to 80.

The above-mentioned fluorine compound (B) has a cyclic polysiloxane structure, and for example, the structure represented by the following formula (2) can be exemplified.

(In the above formula (2), R ¹ is a methyl group, R ³ is a divalent organic group bonded to a poly(perfluoroalkylene ether) chain, and R ⁴ is a group having a (meth)acryl fluorenyl group. The price is organic. In addition, m is an integer from 2 to 5.)

Among the above cyclopropane structures, a cyclotetraoxane structure in which m in the above formula (2) is 3 is preferred.

The divalent linking group to which the poly(perfluoroalkylene ether) chain and the cyclopolyoxyalkylene structure are bonded is not particularly limited as long as it is a divalent organic group, and for example, the following formula (3) can be exemplified. .

(In the above formula (3), Y is an alkylene group having 1 to 6 carbon atoms.)

In addition, the divalent linking group of the cyclomethoxane structure and the (meth)acryl fluorenyl group is not particularly limited as long as it is a divalent organic group, and examples thereof include the following formula (4).

(In the above formula (4), Z ¹ , Z ² and Z ³ are each independently an alkylene group having 1 to 6 carbon atoms.)

The method for producing the fluorine compound (B) can be, for example, a method produced by the following steps (1) to (3). (1) reacting a compound having an allyl group at both ends of a poly(perfluoroalkylene ether) chain with a cyclic polyoxyalkylene compound having a hydrofluorenyl group in the presence of a platinum-based catalyst to obtain a poly( The step of having a compound having a cyclic polyoxyalkylene structure at both ends of the perfluoroalkylene ether chain). (2) a step of reacting the compound obtained in (1) with an allyloxyalkanol in the presence of a platinum-based catalyst, and adding a hydroxyl group to the cyclic polyoxyalkylene structural moiety of the compound obtained in (1). (3) A step of reacting a (meth) acrylate having an isocyanate group with a hydroxyl group added to the (2) to introduce a (meth) acrylonitrile group.

The active energy ray hardening composition of the present invention is obtained from the viewpoint of imparting higher pencil hardness to the surface of the cured coating film of the active energy ray-curable composition of the present invention and further improving scratch resistance, antifouling property and slidability. The amount of the fluorine compound (B) blended in the product is relative to the amine ester (meth) acrylate (A1), the polyfunctional (meth) acrylate (A2), and any other blend (methyl) The total amount of the acrylate is 100 parts by mass, preferably in the range of 0.05 to 5 parts by mass, preferably in the range of 0.1 to 2 parts by mass.

The reactive ceria (C1) is obtained by introducing a reactive group such as a (meth) acrylonitrile group onto the surface of the ceria particle by surface modification. Moreover, from the viewpoint of further improving the transparency of the cured coating film of the active energy ray-curable composition of the present invention and the surface pencil hardness, the reactive ceria (C1) is preferably a nano-sized size, and is a colloid. Cerium oxide is preferred. The specific average particle diameter is preferably in the range of 5 to 200 nm, preferably in the range of 5 to 100 nm.

The non-reactive ceria (C2) does not have a reactive group on the surface of the ceria particles, but may be a surface-modified non-reactive organic group. Moreover, from the viewpoint of further improving the transparency and the surface pencil hardness of the cured coating film of the active energy ray-curable composition of the present invention, and also improving the curl resistance, the non-reactive cerium oxide (C2) is Nano-size is preferred, and colloidal ruthenium dioxide is preferred. The specific average particle diameter is preferably in the range of 5 to 200 nm, preferably in the range of 5 to 100 nm.

The ratio of the use of the reactive ceria (C1) to the non-reactive ceria (C2) [(C1)/(C 2)] can further enhance the hardening of the active energy ray-curable composition of the present invention. The viewpoint of the pencil hardness of the surface of the coating film is preferably in the range of 0.5 to 1.5, preferably in the range of 0.6 to 1.

The foregoing reaction in the active energy ray-curable composition of the present invention from the viewpoints of the pencil hardness, the scratch resistance, the antifouling property and the slidability of the surface of the cured coating film of the active energy ray-curable composition of the present invention The total blending amount of the cerium oxide (C1) and the aforementioned non-reactive cerium oxide (C2) relative to the aforementioned amine ester (meth) acrylate (A1) and the aforementioned polyfunctional (meth) acrylate (A2) And 100 parts by mass of the total of other (meth) acrylates to be blended, preferably in the range of 100 to 300 parts by mass, preferably in the range of 150 to 280 parts by mass.

Further, the active energy ray-curable composition of the present invention can be formed by applying it to a substrate and irradiating an active energy ray to form a cured coating film. The active energy ray refers to an ionizing radiation such as an ultraviolet ray, an electron beam, an α line, a β line, or a γ line. When a cured coating film is formed by irradiating ultraviolet rays as an active energy ray, it is preferred to add a photopolymerization initiator (D) to the active energy ray-curable composition of the present invention to improve the hardenability. Further, if necessary, a photo sensitizer may be added to improve the curability. On the other hand, when ionizing radiation such as an electron beam, an α line, a β line, or a γ line is used, even if the photopolymerization initiator (D) or the photosensitizer is not used, it is rapidly hardened, so that it is not necessary to specifically add photopolymerization. Starting agent (D) or photosensitizer.

The above photopolymerization initiator (D) can be exemplified by an intramolecular split type photopolymerization initiator and a dehydrogenation type photopolymerization initiator. The intramolecular split type photopolymerization initiator may, for example, be diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, or oligo[2-hydroxy-2-methyl Base-1-[4-(1-methylvinyl)phenyl]acetone], Dimethyl acetal, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxyl -2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2- Oxo (4-thiomethylphenyl)propan-1-one, 2- G-2-dimethylamino-1-(4- Acetophenone-based compound such as phenylphenyl)-butanone; benzoin such as benzoin, benzoin methyl ether and benzoin isopropyl ether; 2,4,6-trimethylphenylene diphenyl A fluorenylphosphine-based compound such as phosphine oxide or bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide; benzil, methylphenylglyoxylate Wait.

On the other hand, examples of the dehydrogenation type photopolymerization initiator include benzophenone, o-benzhydrylbenzoic acid methyl-4-phenylbenzophenone, and 4,4'-dichlorobenzophenone. Hydroxybenzophenone, 4-benzylidene-4'-methyl-diphenyl sulfide, propylene deuterated benzophenone, 3,3',4,4'-tetrakis (tertiary butylperoxycarbonyl) a benzophenone compound such as benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 2,4,6-trimethylbenzophenone or 4-methylbenzophenone; a thioxanthone compound such as 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone or 2,4-dichlorothioxanthone; (Michler's Ketone), an aminobenzophenone compound such as 4,4'-diethylaminobenzophenone; 10-butyl-2-chloroacridone, 2-ethylhydrazine, 9,10- Phenanthrene, camphorquinone, 1-[4-(4-benzylidylphenylsulfanyl)phenyl]-2-methyl-2-(4-methylphenylsulfonyl)propane-1- Ketones, etc. These photopolymerization initiators (D) may be used singly or in combination of two or more.

Further, examples of the photosensitizer include a tertiary amine compound such as diethanolamine, N-methyldiethanolamine or tributylamine, a urea compound such as o-tolylthiourea, sodium diethyldithiophosphate, and s. - A sulfur compound such as p-toluenesulfonate or the like.

The amount of the photopolymerization initiator and the photosensitizer to be used is preferably 0.05 to 20 parts by mass, preferably 0.5, per 100 parts by mass of the nonvolatile matter in the active energy ray-curable composition of the present invention. ~15% by mass.

Further, in the active energy ray-curable composition of the present invention, in addition to the above components (A) to (D), blending may be carried out as needed: a polymerization inhibitor, a surface conditioner, an antistatic agent, an antifoaming agent, and a viscosity. Adjusting agent, light stabilizer, weathering stabilizer, heat stabilizer, UV absorber, antioxidant, coating agent, organic pigment, inorganic pigment, pigment dispersant, cerium oxide bead, organic beads and other additives; cerium oxide, oxidation An inorganic filler such as aluminum, titanium oxide, zirconium oxide or antimony pentoxide. These other blends may be used singly or in combination of two or more.

The method of applying the active energy ray-curable composition of the present invention to a substrate varies depending on the application, and examples thereof include die coating, micro gravure coating, gravure coating, roll coating, and comma coating. , air knife coating, conformal coating, spray coating, dip coating, spin coating, wheeler coating, brush coating, solid coating by a silk screen, wire bar coating , curtain flow coating, etc.

The active energy ray that hardens the active energy ray-curable composition of the present invention is an apparatus that irradiates an active energy ray, such as an ultraviolet ray, an electron beam, an alpha ray, a beta ray, or a gamma ray ionizing radiation, as described above. In the case of using ultraviolet rays, low pressure mercury lamps, high pressure mercury lamps, ultra high pressure mercury lamps, metal halide lamps, electrodeless lamps, chemical lamps, black lamps, mercury-xenon lamps, short arc lamps, cadmium cadmium lasers, argon lasers can be exemplified. , sunlight, LED, etc. as a source of ultraviolet light. Further, when the substrate to which the active energy ray-curable composition of the present invention is applied is a film substrate, it is preferable to use a xenon-flash lamp which is irradiated by a flash to reduce the thermal influence on the film substrate. On the other hand, when an electron beam is used, a scanning electron beam accelerator, a curtain electron beam accelerator, or the like can be exemplified as a source of electron beam generation.

Further, when the active energy ray-curable composition of the present invention is irradiated with ultraviolet rays to form a cured coating film, it can be carried out in an air atmosphere, but a cured coating film having a higher pencil hardness is obtained, and further excellent scratch resistance is obtained. The viewpoint of the slidable cured coating film is preferably carried out in an environment having an oxygen concentration of 5,000 ppm or less.

Since the cured coating film of the active energy ray-curable composition of the present invention has excellent antifouling properties and is excellent in scratch resistance and slidability, the active energy ray-curable composition of the present invention can be applied to various types. The surface of the article is hardened to impart a high pencil hardness to the surface of various articles, and excellent antifouling properties, scratch resistance, and slidability. Therefore, the active energy ray-curable composition of the present invention is very useful as a hard coating agent which can impart high scratch resistance, antifouling property and the like to the surface of various articles.

The object to which the active energy ray-curable composition of the present invention can be applied is, for example, a casing of a home appliance such as a television, a refrigerator, a washing machine, an air conditioner, or a frame of an electronic device such as a computer, a smart phone, a mobile phone, a digital camera, or a game machine. Body; automotive, railway vehicles and other vehicles; various decorative materials such as decorative panels; woodworking materials such as furniture, artificial ‧ synthetic leather; FRP bath; liquid crystal display (LCD) such as triethylene cellulose (TAC) film Optical film; cymbal or diffuser for backlight parts of LCD; various display screens (hard coating layer, anti-reflection layer) such as plasma display (PDP), organic EL display; touch panel; mobile phone, smart phone, etc. Screen for terminal; color filter for liquid crystal display (hereinafter referred to as "CF"); transparent protective film; optical recording medium such as CD, DVD, Blu-ray disc; transfer film for inserting mold (IMD, IMF); photocopier, Rubber roller for OA equipment such as printers; glass surface for reading unit of OA equipment such as photocopiers and scanners; optical lenses for cameras, cameras, glasses, etc.; windproof and glass surfaces for watches and other watches Car windows for various vehicles such as automobiles and railway vehicles; cover glass or film for solar cells; various building materials such as decorative panels; window glass for houses; woodworking materials for furniture, etc.

The hard coat film of the present invention has a hard coat layer obtained by curing the active energy ray-curable composition of the present invention on at least one side of the film substrate. As the film substrate, various resin film substrates generally used can be used, and examples thereof include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polyethylene. , polypropylene, sedum, diacetyl cellulose, triacetyl cellulose, acetyl cellulose butyrate, cellulose acetate propionate, cycloolefin polymer, cyclic olefin copolymer, polyvinyl chloride , polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polymethylpentene, polyfluorene, polyetheretherketone, polyether oxime, polyether quinone A resin film such as polyimine, fluororesin, nylon, or acrylic resin. In particular, since the resin film of polyethylene terephthalate, triethylene glycol, and acrylic resin is excellent in transparency and workability, it can be preferably used.

Further, the film substrate may be a substrate composed only of the resin film exemplified above, but in order to improve adhesion to the active energy ray-curable composition of the present invention, primer coating may be applied to the resin film. A film substrate formed by a layer. The primer coating layer may, for example, be composed of a polyester resin, a polyurethane resin, an acrylic resin or the like. Further, for the purpose of improving the adhesion to the hard coat layer, the surface roughening treatment, the corona discharge treatment, the chromic acid treatment, the flame treatment, the hot air treatment, and the ozone may be performed by a sandblasting method or a solvent treatment method. A treatment is applied to the surface of the resin film by ultraviolet irradiation treatment, oxidation treatment, or the like.

Further, the thickness of the film substrate is preferably in the range of 50 to 200 μm, preferably in the range of 80 to 150 μm, more preferably in the range of 90 to 130 μm. In the present invention, by setting the thickness of the film substrate to this range, it is easy to suppress curling when a hard coat layer is provided on one surface of the film substrate.

Further, as the film substrate, a film substrate having a modulus of elasticity of 3 to 7 GPa is preferably used, and a film substrate having a range of 3 to 5 GPa is particularly preferably used. When the modulus of elasticity is in this range, deformation of the film substrate is less likely to occur at the time of forming the protective film, and cracking of the hard coat layer can be suppressed, and it is easy to suppress a decrease in hardness of the surface of the hard coat film. Moreover, since the flexibility of the film substrate can be ensured, it is easy to follow the gentle curved surface when the protective film is attached as described later.

The protective film of the present invention is one in which an adhesive layer is provided on one surface of the hard coat film. The adhesive layer may be provided by bonding an adhesive tape to the film substrate or by directly applying an adhesive layer on a surface of the film substrate opposite to the hard coated surface.

The thickness of the adhesive layer of the protective film of the present invention is preferably in the range of 5 to 50 μm, preferably in the range of 8 to 30 μm, more preferably in the range of 10 to 25 μm. In the present invention, by setting the thickness of the pressure-sensitive adhesive layer to this range, the adhesion reliability can be excellent, and the surface hardness of the hard coating film can be maintained without significant deterioration.

As the adhesive to be used in the adhesive layer of the present invention, a known acrylic resin, a rubber-based or an anthrone-based adhesive resin can be used. In particular, the acrylic copolymer having a (meth) acrylate monomer having an alkyl group having 2 to 14 carbon atoms as a main component and polymerized as a repeating unit has adhesion to a film substrate, The viewpoint of transparency and weather resistance is ideal.

The (meth) acrylate monomer having 2 to 14 carbon atoms may, for example, be ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, secondary butyl acrylate or tertiary butyl acrylate. Ester, n-hexyl acrylate, cyclohexyl acrylate, n-octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, isodecyl acrylate, lauryl acrylate, methyl methacrylate, A Ethyl acrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, butyl methacrylate, butyl methacrylate, n-hexyl methacrylate, methyl Cyclohexyl acrylate, n-octyl methacrylate, isooctyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, isodecyl methacrylate, lauryl methacrylate, and the like.

Among the above (meth) acrylate monomers, an alkyl (meth) acrylate having an alkyl group having 4 to 9 carbon atoms is preferred, and an alkyl acrylate having an alkyl group having 4 to 9 carbon atoms is preferred. The ester is better. Among the alkyl acrylates, n-butyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, and ethyl acrylate are particularly preferred. By using an alkyl (meth)acrylate having an alkyl group having a carbon number in the range, the desired adhesion can be easily ensured.

The content of the (meth) acrylate having 2 to 14 carbon atoms in the monomer of the acrylic copolymer used in the adhesive layer of the present invention is preferably 90 to 99% by mass, preferably 90. ~96% by mass. By setting the content of the aforementioned (meth) acrylate in this range, the desired adhesion can be easily ensured.

As the acrylic copolymer, a (meth) acrylate monomer having a polar group such as a hydroxyl group, a carboxyl group or a decylamino group or another vinyl group having a polar group is preferably used as a monomer component.

Examples of the hydroxyl group-containing (meth) acrylate monomer include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-hydroxyhexyl (meth) acrylate. Hydroxypropyl (meth)acrylate, caprolactone modified (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and the like. Among these, 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 6-hydroxyhexyl (meth)acrylate are preferably used.

The above-mentioned carboxyl group-containing (meth) acrylate monomer may, for example, be acrylic acid, methacrylic acid, itaconic acid, maleic acid, crotonic acid, acrylic acid or methacrylic acid 2-polymer, ethylene oxide modification. Succinic acid acrylate and the like. Among these, acrylic acid is preferred.

The above-mentioned (meth) acrylate monomer having a mercaptoamine group may, for example, be N-vinyl-2-pyrrolidone, N-vinylcaprolactam, or acrylonitrile. Porphyrin, acrylamide, N,N-dimethylpropenamide, N-propyleneoxyethyl-3,4,5,6-tetrahydrophthalimide, and the like. Among these, N-vinyl-2-pyrrolidone, N-vinyl caprolactam, and acrylonitrile are used. Porphyrin is preferred.

Examples of the other polar group-containing vinyl monomer include vinyl acetate, acrylonitrile, maleic anhydride, and itaconic anhydride.

The content of the monomer having a polar group is preferably from 0.1 to 20% by mass, preferably from 1 to 13% by mass, more preferably from 1.5 to 8% by weight, based on the monomer component constituting the acrylic copolymer. When a monomer having a polar group is contained in this range, the cohesive force, retention, and adhesion of the adhesive can be easily adjusted to a desired range.

The weight average molecular weight Mw of the acrylic copolymer used in the adhesive layer is preferably from 400,000 to 1,400,000, preferably from 600,000 to 1,200,000. When the weight average molecular weight Mw of the acrylic copolymer is within this range, the adhesion is easily adjusted to a specific range.

Further, the weight average molecular weight Mw can be measured by gel permeation chromatography (GPC). More specifically, "SC8020" manufactured by Tosoh Corporation can be used as a GPC measuring device, and the polystyrene-converted value can be obtained by measuring the following GPC measurement conditions. (Measurement conditions of GPC) ‧ Sample concentration: 0.5% by weight (tetrahydrofuran solution) ‧ Sample injection amount: 100 μL ‧ Dissolved solution: Tetrahydrofuran (THF) ‧ Flow rate: 1.0 mL/min ‧ Column temperature (measured temperature): 40 ° C ‧ Pipe column: "TSKgel GMHHR-H" manufactured by Tosoh Co., Ltd. ‧Detector: Differential refractometer

In order to further improve the cohesive force of the adhesive layer, it is preferred to add a crosslinking agent to the adhesive. Examples of the crosslinking agent include an isocyanate crosslinking agent, an epoxy crosslinking agent, and a chelate crosslinking agent. The amount of the crosslinking agent to be added is preferably adjusted so that the gel fraction of the adhesive layer is 25 to 80% by mass, more preferably 40 to 75% by mass, and the optimum is 50. 70% by mass adjustment. By adjusting the gel fraction to this range, it is possible to suppress a decrease in the surface pencil hardness when the protective film is attached to the substrate, and it is also possible to make the adhesion sufficient. Further, in the gel fraction of the present invention, the cured adhesive layer was immersed in toluene, and after leaving for 24 hours, the dried mass of the residual insoluble component was measured and expressed as a percentage with respect to the original mass.

In order to further improve the adhesion of the adhesive layer, an adhesive-imparting resin may be added. When the adhesive resin is an acrylic copolymer, it is preferably added in an amount of 10 to 60 parts by mass based on 100 parts by mass of the acrylic copolymer. When the adhesion is further emphasized, it should be added in the range of 20 to 50 parts by mass.

Further, in the adhesive, a conventionally known additive other than the above may be added. For example, in order to improve the adhesion to the glass substrate, the decane coupling agent is preferably added in an amount of 0.001 to 0.005 parts by mass based on 100 parts by mass of the adhesive. Further, a plasticizer, a softener, a filler, a pigment, a flame retardant or the like may be added as other additives as needed.

Since the protective film of the present invention has excellent scratch resistance and slidability, it can be used in various applications, and can be suitably applied to an image display unit of a video display device such as a liquid crystal display (LCD) or an organic EL display. In particular, even if it is a thin type, it can achieve excellent scratch resistance and slidability. Therefore, it is highly demanded for miniaturization and thinning as an electronic notebook, a mobile phone, a smart phone, a portable audio player, a portable computer, and a tablet terminal. The protective film of the image display unit of the video display device of the mobile electronic terminal is ideal. For example, the image display device has an image display module such as an LCD module or an organic EL module, and a transparent panel for protecting the image display module is provided on the upper portion of the image display module. In the video display device of the present invention, the protective film of the present invention is attached to the surface or the inner surface of the transparent panel, thereby being effective for preventing scratches or preventing scattering of the transparent panel. [Examples]

The invention will be more specifically described below by way of examples.

(Synthesis Example 1: Synthesis of Amine Ester Acrylate (A1-1)) In a flask equipped with a stirrer, a gas introduction tube, a cooling tube, and a thermometer, neopentyl alcohol triacrylate (hereinafter referred to as "PE3A") was added. And a mixture of pentaerythritol tetraacrylate (hereinafter referred to as "PE4A") (PE3A/PE4A=60/40 (mass ratio)) 549.1 parts by mass, dibutyltin diacetate 0.1 parts by mass, dibutylhydroxytoluene 0.6 The mass fraction, 0.1 part by mass of p-methoxyphenol, and 160 parts by mass of butyl acetate were slowly heated while blowing air and uniformly mixing. When the temperature reached 60 ° C, 90.9 parts by mass of hexamethylene diisocyanate was added, and then the reaction was carried out at 80 ° C for 5 hours to obtain a nonvolatile content of the amine ester acrylate (A1-1) having 6 propylene groups in one molecule. 80% by mass solution. Further, this solution contained 34.3% by mass of PE4A in addition to the amine ester acrylate (A1-1) in the nonvolatile matter.

(Synthesis Example 2: Synthesis of Amine Ester Acrylate (A1-2)) In a flask equipped with a stirrer, a gas introduction tube, a cooling tube, and a thermometer, 254 parts by mass of butyl acetate and 222 parts by mass of isophorone diisocyanate were added. , 0.5 parts by mass of p-methoxyphenol and 0.5 parts by mass of dibutyltin diacetate, and after heating to 70 ° C while blowing air, a mixture of PE3A and PE4A was added dropwise for 1 hour (PE3A/PE4A=75/25 (mass ratio) )) 795 parts by mass. After the completion of the dropwise addition, the reaction was carried out at 70 ° C for 3 hours, and the reaction was further carried out until the infrared absorption spectrum of 2250 cm ^-1 of the isocyanate group disappeared, and an amine ester acrylate having 6 propylene fluorenyl groups in one molecule was obtained (A1- The nonvolatile content of 2) is a solution of 80% by mass. Further, this solution contained 19.5% by mass of PE4A in addition to the amine ester acrylate (A1-2) in the nonvolatile matter.

(Synthesis Example 3: Synthesis of Amine Ester Acrylate (A1-3)) A mixture of PE3A and PE4A (PE3A/PE4A=60/40 (mass ratio) was added to a flask equipped with a stirrer, a gas introduction tube, a cooling tube, and a thermometer. )) 242 parts by mass, 0.23 parts by mass of p-methoxyphenol, 0.13 parts by mass of dibutyltin dilaurate, and 100 parts by mass of methyl ethyl ketone, and the temperature was raised to 75 ° C while blowing air, and the hexamethylene group was added dropwise over 2 hours. 3 isocyanate (isocyanurate) ("DESMODUR N3390BA" manufactured by Bayer Polyurethane Co., Ltd., 90% by mass of nonvolatile matter, NCO%: 19.6, NCO equivalent: 214 g/eq.) 107 mass A mixed solution of 50 parts by mass of methyl ethyl ketone. After the completion of the dropwise addition, the reaction was carried out at 75 ° C for 4 hours, and the reaction was further carried out until the infrared absorption spectrum of 2250 cm ^-1 of the isocyanate group disappeared, and an amine ester acrylate having 9 propylene groups in one molecule was obtained (A1- The nonvolatile content of 3) was a solution of 67.8% by mass. Further, this solution contained 28.6% by mass of PE4A in addition to the amine ester acrylate (A1-3) in the nonvolatile content.

(Synthesis Example 4: Synthesis of Fluorine Compound (B-1)) In a flask equipped with a stirrer and a cooling tube, a perfluoropolyether having an allyl group at both terminals represented by the following formula (5) was added under a dry nitrogen atmosphere. 500 parts by mass, 700 parts by mass of hexafluoro-m-xylene, and 361 parts by mass of tetramethylcyclotetraoxane were heated to 90 ° C with stirring. To this, 0.442 parts by mass of a toluene solution of chloroplatinic acid/vinyloxirane complex (containing 1.1 × 10 ^-6 mol of Pt element) was added, and the internal temperature was maintained at 90 ° C or higher and stirred for 4 hours. After confirming the disappearance of the allyl group of the raw material by ¹ H-NMR spectrum, the solvent and excess tetramethylcyclotetraoxane were distilled off under reduced pressure, and subjected to activated carbon treatment, whereby the following formula (6) was obtained as colorless. Transparent liquid perfluoropolyether compound (1).

(where m/n is 0.9, and the sum of m and n is 45 on average.)

50 parts by mass of the perfluoropolyether compound (1) obtained above, 7.05 parts by mass of 2-allyloxyethanol, 50 parts by mass of hexafluoro-m-xylene, and chloroplatinic acid/vinyl oxime in a dry air atmosphere 0.0442 parts by mass of a toluene solution of the alkane complex (containing Pt elemental substance 1.1 × 10 ^-7 mol) was mixed and stirred at 100 ° C for 4 hours. After confirming the disappearance of the Si-H group by ¹ H-NMR spectrum and infrared absorption spectrum, the solvent and excess 2-allyloxyethanol were distilled off under reduced pressure, and subjected to activated carbon treatment to obtain a pale formula (7). a yellow transparent liquid perfluoropolyether compound (2).

50 parts by mass of the perfluoropolyether compound (2) obtained above, 50 parts by mass of tetrahydrofuran, and 9 parts by mass of 2-propenyloxyethyl isocyanate were mixed in a dry air atmosphere, and heated to 50 °C. Next, 0.05 parts by mass of dioctyltin laurate was added, and the mixture was stirred at 50 ° C for 24 hours. After the completion of the heating, the mixture was distilled off under reduced pressure at 80 ° C and 0.27 kPa to obtain a fluorine compound (B-1) represented by the following formula (8) as a pale yellow paste. To the fluorine compound (B-1), a mixed solvent of methyl ethyl ketone and methyl isobutyl ketone (methyl ethyl ketone / methyl isobutyl ketone = 1/3 (mass ratio)) was added to prepare a fluorine compound having a nonvolatile content of 20% by mass. (B-1) solution.

Using the amine ester acrylates (A1-1) to (A1-3) and the fluorine compound (B-1) obtained above, an active energy ray hardening type composition was prepared as follows.

(Example 1) 62 parts by mass of a solution containing the amine ester acrylate (A1-1) obtained in Synthesis Example 1 (containing 32.6 parts by mass of the amine ester acrylate (A1-1) and 17 parts by mass of PE4A), 18.3 parts by mass of a solution containing the amine ester acrylate (A1-3) obtained in Synthesis Example 3 (containing 8.9 parts by mass of the amine ester acrylate (A1-3), 3.5 parts by mass of PE4A), a mixture of PE4A and PE3A (PE4A/ PE3A=60/40 (mass ratio)) 7.5 parts by mass of a solution of 20% by mass of the fluorine-containing compound (B-1) obtained in Synthesis Example 4 (1.5 parts by mass of the fluorine compound (B-1)), Reactive colloidal cerium oxide (MEK-AC-2140Z manufactured by Nissan Chemical Industries Co., Ltd.), a methyl ethyl ketone dispersion having a nonvolatile content of 40% by mass; hereinafter referred to as "reactive cerium oxide (C1-1)". 287.5 parts by mass (115 parts by mass of reactive ceria (C1-1)), non-reactive colloidal ceria ("MEK-ST40" manufactured by Nissan Chemical Industries Co., Ltd., 40% by mass of nonvolatile matter) Methyl ethyl ketone dispersion; hereinafter referred to as "non-reactive ceria (C2-1)".) 312.5 parts by mass (non-reactive ceria (C2-1): 125 parts by mass), photopolymerization initiator (BASF) JAPAN (shares) "Irgacure 184", 1-hydroxycyclohexyl phenyl ketone; hereinafter referred to as "photopolymerization initiator (D-1)".) 10.9 parts by mass and photopolymerization initiator (BASF JAPAN Co., Ltd.) Irgacure 754", a mixture of 2-[2-oxo-2-phenylethenyloxyethoxy]ethyl hydroxyphenylacetate and 2-(2-hydroxyethoxy)ethyl hydroxyphenylacetate; Hereinafter, it is simply referred to as "photopolymerization initiator (D-2)".) 1.6 parts by mass of the mixture was uniformly stirred, and then diluted with methyl ethyl ketone to prepare an active energy ray-curable composition (1) having a nonvolatile content of 40% by mass.

[Evaluation of Appearance of Coating Agent] In order to determine whether or not the active energy ray-curable composition (1) obtained above can be used as a coating agent, the appearance was visually observed, and the appearance of the coating agent was evaluated according to the following criteria. ○: No white turbidity and separation of components. ×: There is white turbidity or separation of components.

[Production of the test piece film] The active energy ray-curable composition (1) obtained above was applied to a polyethylene terephthalate film (manufactured by Toyobo Co., Ltd.) by the wire rod (#40) (COSMOSHINE) A4100", a thickness of 100 μm) on the easy-to-adhere treatment surface, and after drying at 60 ° C for 1 minute, an ultraviolet irradiation device ("MIDN-042-C1" manufactured by Eye Graphics Co., Ltd.) was used in an environment with an oxygen concentration of 5,000 ppm or less. Lamp: 120 W/cm, high-pressure mercury lamp), and irradiated with ultraviolet light at an irradiation amount of 0.5 J/cm ² to obtain a test piece film having a hard coat film (hard coat layer) having a thickness of 15 μm.

[Evaluation of Appearance of Hardened Coating Film] The surface of the cured coating film of the test piece film obtained above was visually observed, and the appearance of the cured coating film was evaluated according to the following criteria. ○: No coating unevenness, coating texture, and particles. ×: There is uneven coating, coating texture or particles.

With respect to the test piece film obtained above, the following evaluation, or measurement of curl, pencil hardness, scratch resistance, water contact angle, antifouling property, and slidability were performed.

[Evaluation of Curing Resistance] The film for evaluation obtained above was cut into 10 cm squares, and after standing overnight at 23 ° C and 50% RH, the floating of the four corners of the curl was measured from the bottom surface, and the resistance was evaluated according to the following criteria. Curl. ◎: The average value of the four corners is less than 10 mm. ○: The average value of the four-corner float is 10 mm or more and less than 25 mm. ×: The average value of the four-corner float is 25 mm or more.

[Measurement of Pencil Hardness] The hardest pencil on the surface of the cured coating film obtained as described above was measured using a pencil prescribed in JIS S 6006:2007, and the hardest pencil without scratches was measured in accordance with JIS K 5600-5-4:1999. Hardness is used as pencil hardness.

[Evaluation of the scratch resistance] The test piece film obtained above was cut into a rectangular shape of 30 cm × 2 cm, and fixed by a jig to a flat friction tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.) for use of steel wool #0000. The scratched state of the test piece after reciprocating 200 times under a load of 1 kg/cm ² , a stroke of 10 cm, and a speed of 20 cm/sec was visually observed, and the scratch resistance was evaluated according to the following criteria. ◎: No scratches. ○: There are less than 5 scratches. △: There were 5 or more scratches, but there was no scratch on the entire surface of the test piece. ×: The test piece film was scratched as a whole.

[Measurement of water contact angle] The test piece film obtained above was cut into a rectangle of 1 × 5 cm, and the hardened coating film of the test piece film was made into a surface side and fixed on a glass plate with a double-sided tape to form a synergistic interface science. The company's automatic contact angle meter "DROMPAMSTER500" measures the contact angle of 4 to 4.5 μL of purified water.

[Evaluation of the antifouling property] On the hardened coating film of the test piece film obtained above, the ink was applied in a circular shape by "unimediax (black)" manufactured by Mitsubishi Pencil Co., Ltd., and the degree of repulsion of the ink was visually observed. . From this observation, the antifouling property was evaluated in accordance with the following criteria. 5: Repel the ink into dots. 4: Repel the ink into dots and lines. 3: The ink is repelled into a line shape. 2: Only slightly repelled ink. 1: Does not reject ink.

[Evaluation of slidability] From the ease of sliding when the surface of the cured coating film of the test piece film obtained above was rubbed by BEMCOT (made by Asahi Kasei Fiber Co., Ltd.), the slidability was evaluated according to the following criteria. ◎: The sliding is good. ○: It will slide. △: It is difficult to slide. ×: Do not slide.

(Example 2) The solution of 20% by mass of the fluorine-containing compound (B-1) used in Example 1 was 5 parts by mass (the fluorine compound (B-1) was 1 part by mass), and In the same manner as in Example 1, 40% by mass of the active energy ray-curable composition (2) having a nonvolatile content was prepared. Using the obtained active energy ray-curable composition (2), in the same manner as in Example 1, the test piece film was produced and evaluated or measured.

(Example 3) The mixture containing PE4A and PE3A (PE4A/PE3A=60/40 (mass ratio)) used in Example 1 was used, and the amine ester-containing acrylate (A1-2) obtained in Synthesis Example 2 was used. 23.8 parts by mass of the solution (containing 15.3 parts by mass of the amine ester acrylate (A1-2), 3.7 parts by mass of PE4A), and a mixture of DPHA and DPPA (DPHA/DPPA = 60/40 (mass ratio)), 19 parts by mass, An active energy ray-curable composition (3) having a nonvolatile content of 40% by mass was prepared in the same manner as in Example 1. Using the obtained active energy ray-curable composition (3), the test piece film was produced and evaluated or measured in the same manner as in Example 1.

(Example 4) The blending amount of the methyl ethyl ketone dispersion of 40% by mass of the nonvolatile content of the reactive cerium oxide (C1-1) used in Example 1 was changed from 287.5 parts by mass to 187.5 parts by mass (reactive two) An active energy ray-curable composition (4) having a nonvolatile content of 40% by mass was prepared in the same manner as in Example 1 except that the cerium oxide (C1-1) was 75 parts by mass. Using the obtained active energy ray-curable composition (4), the test piece film was produced and evaluated or measured in the same manner as in Example 1.

(Comparative Example 1) No preparation was carried out in the same manner as in Example 1 except that the reactive ceria (C1-1) and the non-reactive ceria (C2-1) used in Example 1 were not blended. An active energy ray-curable composition (R1) having a volatile component content of 40% by mass. Using the obtained active energy ray-curable composition (R1), the test piece film was produced and evaluated or measured in the same manner as in Example 1.

(Comparative Example 2) A fluorine compound having an acrylonitrile group at a single terminal of a poly(perfluoroalkylene ether) chain was used without using a solution of 20% by mass of the fluorine-containing compound (B-1) used in Example 1. (OPTOOL DAC-HP, manufactured by DAIKIN Industrial Co., Ltd., 20 parts by mass of non-volatile components; hereinafter referred to as "fluorine compound (RB-1)".) 7.5 parts by mass (fluorine compound (RB-1) is 1.5 masses) In the same manner as in Example 1, an active energy ray-curable composition (R2) having a nonvolatile content of 40% by mass was prepared in the same manner as in Example 1. Using the obtained active energy ray-curable composition (R2), the test piece film was produced and evaluated or measured in the same manner as in Example 1.

(Comparative Example 3) The blending amount of the methyl ethyl ketone dispersion of 40% by mass of the nonvolatile content of the reactive cerium oxide (C1-1) used in Example 1 was changed from 287.5 parts by mass to 500 parts by mass (reactive two) The active energy of 40% by mass of the nonvolatile matter was prepared in the same manner as in Example 1 except that the cerium oxide (C1-1) was 200 parts by mass) and the non-reactive cerium oxide (C2-1) was not blended. Ray hardening composition (R3). Using the obtained active energy ray-curable composition (R3), the test piece film was produced and evaluated or measured in the same manner as in Example 1.

(Comparative Example 4) The blending amount of the methyl ethyl ketone dispersion of 40% by mass of the non-volatile ceria (C2-1) used in Example 1 was changed from 312.5 parts by mass to 500 parts by mass (non-reaction). Preparation of 40% by mass of nonvolatile matter in the same manner as in Example 1 except that the cerium dioxide (C2-1) was 200 parts by mass) and the reactive cerium oxide (C1-1) was not blended. Energy ray hardening composition (R4). Using the obtained active energy ray-curable composition (R4), the test piece film was produced and evaluated or measured in the same manner as in Example 1.

The composition and evaluation results of the active energy ray-curable compositions obtained in the above Examples 1 to 4 and Comparative Examples 1 to 4 are shown in Table 1. In addition, all the compositions in Table 1 are described as the nonvolatile content, and the amine ester acrylates (A1-1) to (A1-3) are described as including the blending amount of PE4A.

From the evaluation results shown in Table 1, it was confirmed that the examples 1 to 4 of the active energy ray-curable composition of the present invention have no problem in appearance as a coating agent, and there is no problem in the appearance of the cured coating film. Further, it was confirmed that the active energy ray-curable composition of the present invention has a small curl after curing and has high curl resistance. Further, it was confirmed that the surface of the cured coating film of the active energy ray-curable composition of the present invention has high pencil hardness and excellent scratch resistance, pencil hardness, antifouling property, and slidability.

On the other hand, in Comparative Example 1, an active energy ray-curable composition which does not use both the reactive ceria (C1) and the non-reactive ceria (C2) used in the present invention is used, and it can be confirmed. The pencil hardness is not sufficient.

Comparative Example 2 is an example of an active energy ray-curable composition using a fluorine compound other than the fluorine compound (B) used in the present invention, and it was confirmed that the pencil hardness, the scratch resistance, and the slidability were insufficient.

Comparative Example 3 is an example of an active energy ray-curable composition in which non-reactive ceria (C2) used in the present invention is not used, and it is confirmed that the pencil hardness is insufficient, and the curl after curing is large and the curl resistance is high. Not enough.

Comparative Example 4 is an example of an active energy ray-curable composition in which the reactive cerium oxide (C1) used in the present invention is not used, and it is confirmed that the pencil hardness and the scratch resistance are insufficient.

no.

no.

Claims (14)

An active energy ray-curable composition comprising: an active energy ray-curable compound (A) having a cyclic polyoxyalkylene structure interposed between two ends of a poly(perfluoroalkyl ether) chain via a divalent linking group And a (meth)acryloyl group-based fluorine compound (B), a reactive cerium oxide (C1), and a non-reactive oxidizing agent which are bonded to the cyclic polyoxyalkylene structure via a divalent linking group.矽 (C2). The active energy ray-curable composition according to the first aspect of the invention, wherein the active energy ray-curable compound (A) is an aliphatic polyisocyanate (a1) and a hydroxyl group-containing (meth) acrylate (a2). An amine ester (meth) acrylate (A1) having four or more (meth) acrylonitrile groups in one molecule obtained by the reaction, and a plurality of (meth) acryl fluorenyl groups having one or more molecules in one molecule Functional (meth) acrylate (A2). An active energy ray-curable composition according to claim 2, wherein the aliphatic polyisocyanate (a1) is selected from the group consisting of hexamethylene diisocyanate, norbornane diisocyanate, and isophorone diisocyanate. One or more polyisocyanates of the group consisting of methylene bis(4-cyclohexyl isocyanate) and the above-mentioned trimers. The active energy ray-curable composition of claim 2, wherein the (meth) acrylate (a2) is selected from the group consisting of pentaerythritol penta (meth) acrylate and pentaerythritol. One or more (meth) acrylates in the group consisting of tris(meth)acrylate. The active energy ray-curable composition of claim 2, wherein the poly(meth)acrylate (A2) has a (meth) acrylonitrile equivalent of 50 to 200 g/eq. The active energy ray-curable composition of claim 2, wherein the polyfunctional (meth) acrylate (A2) is selected from the group consisting of dipentaerythritol hexa(meth) acrylate, bis new One or more polyfunctional (methyl) groups of pentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, and pentaerythritol tri(meth) acrylate Acrylate. A cured product obtained by irradiating an active energy ray-curable composition of any one of claims 1 to 6 with an active energy ray. A cured product obtained by irradiating ultraviolet rays in an atmosphere having an oxygen concentration of 5,000 ppm or less in an active energy ray-curable composition according to any one of claims 1 to 6. An article having a cured coating film of an active energy ray-curable composition according to any one of claims 1 to 6. A hard coating film having a hard coat layer on at least one side of a film substrate, and the hard coat layer is hardened by an active energy ray hardening type composition according to any one of claims 1 to 6. Composition. The hard coat film of claim 10, wherein the hard coat layer has a thickness of 1 to 20 μm, and the film substrate has a thickness of 50 to 200 μm. A protective film characterized by having an adhesive layer on one side of a hard coat film as in claim 10 of the patent application. The protective film of claim 12, wherein the adhesive layer has a thickness of 5 to 50 μm. The protective film of claim 12 is for protecting the image display portion of the mobile electronic terminal.