TWI660995B - Active energy ray-curable composition and cured product thereof, and article having cured coating film - Google Patents

Abstract

The present invention provides an active-energy-ray-curable composition, which contains: an active-energy-ray-curable compound (A) and a poly (perfluoroalkylene ether) bonded to a poly (perfluoroalkylene ether) through a divalent linking group with a cyclopolysiloxane structure. A fluorine compound (B), a reactive silicon dioxide (C1), and a non-fluorine compound (B), a structure in which a (meth) acryl group is bonded to the cyclopolysiloxane structure through a divalent linking group at both ends of the chain Reactive silicon dioxide (C2). By using the active energy ray-curable composition of the present invention, a hardened coating film having high pencil hardness and also excellent scratch resistance, stain resistance, and sliding properties can be obtained.

Description

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

The present invention relates to an active energy ray-curable composition, a hardened product thereof, and a hardened coating film which can impart high pencil hardness to the surface of various articles, and can also provide excellent scratch resistance, stain resistance, and sliding properties. article.

The active energy ray-curable composition has the characteristics of less thermal history on the coated substrate, excellent coating film hardness, and excellent abrasion resistance. Therefore, for example, it can be used to impart abrasion resistance to the surface of a plastic molded product that has the disadvantages of softness and abrasion resistance. Used as a hard coating agent. In addition, in order to impart antifouling properties to a cured coating film of an active energy ray-curable composition, a fluorine compound having a perfluoropolyether group and a polymerizable group has been proposed as a material added to the active energy ray-curable composition (for example, refer to Patent document 1.).

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

[Patent Document 1] Japanese Patent No. 3963169

[Questions to be Solved by the Invention]

An object to be solved by 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 abrasion resistance, stain resistance, and sliding properties; a cured product thereof; and Articles with a hardened coating. [Means for solving problems]

As a result of continuous research to solve the above-mentioned problems, the inventors of the present case have found that an active energy ray-curable type is obtained by adding a fluorine compound having a specific structure, reactive silicon dioxide, and non-reactive silicon dioxide to the 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, stain resistance, and sliding properties, and completed the present invention.

That is, the present invention relates to an active energy ray-curable composition, a hardened product thereof, and an article having a hardened coating film thereon. The active energy ray-curable composition contains: an active energy ray-curable compound (A), which has a cyclic polymerization. The siloxane structure is bonded to the two ends of the poly (perfluoroalkylene ether) chain via a divalent linking group and the (meth) acrylfluorenyl group is bonded to the cyclopolysiloxane structure via a divalent linking group. The resulting structure is a fluorine compound (B), a reactive silicon dioxide (C1), and a non-reactive silicon dioxide (C2). Moreover, this invention relates to the hard-coating film which used the hardened | cured material of the active energy ray hardening composition as a hard-coating layer, and the protective film which provided the adhesive layer on this hard-coating film. [Effect of the invention]

The active energy ray-curable composition of the present invention has a high pencil hardness on the surface of the hardened coating film, and also has excellent scratch resistance, antifouling, and sliding properties. Therefore, it is a hard coating agent for protecting the surface of various articles. The system is extremely useful.

The active-energy-ray-curable composition of the present invention contains: an active-energy-ray-curable compound (A), a cyclopolysiloxane structure with two divalent linking groups bonded to two poly (perfluoroalkylene ether) chains A fluorine compound (B), a reactive silicon dioxide (C1), and a non-reactive difluoride (B) structure in which a (meth) acrylfluorenyl group is bonded to the cyclopolysiloxane structure via a divalent linking group at the terminal. Silicon oxide (C2).

In addition, in the present invention, "(meth) acrylate" means one or both of acrylate and methacrylate; "(meth) acrylmethyl" means acrylmethyl and methacryl Either one of the bases or both.

Examples of the active energy ray-curable compound (A) include amine ester (meth) acrylate and polyfunctional acrylate.

As the aforementioned amine ester (meth) acrylate, (A1) is a compound obtained by reacting an aliphatic polyisocyanate (a1) with a hydroxyl group-containing (meth) acrylate (a2). Base) Acrylic base.

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

The (meth) acrylic acid ester (a2) is a compound having a hydroxyl group and a (meth) acrylfluorenyl group, but in order that the amine ester (meth) acrylic acid ester (A1) has four or more (a) In the case of acryl) acryl group, it is preferred that the (meth) acryl group be two or more. Examples of the (meth) acrylate (a2) include, for example, trimethylolpropane di (meth) acrylate, ethylene oxide-modified trimethylolpropane di (meth) acrylate, and epoxy resin. Propane-modified trimethylolpropane di (meth) acrylate, glycerol di (meth) acrylate, bis (2- (meth) acryloxyethyl) hydroxyethyl isocyanurate, new Pentaerythritol tri (meth) acrylate, bistrimethylolpropane tri (meth) acrylate, dineopentaerythritol penta (meth) acrylate, and the like. These (meth) acrylates (a2) may be used alone or in combination of two or more kinds with respect to one of the aforementioned aliphatic polyisocyanates (a1). Among the (meth) acrylates (a2), neopentyl tetraol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate can further improve the active energy ray hardening of the present invention. The pencil hardness and scratch resistance of the hardened coating film surface of the type composition are preferred.

The reaction between the aliphatic polyisocyanate (a1) and the (meth) acrylate (a2) can be carried out by a conventional amine esterification reaction. In addition, in order to promote the progress of the amine esterification reaction, the amine esterification reaction is preferably performed in the presence of an amine esterification catalyst. Examples of the amine esterification catalyst include, for example, amine compounds such as pyridine, pyrrole, triethylamine, diethylamine, and dibutylamine; phosphides such as triphenylphosphine and triethylphosphine; dibutyltin dilaurate; Organic tin compounds such as octyltin laurate, octyltin diacetate, dibutyltin diacetate, tin octoate, and organic zinc compounds such as zinc octoate.

The said amine ester (meth) acrylate (A1) obtained by the said amine esterification reaction may use 1 type, and may use 2 or more types together. When two or more kinds are used, an amine acrylate obtained by using hexamethylene diisocyanate as the aliphatic polyisocyanate (a1) and a terpolymer using hexamethylene diisocyanate as the aliphatic polyisocyanate The combined use of the amine ester acrylate obtained from the isocyanate (a1) can further improve the pencil hardness and scratch resistance of the hardened coating film surface of the active energy ray-curable composition of the present invention, so it is preferred.

The polyfunctional (meth) acrylate (A2) is a compound having three or more (meth) acrylfluorenyl 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, bistrimethylolpropane tri (meth) acrylate, bistrimethylolpropane tetra (meth) acrylate, ginseng (2 -(Meth) acryloxyethyl) isocyanurate, neopentaerythritol tri (meth) acrylate, neopentaerythritol tetra (meth) acrylate, dinepentaerythritol tri (methyl) Group) 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. Among these polyfunctional (meth) acrylates (A2), from the viewpoint of improving pencil hardness and scratch resistance of the hardened coating film surface of the active-energy-ray-curable composition of the present invention, ( Meth) acrylfluorene equivalent is preferably in the range of 50 to 200 g / eq., More preferably in the range of 70 to 150 g / eq., And more preferably in the range of 80 to 120 g / eq. Specific examples of the polyfunctional (meth) acrylate (A2) having a (meth) acrylfluorenyl equivalent in the range of 80 to 200 g / eq. Include neopentyltetraol tetraacrylate (acrylfluorenyl equivalent: 88g / eq.), dinepentaerythritol hexaacrylate (acrylfluorene equivalent: 118 g / eq.), and the like.

The mass ratio [(A1) / (A2)] of the amine ester (meth) acrylate (A1) to the polyfunctional (meth) acrylate (A2) is 90 / from the viewpoint of improving the abrasion resistance. A range of 10 to 10/90 is suitable, a range of 80/20 to 20/80 is more preferable, and a range of 75/25 to 25/75 is more preferable.

In addition, in the active energy ray-curable composition of the present invention, in addition to the amine ester (meth) acrylate (A1) and the multifunctional (meth) acrylate (A2), the composition of the present invention can be used without impairing the present invention. Range of effects Blends mono (meth) acrylate with one (meth) acrylfluorene group in one molecule, di (meth) acrylate with two (meth) acrylfluorene groups in one molecule, etc. (Meth) acrylate. When other (meth) acrylates are blended in the active energy ray-curable composition of the present invention, the blending amount is relative to the aforementioned amine ester (meth) acrylate (A1) and the aforementioned multifunctional (methyl) The total of 100 parts by mass of the acrylate (A2) is preferably 40 parts by mass or less, and more preferably 20 parts by mass or less.

The fluorine compound (B) has a cyclic polysiloxane structure with a divalent linking group bonded to both ends of the poly (perfluoroalkylene ether) chain and a (meth) acrylfluorenyl group through the divalent linking group. A compound having a structure bonded to the aforementioned cyclopolysiloxane structure. In the present invention, "poly (perfluoroalkylene ether)" is sometimes referred to as "perfluoropolyether".

Examples of the poly (perfluoroalkylene ether) chain possessed by the fluorine compound (B) include a structure in which a divalent fluorocarbon group having 1 to 3 carbon atoms and an oxygen atom are alternately connected. The bivalent fluorinated carbon group having 1 to 3 carbon atoms may be one type or a combination of two or more types. Specifically, examples of the fluorinated carbon group include the following structural formula (1).

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

Among the aforementioned poly (perfluoroalkylene ether) chains, 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 perfluoro represented by the aforementioned formula (1-1) is combined. A poly (perfluoroalkylene ether) chain formed by a methylene group and a perfluoroethylene group represented by the aforementioned formula (1-2) is preferred. Here, the molar ratio of the perfluoromethylene group represented by the aforementioned formula (1-1) to the perfluoroethylene group represented by the aforementioned formula (1-2) [(1-1) / (1-2)] , Should be in the range of 1/10 ~ 10/1. The value of n in the aforementioned general formula (1) is preferably in the range of 2 to 200, preferably in the range of 10 to 100, and more preferably in the range of 20 to 80.

Examples of the cyclic polysiloxane structure that the fluorine compound (B) has include a structure represented by the following general formula (2).

(In the above general 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 1 having a (meth) acrylfluorenyl group. Valence organic group. M is an integer of 2 to 5.)

Among the aforementioned cyclopolysiloxane structures, a cyclotetrasiloxane structure in which m in the general formula (2) is 3 is preferred.

The divalent linking group that bonds the aforementioned poly (perfluoroalkylene ether) chain to the cyclic polysiloxane structure is not particularly limited as long as it is a divalent organic group. For example, the following formula (3) .

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

The divalent linking group that bonds the cyclopolysiloxane structure and the (meth) acrylfluorenyl group is not particularly limited as long as it is a divalent organic group, and examples thereof include those represented by the following general formula (4).

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

Examples of the method for producing the fluorine compound (B) include a method produced through the following steps (1) to (3). (1) In the presence of a platinum-based catalyst, a compound having an allyl group at both ends of a poly (perfluoroalkylene ether) chain is reacted with a cyclic polysiloxane compound having a hydrosilyl group to obtain a poly ( A step of a compound having a cyclic polysiloxane structure at both ends of a perfluoroalkylene ether) chain. (2) A step of reacting the compound obtained in (1) with allyloxyalkanol in the presence of a platinum-based catalyst, and adding a hydroxyl group to the cyclopolysiloxane structure site of the compound obtained in (1). (3) A step of introducing a (meth) acrylfluorenyl group by reacting a (meth) acrylic acid ester having an isocyanate group with a hydroxyl group added in (2).

The active energy ray-curable composition of the present invention has a higher pencil hardness on the surface of the hardened coating film of the active energy ray-curable composition of the present invention, and can further improve scratch resistance, stain resistance, and sliding properties. The blending amount of the fluorine compound (B) in the content is relative to the aforementioned amine ester (meth) acrylate (A1), the aforementioned multifunctional (meth) acrylate (A2), and other blended (meth) The total amount of acrylate is 100 parts by mass, preferably in the range of 0.05 to 5 parts by mass, and more preferably in the range of 0.1 to 2 parts by mass.

The reactive silicon dioxide (C1) is obtained by introducing a reactive group such as a (meth) acrylfluorenyl group on the surface of the silica particles by surface modification. In addition, from the viewpoint of further improving the transparency of the hardened coating film and the surface pencil hardness of the active energy ray-curable composition of the present invention, it is preferable that the reactive silica (C1) has a nanometer size, and colloidal Silicon dioxide is preferred. The specific average particle diameter is preferably in a range of 5 to 200 nm, and more preferably in a range of 5 to 100 nm.

The non-reactive silicon dioxide (C2) is one having no reactive group on the surface of the silicon dioxide particle, but may be obtained by modifying the surface of a non-reactive organic group. In addition, from the viewpoint that the transparency of the hardened coating film of the active energy ray-curable composition of the present invention and the surface pencil hardness can be further improved, and the curl resistance is further improved, the non-reactive silicon dioxide (C2) is Nanometer size is preferred, colloidal silica is preferred. The specific average particle diameter is preferably in a range of 5 to 200 nm, and more preferably in a range of 5 to 100 nm.

The use ratio [(C1) / (C 2)] of the reactive silicon dioxide (C1) and the non-reactive silicon dioxide (C2) can improve the hardening of the active energy ray-curable composition of the present invention. From the viewpoint of pencil hardness on the surface of the coating film, a range of 0.5 to 1.5 is preferable, and a range of 0.6 to 1 is preferable.

The aforementioned reaction in the active energy ray-curable composition of the present invention is from the viewpoint of further improving the pencil hardness, scratch resistance, stain resistance, and sliding properties of the hardened coating film surface of the active energy ray-curable composition of the present invention. The total blending amount of the non-reactive silica (C1) and the non-reactive silica (C2) is relative to the amine ester (meth) acrylate (A1) and the polyfunctional (meth) acrylate (A2). ) And other blended (meth) acrylic acid esters in a total amount of 100 parts by mass, preferably in a range of 100 to 300 parts by mass, and more preferably in a range of 150 to 280 parts by mass.

In addition, the active energy ray-curable composition of the present invention can form a hardened coating film by applying the active energy ray to the substrate and then irradiating the active energy ray. This active energy ray refers to ionizing radiation such as ultraviolet rays, electron beams, alpha rays, beta rays, and gamma rays. When a hardened coating film is formed by irradiating ultraviolet rays as active energy rays, it is suitable to add a photopolymerization initiator (D) to the active energy ray-curable composition of the present invention to improve the hardenability. If necessary, a photosensitizer may be further added to improve the hardenability. On the other hand, when ionizing radiation such as electron beam, α-ray, β-ray, or γ-ray is used, even if no photopolymerization initiator (D) or photosensitizer is used, it will harden quickly, so there is no need to add photopolymerization. Initiator (D) or photosensitizer.

Examples of the photopolymerization initiator (D) include intramolecular split photopolymerization initiators and dehydrogenation photopolymerization initiators. Intramolecular split-type photopolymerization initiators, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, oligo [2-hydroxy-2-methyl Phenyl-1- [4- (1-methylvinyl) phenyl] acetone], Dimethyl acetal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy 2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-2- Phenolin (4-thiomethylphenyl) propane-1-one, 2- Propyl-2-dimethylamino-1- (4- Acetophenone compounds such as chlorophenyl) -butanone; benzoin such as benzoin, benzoin methyl ether, benzoin isopropyl ether; 2,4,6-trimethylbenzoin diphenyl Phosphonium oxide, bis (2,4,6-trimethylbenzylidene) -phenylphosphine oxide, and other fluorenyl phosphine oxide-based compounds; benzil, methylphenylglyoxylate Wait.

On the other hand, examples of the dehydrogenation type photopolymerization initiator include, for example, benzophenone, o-benzoylbenzoic acid methyl-4-phenylbenzophenone, 4,4'-dichlorobenzophenone, Hydroxybenzophenone, 4-benzylidene-4'-methyl-diphenylsulfide, acrylated benzophenone, 3,3 ', 4,4'-tetrakis (tert-butylperoxycarbonyl) ) Benzophenone compounds such as benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone; 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone and other thioxanthone-based compounds; Michler's ketone (Michler's Ketone), 4,4'-diethylaminobenzophenone and other amino benzophenone-based compounds; 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10- Phenanthrenequinone, camphorquinone, 1- [4- (4-benzylidenephenylsulfanyl) phenyl] -2-methyl-2- (4-methylphenylsulfonyl) propane-1- Ketones, etc. These photopolymerization initiators (D) may be used alone or in combination of two or more kinds.

Examples of the photosensitizer include tertiary amine compounds such as diethanolamine, N-methyldiethanolamine, and tributylamine; urea compounds such as o-tolylthiourea; sodium diethyldithiophosphate; and s - Sulfur compounds such as p-toluenesulfonate and the like.

The amount of the photopolymerization initiator and photosensitizer is preferably 0.05 to 20 parts by mass, and more preferably 0.5 to 20 parts by mass of the non-volatile component in the active energy ray-curable composition of the present invention. ~ 15% by mass.

In addition, in the active energy ray-curable composition of the present invention, in addition to the above-mentioned components (A) to (D), it may be blended as necessary: a polymerization inhibitor, a surface modifier, an antistatic agent, an antifoaming agent, and a viscosity Additives such as regulators, light-resistant stabilizers, weather-resistant stabilizers, heat-resistant stabilizers, ultraviolet absorbers, antioxidants, levelling agents, organic pigments, inorganic pigments, pigment dispersants, silica beads, organic beads, etc .; silica, oxidation Inorganic fillers such as aluminum, titanium oxide, zirconia, and antimony pentoxide. These other blends may be used alone or in combination of two or more kinds.

The method for coating the active energy ray-curable composition of the present invention on a substrate depends on the application, and examples thereof include die coating, micro gravure coating, gravure coating, roll coating, and comma coating. , Air knife coating, anastomotic coating, spray coating, dip coating, spin coating, wheel coating, brush coating, solid coating by a silk screen, wire bar coating , Curtain coating, etc.

The active energy rays which harden the active energy ray-curable composition of the present invention are ionizing radiations such as ultraviolet rays, electron beams, α rays, β rays, and γ rays, as described above, and a specific device for irradiating active energy rays, if For the use of ultraviolet rays, examples include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, electrodeless lamps, chemical lamps, black light lamps, mercury-xenon lamps, short-arc lamps, helium-cadmium lasers, and argon lasers. , Sunlight, LED, etc. as the source of ultraviolet radiation. When the substrate coated with the active energy ray-curable composition of the present invention is a film substrate, it is preferable to use a xenon-flash lamp that is irradiated in a flash manner because it can 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 the electron beam.

In addition, when the active energy ray-curable composition of the present invention is irradiated with ultraviolet rays to form a hardened coating film, it can be performed in an air environment. From the viewpoint of sliding hardened coating film, it is preferable to perform it in an environment with an oxygen concentration of 5,000 ppm or less.

Since the hardened coating film of the active energy ray-curable composition of the present invention has excellent antifouling properties, and also has excellent scratch resistance and sliding properties, the active energy ray-curable composition of the present invention can be applied to various The surface of the article is hardened to give the surface of various articles a high pencil hardness, and excellent stain resistance, scratch resistance, and sliding properties. Therefore, the active energy ray-curable composition of the present invention is very useful as a hard coating agent capable of imparting high scratch resistance, stain resistance, and the like to the surface of various articles.

Examples of the items to which the active energy ray-curable composition of the present invention can be applied include: housings of household appliances such as televisions, refrigerators, washing machines, and air conditioners; housings of electronic devices such as computers, smartphones, mobile phones, digital cameras, and game consoles Interior materials of various vehicles such as automobiles and railway vehicles; various building materials such as decorative boards; woodworking materials such as furniture, artificial and synthetic leather; FRP baths; triethyl cellulose (TAC) film and other liquid crystal displays (LCD) Optical films; cymbals or diffusers for backlight components of LCDs; various display screens (hard coatings, anti-reflective layers) such as plasma displays (PDP), organic EL displays; touch panels; mobile phones, smartphones and other electronics Terminal screens; color filters for liquid crystal displays (hereinafter referred to as "CF"); transparent protective films; optical recording media such as CDs, DVDs, and Blu-ray discs; transfer films for insert molds (IMD, IMF); photocopiers, Rubber rollers for OA equipment such as printers; glass surfaces of the reading section of OA equipment such as photocopiers and scanners; optical lenses for cameras, camcorders, glasses, etc .; windproof and glass surfaces for watches such as watches Windows of various vehicles such as automobiles and railway vehicles; cover glass or membranes for solar cells; various building materials such as decorative panels; window glass for houses; woodworking materials such as furniture.

The hard-coated film of the present invention has a hard-coated layer formed on at least one side of a film substrate and hardened of the active energy ray-curable composition of the present invention. 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, Cellulose, Diacetyl cellulose, Triethyl cellulose, Acetyl cellulose butyrate, Cellulose acetate propionate, Cyclic olefin polymer, Cyclic olefin copolymer, Polyvinyl chloride , Polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polymethylpentene, polyfluorene, polyetheretherketone, polyetherfluorene, polyetherfluorine , Polyimide, fluororesin, nylon, acrylic resin and other resin films. In particular, resin films of polyethylene terephthalate, triethylcellulose, and acrylic resins are excellent in transparency and processability, and thus can be preferably used.

The film substrate may be a substrate composed of only the resin film exemplified above, but in order to improve the adhesion with the active energy ray-curable composition of the present invention, a primer coating may be provided on the resin film. Layered film substrate. Examples of the primer coating layer include polyester resins, polyurethane resins, and acrylic resins. In addition, for the purpose of improving the adhesiveness with the hard coating layer, surface embossing treatment, corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, ozone, etc., can be performed by a sandblasting method, a solvent treatment method, or the like. The surface of the resin film is subjected to an ultraviolet irradiation treatment, an oxidation treatment, or the like.

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, and more preferably in the range of 90 to 130 μm. In the present invention, by setting the thickness of the film base material within this range, curl is easily suppressed even when a hard coating layer is provided on one side of the film base material.

Furthermore, it is preferable to use a film substrate having a modulus of elasticity in a range of 3 to 7 GPa, and particularly a film substrate in a range of 3 to 5 GPa. If the elastic coefficient is within this range, deformation of the film base material is unlikely to occur during formation of the protective film, cracking of the hard coating layer can be suppressed, and reduction in hardness of the surface of the hard coating film can be easily suppressed. In addition, since the flexibility of the film substrate can be ensured, it is easy to follow a gentle curved surface when a protective film is attached as described later.

The protective film of the present invention is one having an adhesive layer on one side of the hard coating film. The said adhesive layer can be provided by sticking an adhesive tape to the said film base material, or applying an adhesive layer directly on the surface of the said film base material which is opposite to a hard coating surface.

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

As the adhesive used in the adhesive layer of the present invention, known adhesive resins such as acrylic, rubber, and silicone can be used. Among them, an acrylic copolymer formed by using a (meth) acrylic acid ester monomer having an alkyl group having 2 to 14 carbon atoms as a main component and polymerizing it as a repeating unit, from the adhesion with the film substrate, The viewpoint of transparency and weather resistance is preferable.

Examples of the (meth) acrylate monomer having 2 to 14 carbon atoms include, for example, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, secondary butyl acrylate, and tertiary butyl acrylate. Esters, n-hexyl acrylate, cyclohexyl acrylate, n-octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, isononyl acrylate, isodecyl acrylate, lauryl acrylate, methyl methacrylate, formic acid Ethyl acrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, secondary butyl methacrylate, tertiary butyl methacrylate, n-hexyl methacrylate, methyl Cyclohexyl acrylate, n-octyl methacrylate, isooctyl methacrylate, 2-ethylhexyl methacrylate, isononyl methacrylate, isodecyl methacrylate, lauryl methacrylate, and the like.

Among the (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 more preferred. Ester is better. Among the alkyl acrylates, n-butyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, isononyl acrylate, and ethyl acrylate are particularly preferred. By using an alkyl (meth) acrylate having an alkyl group having a carbon number in this range, it is possible to easily secure an ideal adhesive force.

The content of the (meth) acrylic acid ester having 2 to 14 carbon atoms in the monomer constituting the acrylic copolymer used in the adhesive layer of the present invention is preferably 90 to 99% by mass, and more preferably 90 ~ 96% by mass. By setting the content of the aforementioned (meth) acrylic acid ester within this range, it is possible to easily secure an ideal adhesive force.

For the acrylic copolymer, it is preferable to further use a (meth) acrylic acid ester monomer having a polar group such as a hydroxyl group, a carboxyl group, and an amino group, or another polar monomer having a vinyl group as a monomer component.

Examples of the (meth) acrylate monomer having a hydroxyl group include, for example, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 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.

Examples of the (meth) acrylate monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, maleic acid, crotonic acid, a dimer of acrylic acid or methacrylic acid, and ethylene oxide modification. Succinate acrylate and the like. Among these, it is preferable to use acrylic acid.

Examples of the (meth) acrylate monomer having amidino group include, for example, N-vinyl-2-pyrrolidone, N-vinylcaprolactam, and acrylfluorenyl Phenol, acrylamide, N, N-dimethylacrylamide, N-acrylacetoxyethyl-3,4,5,6-tetrahydrophthalimide and the like. Among these, N-vinyl-2-pyrrolidone, N-vinyl caprolactam, and acrylfluorenyl are used. Porphyrin is preferred.

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

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

The weight average molecular weight Mw of the acrylic copolymer used in the adhesive layer is preferably 400,000 to 1.4 million, and more preferably 600,000 to 1.2 million. If the weight average molecular weight Mw of the acrylic copolymer is within this range, it is easy to adjust the adhesive force to a specific range.

The weight average molecular weight Mw can be measured by gel permeation chromatography (GPC). More specifically, it can be obtained by measuring "SC8020" manufactured by Tosoh Corporation as a GPC measurement device and measuring the polystyrene conversion value under the following GPC measurement conditions. (GPC measurement conditions) ‧ Sample concentration: 0.5% by weight (tetrahydrofuran solution) ‧ Sample injection volume: 100 μL ‧ Eluent: Tetrahydrofuran (THF) ‧ Flow rate: 1.0mL / min ‧ Column temperature (measurement temperature): 40 ° C ‧ Column: "TSKgel GMHHR-H" manufactured by Tosoh Corporation ‧ Detector: Differential refractometer

In order to further improve the cohesive force of the adhesive layer, it is suitable to add a crosslinking agent to the adhesive. Examples of the crosslinking agent include isocyanate-based crosslinking agents, epoxy-based crosslinking agents, and chelate-based crosslinking agents. The addition amount of the cross-linking agent is preferably adjusted so that the gel fraction of the adhesive layer becomes 25 to 80% by mass, more preferably it is adjusted so as to become 40 to 75% by mass, and the best is to become 50 to 70% by mass adjustment. By adjusting the gel fraction within this range, it is possible to suppress a decrease in the pencil hardness of the surface when the protective film is attached to the substrate, and it is also possible to make the adhesiveness sufficient. In addition, the gel fraction of the present invention is obtained by immersing the hardened adhesive layer in toluene, and measuring the dry mass of the remaining insoluble components after standing for 24 hours, and expressing it as a percentage relative to the original mass.

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

Moreover, well-known and conventional additives other than the above may be added to an adhesive. For example, in order to improve the adhesion to a glass substrate, a silane coupling agent is preferably added in a range of 0.001 to 0.005 parts by mass relative to 100 parts by mass of the adhesive. Moreover, plasticizers, softeners, fillers, pigments, flame retardants, etc. may be added as other additives as needed.

Since the protective film of the present invention has ideal abrasion resistance and sliding properties, it can be applied to various applications. Among them, it can be ideally applied to an image display portion of an image display device such as a liquid crystal display (LCD) or an organic EL display. In particular, it is possible to realize ideal scratch resistance and sliding properties even in a thin type. Therefore, it is highly required to be miniaturized and thin as electronic notebooks, mobile phones, smartphones, portable sound players, portable computers, and tablet terminals. The protective film of the image display portion of the image display device of the mobile electronic terminal is ideal. For such an image display device, for example, it has an image display module such as an LCD module and an organic EL module in its structure, and a transparent panel for protecting the image display module is provided on the upper part of the image display module. The image display device constituted by applying the protective film of the present invention to the surface or the inner surface of the transparent panel is effective for preventing abrasion or scattering when the transparent panel is damaged. [Example]

Hereinafter, the present invention will be described more specifically by way of examples.

(Synthesis example 1: Synthesis of amine ester acrylate (A1-1)) To a flask equipped with a stirrer, a gas introduction pipe, a cooling pipe, and a thermometer, neopentyltetraol triacrylate (hereinafter referred to as "PE3A") was added. And neopentaerythritol tetraacrylate (hereinafter referred to as "PE4A") (54.91 parts by mass of PE3A / PE4A = 60/40 (mass ratio)), 0.1 parts by mass of dibutyltin diacetate, 0.6 of dibutylhydroxytoluene Parts by mass, 0.1 parts by mass of p-methoxyphenol, and 160 parts by mass of butyl acetate. While blowing in air and mixing uniformly, the temperature was gradually raised. When it reached 60 ° C, 90.9 parts by mass of hexamethylene diisocyanate was added, and then reacted at 80 ° C for 5 hours to obtain a nonvolatile component containing an amine ester acrylate (A1-1) having 6 acrylamido groups in one molecule. 80% by mass solution. In addition, this solution contains 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. 1. 0.5 parts by mass of p-methoxyphenol and 0.5 parts by mass of dibutyltin diacetate. After heating to 70 ° C while blowing air, the mixture of PE3A and PE4A (PE3A / PE4A = 75/25 (mass ratio) )) 795 parts by mass. After the dropwise addition was completed, the reaction was carried out at 70 ° C for 3 hours, and the reaction was continued until the infrared absorption spectrum of 2250 cm ^-1 showing isocyanate groups disappeared, and an amine ester acrylate (A1- 2) A solution having a non-volatile content of 80% by mass. This solution contains 19.4% 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)) In a flask equipped with a stirrer, a gas introduction tube, a cooling tube, and a thermometer, a mixture of PE3A and PE4A (PE3A / PE4A = 60/40 (mass ratio) )) 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. After heating to 75 ° C while blowing in air, it took 2 hours to dropwise add hexamethylene dichloride. Terpolymer of isocyanate (isocyanurate body) ("DESMODUR N3390BA" manufactured by Sumitomo Bayer Polyurethane Co., Ltd., non-volatile content 90% by mass, NCO%: 19.6, NCO equivalent: 214g / eq.) 107 mass And 50 parts by mass of methyl ethyl ketone. After the dropwise addition was completed, the reaction was carried out at 75 ° C for 4 hours, and the reaction was continued until the infrared absorption spectrum of 2250 cm ^-1 showing an isocyanate group disappeared to obtain an amine ester acrylate (A1- 3) A solution having a non-volatile content of 67.8% by mass. In addition, this solution contained 28.6% by mass of PE4A in addition to the amine ester acrylate (A1-3) in the nonvolatile matter.

(Synthesis Example 4: Synthesis of fluorine compound (B-1)) In a flask equipped with a stirrer and a cooling tube, a perfluoropolyether having allyl groups at both ends represented by the following formula (5) was added under a dry nitrogen atmosphere. 500 parts by mass, 700 parts by mass of hexafluorom-xylene, and 361 parts by mass of tetramethylcyclotetrasiloxane, and the temperature was raised to 90 ° C while stirring. Here, 0.442 parts by mass of a toluene solution of a chloroplatinic acid / vinylsiloxane complex (containing 1.1 × 10 ⁻⁶ mol of Pt elementary substance) 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 materials by ¹ H-NMR spectrum, the solvent and excess tetramethylcyclotetrasiloxane were distilled off under reduced pressure, and activated carbon treatment was performed to obtain a colorless formula represented by the following formula (6): Perfluoropolyether compound (1) as a transparent liquid.

(In the formula, m / n is 0.9, and the total of m and n is 45 on average.)

In a dry air environment, 50 parts by mass of the perfluoropolyether compound (1) obtained above, 7.05 parts by mass of 2-allyloxyethanol, 50 parts by mass of hexafluorom-xylene, and chloroplatinic acid / vinylsiloxane 0.0442 parts by mass of a toluene solution of an alkane complex (containing Pt simple substance 1.1 × 10 ^-7 moles) 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 activated carbon treatment was performed to obtain the following formula (7). Perfluoropolyether compound (2) as a yellow transparent liquid.

In a dry air environment, 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 and heated to 50 ° C. Next, 0.05 mass part of dioctyltin laurate was added, and it stirred at 50 degreeC for 24 hours. After the heating was completed, the pressure-reduced distillation was performed 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. A mixed solvent of methyl ethyl ketone and methyl isobutyl ketone (methyl ethyl ketone / methyl isobutyl ketone = 1/3 (mass ratio)) was added to the fluorine compound (B-1) 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 as described above, an active energy ray-curable composition was prepared as follows.

(Example 1) 62 parts by mass of the amine ester acrylate (A1-1) -containing solution (containing 32.6 parts by mass of the amine ester acrylate (A1-1) and 17 parts by mass of PE4A) obtained in Synthesis Example 1 was used in 18.3 parts by mass of a solution containing an urethane acrylate (A1-3) obtained in Synthesis Example 3 (containing 8.9 parts by mass of an urethane acrylate (A1-3) and 3.5 parts by mass of PE4A), a mixture of PE4A and PE3A (PE4A / PE3A = 60/40 (mass ratio)) 38 parts by mass, 7.5 parts by mass of a 20% by mass solution 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 silicon dioxide ("MEK-AC-2140Z" manufactured by Nissan Chemical Industries, Ltd.), a methyl ethyl ketone dispersion with a non-volatile content of 40% by mass; hereinafter referred to as "reactive silicon dioxide (C1-1)". ) 287.5 parts by mass (115 parts by mass of reactive silica (C1-1)), non-reactive colloidal silica ("MEK-ST40" manufactured by Nissan Chemical Industries, Ltd., and 40 mass% of nonvolatile matter Methyl ethyl ketone dispersion; hereinafter referred to as "non-reactive silica (C2-1)".) 312.5 parts by mass (125 parts by mass of non-reactive silica (C2-1)), photopolymerization initiator (BASF JAPAN (shares) "Irgacure184" made by the company, 1-hydroxycyclohexylphenyl ketone; hereinafter referred to as "photopolymerization initiator (D-1)".) 10.9 parts by mass and photopolymerization initiator (manufactured by BASF Japan Co., Ltd. " Irgacure754 ", a mixture of 2- [2- pendantoxy-2-phenylethoxyethoxy] ethyl hydroxyphenylacetate and 2- (2-hydroxyethoxy) ethyl hydroxyphenylacetate; Hereinafter referred to as "photopolymerization initiator (D-2).") After 1.6 parts by mass of uniformly stirring, it was diluted with methyl ethyl ketone to prepare an active energy ray-curable composition (1) having a nonvolatile content of 40% by mass.

[Evaluation of Coating Appearance] In order to determine whether the active energy ray-curable composition (1) obtained above can be used as a coating agent, the external appearance was visually observed, and the external appearance of the coating agent was evaluated according to the following criteria. ○: No cloudiness and component separation. ×: Cloudiness or component separation.

[Production of test film] The active energy ray-curable composition (1) obtained above was applied to a polyethylene terephthalate film ("COSMOSHINE" manufactured by Toyobo Co., Ltd.) using a wire rod (# 40). "A4100", 100 μm thick), and dried at 60 ° C for 1 minute, then use an ultraviolet irradiation device ("MIDN-042-C1" manufactured by Eye Graphics Co., Ltd.) 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 rays at an irradiation light amount of 0.5 J / cm ² to obtain a test piece film having a hardened coating film (hard coating layer) having a thickness of 15 μm.

[Evaluation of the appearance of the cured 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 are uneven coating, coating lines, or particles.

With respect to the test piece film obtained above, the following evaluations or measurements of curl, pencil hardness, abrasion resistance, water contact angle, stain resistance, and sliding properties were performed.

[Evaluation of curl resistance] The obtained evaluation film was cut into 10 cm squares, and after standing at 23 ° C and 50% RH for one night, the four corners of the curl were measured for the float from the bottom surface, and the resistance was evaluated according to the following criteria. Curly. ：: The average of the four corners is less than 10 mm. (Circle): The average value of the four corners is 10 mm or more and less than 25 mm. ×: The average of the four corners is 25 mm or more.

[Measurement of Pencil Hardness] With respect to the hardened coating film surface of the evaluation film obtained as described above, a pencil specified in JIS S 6006: 2007 was used, and the hardest pencil that did not generate a flaw was measured in accordance with JIS K 5600-5-4: 1999. The hardness is taken as the pencil hardness.

[Evaluation of Scratch Resistance] The test piece film obtained above was cut into a rectangle of 30 cm × 2 cm and fixed to a flat friction tester (manufactured by Toyo Seiki Co., Ltd.) with a jig. The scratch state of the test piece after 200 times of reciprocating repetition at a load of 1 kg / cm ² , a stroke of 10 cm, and a speed of 20 cm / sec was observed visually, and the scratch resistance was evaluated according to the following criteria. ：: No abrasion. ○: There are abrasions less than 5 pieces. △: There are 5 or more scratches, but there are no scratches on the entire surface of the test film. ×: The entire test film was scratched.

[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 on the surface side and fixed to the glass plate with double-sided tape. ) The company's automatic contact angle meter "DROMPAMSTER500" measures the contact angle of 4 to 4.5 μL of purified water.

[Evaluation of antifouling property] On the hardened coating film of the test piece film obtained above, the printing ink was coated into a circle with "uni Mediax (black)" made by Mitsubishi Pencil Co., Ltd., and the degree of repellency of the printing ink was visually observed. . From this observation result, the antifouling property was evaluated according to the following criteria. 5: The ink is repelled into dots. 4: The ink is repelled into dots and lines. 3: The ink is repelled into a line. 2: Ink is slightly repelled. 1: Do not repel 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 with BEMCOT (manufactured by Asahi Kasei Fibers Co., Ltd.), the slidability was evaluated according to the following criteria. ：: Good sliding. ○: It slides. △: It is difficult to slide. ×: Does not slide.

(Example 2) A 20 mass% solution of the fluorine-containing compound (B-1) used in Example 1 was set to 5 parts by mass (the fluorine compound (B-1) was 1 part by mass). In Example 1, an active energy ray-curable composition (2) having a nonvolatile content of 40% by mass was prepared in the same manner. Using the obtained active-energy-ray-curable composition (2), evaluation or measurement was performed after the test piece film was produced in the same manner as in Example 1.

(Example 3) Instead of using the mixture of PE4A and PE3A (PE4A / PE3A = 60/40 (mass ratio)) used in Example 1, the amine-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 acrylate (A1-2), 3.7 parts by mass of PE4A), and 19 parts by mass of a mixture of DPHA and DPPA (DPHA / DPPA = 60/40 (mass ratio)), Aside from this, 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. The obtained active energy ray-curable composition (3) was used in the same manner as in Example 1, and evaluation or measurement was performed after the test film was produced.

(Example 4) The blending amount of the methyl ethyl ketone dispersion of 40% by mass of the non-volatile content of the reactive silica (C1-1) used in Example 1 was changed from 287.5 parts by mass to 187.5 parts by mass (Reactive II Except that silicon oxide (C1-1) was 75 parts by mass), 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. Using the obtained active energy ray-curable composition (4), evaluation and measurement were performed after the test piece film was produced in the same manner as in Example 1.

(Comparative Example 1) Except that the reactive silica (C1-1) and non-reactive silica (C2-1) used in Example 1 were not blended, they were prepared in the same manner as in Example 1. An active energy ray-curable composition (R1) with a volatile content of 40% by mass. Using the obtained active energy ray-curable composition (R1), as in Example 1, evaluation or measurement was performed after a test film was produced.

(Comparative Example 2) Instead of using a 20% by mass solution of the fluorinated compound (B-1) used in Example 1, a fluorinated compound having a propenyl group at a single end of a poly (perfluoroalkylene ether) chain was used. ("OPTOOL DAC-HP" manufactured by Daikin Industries Co., Ltd., 20 parts by mass of non-volatile content; hereinafter referred to as "fluorine compound (RB-1).") 7.5 parts by mass (fluoro compound (RB-1) is 1.5 mass Except for this, 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. Using the obtained active energy ray-curable composition (R2), as in Example 1, evaluation or measurement was performed after a test piece film was produced.

(Comparative Example 3) The amount of the methyl ethyl ketone dispersion of 40% by mass of the nonvolatile matter of the reactive silica (C1-1) used in Example 1 was changed from 287.5 parts by mass to 500 parts by mass (reactive second Silicon oxide (C1-1) was 200 parts by mass), and non-reactive silicon dioxide (C2-1) was not blended. An active energy of 40% by mass of the nonvolatile matter was prepared in the same manner as in Example 1. Radiocurable composition (R3). Using the obtained active energy ray-curable composition (R3), evaluation and measurement were performed after the test piece film was produced 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 component of the non-reactive silica (C2-1) used in Example 1 was changed from 312.5 parts by mass to 500 parts by mass (non-reactive The active silicon dioxide (C2-1 was 200 parts by mass), and the reactive silicon dioxide (C1-1) was not blended, and an activity of 40% by mass of the nonvolatile matter was prepared in the same manner as in Example 1. Energy ray hardening composition (R4). Using the obtained active-energy-ray-curable composition (R4), evaluation and measurement were performed after the test piece film was produced in the same manner as in Example 1.

Table 1 shows the composition and evaluation results of the active energy ray-curable compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 4. In addition, all the compositions in Table 1 are described in terms of the amount of non-volatile components, and for the amine ester acrylates (A1-1) to (A1-3), the blending amount including PE4A is described.

From the evaluation results shown in Table 1, it was confirmed that Examples 1 to 4 of the active energy ray-curable composition of the present invention had no problem in appearance as a coating agent, and there was no problem in appearance of the cured coating film. In addition, it was also confirmed that the curl of the active energy ray-curable composition of the present invention after curing is small and has high curl resistance. Furthermore, it was confirmed that the surface of the hardened coating film of the active energy ray-curable composition of the present invention has high pencil hardness, and also has excellent scratch resistance, pencil hardness, stain resistance, and sliding properties.

On the other hand, Comparative Example 1 is an example of an active energy ray-curable composition that does not use both the reactive silica (C1) and non-reactive silica (C2) used in the present invention, and it can be confirmed that 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, scratch resistance, and sliding properties were insufficient.

Comparative Example 3 is an example of an active energy ray-curable composition that does not use the non-reactive silicon dioxide (C2) used in the present invention. It can be confirmed that the pencil hardness is insufficient, and the curl after curing is large, and the curl resistance Not enough.

Comparative Example 4 is an example of an active energy ray-curable composition that does not use the reactive silicon dioxide (C1) used in the present invention. It was confirmed that the pencil hardness and scratch resistance were insufficient.

no.

Claims (14)

An active energy ray-curable composition, comprising: an active energy ray-curable compound (A); a cyclopolysiloxane structure bonded to two ends of a poly (perfluoroalkylene ether) chain via a divalent linking group; In addition, the (meth) acrylfluorenyl group is a fluoro compound (B), a reactive silicon dioxide (C1), and a non-reactive dioxide that are bonded to the cyclopolysiloxane structure through a divalent linking group. Silicon (C2), the use ratio [(C1) / (C2)] of the reactive silicon dioxide (C1) to the non-reactive silicon dioxide (C2) is in the range of 0.5 to 1.5, and the reactive silicon dioxide The total blending amount of (C1) and the non-reactive silicon dioxide (C2) is in a range of 100 to 300 parts by mass relative to 100 parts by mass of the active energy ray-curable compound (A). For example, the active energy ray-curable composition according to item 1 of the application, wherein the active energy ray-curable compound (A) is an aliphatic polyisocyanate (a1) and a hydroxyl group-containing (meth) acrylate (a2). The amine ester (meth) acrylate (A1) having 4 or more (meth) acrylfluorenyl groups in one molecule obtained by the reaction, and the Functional (meth) acrylate (A2). For example, the active energy ray-curable composition according to item 2 of the application, wherein the aliphatic polyisocyanate (a1) is selected from the group consisting of hexamethylene diisocyanate, norbornane diisocyanate, and isophorone diisocyanate. One or more types of polyisocyanates in the group consisting of methylenebis (4-cyclohexyl isocyanate) and these three polymers. For example, the active energy ray-curable composition according to item 2 of the patent application, wherein the (meth) acrylate (a2) is selected from the group consisting of dipentaerythritol penta (meth) acrylate and neopentaerythritol. One or more types of (meth) acrylates in the group consisting of tri (meth) acrylates. For example, the active energy ray-curable composition according to item 2 of the patent application range, wherein the (meth) acrylfluorenyl equivalent of the polyfunctional (meth) acrylate (A2) is in a range of 50 to 200 g / eq. For example, the active energy ray-curable composition according to item 2 of the patent application, wherein the polyfunctional (meth) acrylate (A2) is selected from the group consisting of dipentaerythritol hexa (meth) acrylate, dixin One or more polyfunctional (meth) groups in the group consisting of pentaerythritol penta (meth) acrylate, neopentaerythritol tetra (meth) acrylate, and neopentaerythritol tri (meth) acrylate Acrylate. A hardened material is obtained by irradiating an active energy ray-curable composition as described in any one of claims 1 to 6 of the scope of patent application. A hardened product obtained by irradiating ultraviolet rays to an active energy ray-curable composition according to any one of claims 1 to 6 in a gas environment having an oxygen concentration of 5,000 ppm or less. An article having a hardened coating film of an active energy ray-curable composition according to any one of claims 1 to 6 of the scope of patent application. A hard coating film characterized by having a hard coating layer on at least one side of a film substrate, and the hard coating layer is hardened by an active energy ray hardening composition according to any one of claims 1 to 6物 组合。 Object composition. For example, the hard coating film of the scope of application for item 10, wherein the thickness of the hard coating layer is 1 to 20 μm, and the thickness of the film substrate is 50 to 200 μm. A protective film is characterized in that it has an adhesive layer on one side of the hard-coated film according to item 10 of the patent application scope. For example, the protection film according to item 12 of the application, wherein the thickness of the adhesive layer is 5-50 μm. For example, the protection film in the scope of patent application No. 12 is used to protect the image display part of the mobile electronic terminal.