JP5954505B2 - Active energy ray curable composition, cured product thereof and article having cured coating film thereof - Google Patents

Description

  The present invention provides an active energy ray-curable composition capable of imparting high pencil hardness to the surface of various articles, and further imparting excellent scratch resistance, antifouling property, and slipperiness, a cured product thereof, and a cured coating film thereof. It relates to an article having.

  The active energy ray-curable composition has a low heat history to the substrate to be applied, and is excellent in coating film hardness and scratch resistance. For example, it is soft and has a defect that the surface is easily damaged. It is used as a hard coat agent that imparts scratch resistance to the surface. In addition, 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 is proposed as a material to be added to the active energy ray curable composition. (For example, refer to Patent Document 1).

  However, although the cured coating film of the active energy ray-curable composition to which the fluorine compound described in Patent Document 1 is added has excellent antifouling properties, it has a problem of being inferior in scratch resistance, pencil hardness, and slipperiness. Accordingly, there has been a demand for an active energy ray-curable composition that can provide a cured coating film that has excellent antifouling properties and is excellent in scratch resistance, pencil hardness, and slipperiness.

Japanese Patent No. 3963169

  The problem to be solved by the present invention is an active energy ray-curable composition that has a high pencil hardness, and further provides a cured coating film having excellent scratch resistance, antifouling properties, and slipperiness, a cured product thereof, and It is to provide an article having the cured coating.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have made active energy ray curing in which a fluorine compound having a specific structure, reactive silica and non-reactive silica are added to the active energy ray curable compound. The surface of the cured coating film of the adhesive composition has high pencil hardness, and further has excellent scratch resistance, antifouling property, and slipperiness, and the present invention has been completed.

That is, in the present invention, a cyclopolysiloxane structure is bonded to both ends of the active energy ray-curable compound (A) and the poly (perfluoroalkylene ether) chain via a divalent linking group, and the cyclopolysiloxane structure is bonded to the cyclopolysiloxane structure. Active energy ray-curable composition containing a fluorine compound (B) having a structure in which a (meth) acryloyl group is bonded via a divalent linking group, reactive silica (C1), and non-reactive silica (C2) The use ratio [(C1) / (C2)] of the reactive silica (C1) and the non-reactive silica (C2) is in the range of 0.5 to 1.5. The present invention relates to an active energy ray-curable composition, a cured product thereof, and an article having the cured coating film. Furthermore, this invention relates to the protective film which provided the hard-coat film which used the hardened | cured material of the said active energy ray-curable composition as a hard-coat layer, and provided the adhesive layer in this hard-coat film.

  The active energy ray-curable composition of the present invention has a surface of various articles because the surface of the cured coating film has high pencil hardness and excellent scratch resistance, antifouling property, and slipperiness. It is extremely useful as a hard coat agent for protection.

In the active energy ray-curable composition of the present invention, a cyclopolysiloxane structure is bonded to both ends of the active energy ray-curable compound (A) and the poly (perfluoroalkylene ether) chain via a divalent linking group, Activity containing a fluorine compound (B) having a structure in which a (meth) acryloyl group is bonded to the cyclopolysiloxane structure via a divalent linking group, reactive silica (C1), and non-reactive silica (C2) It is an energy ray curable composition, Comprising: Use ratio [(C1) / (C2)] of the said reactive silica (C1) and the said non-reactive silica (C2) is the range of 0.5-1.5. It is what is.

  In the present invention, “(meth) acrylate” refers to one or both of acrylate and methacrylate, and “(meth) acryloyl group” refers to one or both of acryloyl group and methacryloyl group.

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

  As the urethane (meth) acrylate, (A1) is composed of four or more (meta) in one molecule obtained by reacting an aliphatic polyisocyanate (a1) with a (meth) acrylate (a2) having a hydroxyl group. ) It has an acryloyl group.

  The aliphatic polyisocyanate (a1) is a compound in which a portion excluding an isocyanate group is composed of an aliphatic hydrocarbon. 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), Alicyclic polyisocyanates (a1-2) such as 1,3-bis (isocyanatomethyl) cyclohexane, 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl-1,5-diisocyanatocyclohexane, etc. Is mentioned. Further, a trimerized product obtained by trimming the aliphatic polyisocyanate (a1-1) or the alicyclic polyisocyanate (a1-2) can also be used as the aliphatic polyisocyanate (a1). Among these aliphatic polyisocyanates (a1), hexamethylene diisocyanate, which is a diisocyanate of linear aliphatic hydrocarbons, norbornane diisocyanate, which is an alicyclic diisocyanate, and isophorone diisocyanate are those of the active energy ray-curable composition of the present invention. It is preferable because the pencil hardness and scratch resistance on the surface of the cured coating film can be further improved.

  The (meth) acrylate (a2) is a compound having a hydroxyl group and a (meth) acryloyl group, but the urethane (meth) acrylate (A1) has four or more (meth) acryloyl groups in one molecule. Therefore, it is preferable to have two or more (meth) acryloyl groups. As such (meth) acrylate (a2), for example, trimethylolpropane di (meth) acrylate, ethylene oxide modified trimethylolpropane di (meth) acrylate, propylene oxide modified trimethylolpropane di (meth) acrylate, glycerin di (Meth) acrylate, bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate and the like. . These (meth) acrylates (a2) can be used alone or in combination of two or more with respect to one of the aliphatic polyisocyanates (a1). Among these (meth) acrylates (a2), pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate are pencil hardnesses on the surface of the cured coating film of the active energy ray-curable composition of the present invention. And scratch resistance can be further improved.

  The reaction between the aliphatic polyisocyanate (a1) and the (meth) acrylate (a2) can be carried out by a conventional urethanization reaction. Moreover, in order to accelerate | stimulate progress of a urethanation reaction, it is preferable to perform a urethanation reaction in presence of a urethanization catalyst. Examples of the urethanization catalyst include amine compounds such as pyridine, pyrrole, triethylamine, diethylamine and dibutylamine; phosphorus compounds such as triphenylphosphine and triethylphosphine; dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dibutyltin Examples thereof include organic tin compounds such as diacetate and tin octylate, and organic zinc compounds such as zinc octylate.

  The said urethane (meth) acrylate (A1) obtained by said urethanation reaction can be used individually by 1 type, or can also be used together 2 or more types. Moreover, when using 2 or more types, the urethane acrylate obtained using hexamethylene diisocyanate as said aliphatic polyisocyanate (a1) and the trimer of hexamethylene diisocyanate as said aliphatic polyisocyanate (a1) are used. The combined use with the obtained urethane acrylate is preferable because the pencil hardness and scratch resistance of the cured coating film surface of the active energy ray-curable composition of the present invention can be further improved.

  The polyfunctional (meth) acrylate (A2) is a compound having three or more (meth) acryloyl groups in one molecule. Specific examples of the polyfunctional (meth) acrylate (A2) include trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, ditrile. Methylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol Tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaery Ritoruhekisa (meth) acrylate. These polyfunctional (meth) acrylates (A2) can be used alone or in combination of two or more. Among these polyfunctional (meth) acrylates (A2), since the pencil hardness and scratch resistance of the cured coating film surface of the active energy ray-curable composition of the present invention can be further improved, the (meth) acryloyl group The equivalent weight is 50 to 200 g / eq. In the range of 70 to 150 g / eq. In the range of 80 to 120 g / eq. The thing of the range is more preferable. (Meth) acryloyl group equivalent is 80 to 200 g / eq. Specific examples of the polyfunctional (meth) acrylate (A2) in the range of 5 are pentaerythritol tetraacrylate (acryloyl group equivalent: 88 g / eq.), Dipentaerythritol hexaacrylate (acryloyl group equivalent: 118 g / eq.), And the like. Is mentioned.

  Since the mass ratio [(A1) / (A2)] of the urethane (meth) acrylate (A1) and the polyfunctional (meth) acrylate (A2) can improve the scratch resistance, 90/10 to 10/90 The range of 80/20 to 20/80 is more preferable, and the range of 75/25 to 25/75 is more preferable.

  In addition, the active energy ray-curable composition of the present invention includes one molecule within a range not impairing the effects of the present invention, in addition to the urethane (meth) acrylate (A1) and the polyfunctional (meth) acrylate (A2). Other (meth) acrylates such as mono (meth) acrylate having one (meth) acryloyl group in it and di (meth) acrylate having two (meth) acryloyl groups in one molecule may be blended. . When other (meth) acrylates are blended with the active energy ray-curable composition of the present invention, the blending amounts thereof are the urethane (meth) acrylate (A1) and the polyfunctional (meth) acrylate (A2). 40 parts by mass or less is preferable with respect to a total of 100 parts by mass, and 20 parts by mass or less is more preferable.

  The fluorine compound (B) has a cyclopolysiloxane structure bonded to both ends of the poly (perfluoroalkylene ether) chain via a divalent linking group, and the cyclopolysiloxane structure via a divalent linking group. It is a compound having a structure in which a (meth) acryloyl group is bonded. In the present invention, “poly (perfluoroalkylene ether)” is sometimes referred to as “perfluoropolyether”.

  Examples of the poly (perfluoroalkylene ether) chain of the fluorine compound (B) include those having a structure in which a divalent fluorocarbon group having 1 to 3 carbon atoms and oxygen atoms are alternately connected. The divalent fluorinated carbon group having 1 to 3 carbon atoms may be one type or a combination of two or more types, specifically, those represented by the following structural formula (1) may be mentioned. It is done.

（上記一般式（１）中、Ｘは下記式（１−１）〜（１−５）であり、Ｘが下記式（１−１）〜（１−５）のいずれか１種類のものであってもよいし、また、下記式（１−１）〜（１−５）のうち、２種類以上のものがランダム状又はブロック状に存在していてもよい。また、ｎは繰り返し単位を表す２〜２００の整数である。）

(In the general formula (1), X is the following formulas (1-1) to (1-5), and X is any one of the following formulas (1-1) to (1-5). In addition, two or more of the following formulas (1-1) to (1-5) may be present in a random or block form, and n is a repeating unit. Represents an integer of 2 to 200.)

  Among the poly (perfluoroalkylene ether) chains, since the antifouling property of the cured coating film of the active energy ray-curable composition of the present invention is improved, the perfluoromethylene represented by the formula (1-1) is used. A poly (perfluoroalkylene ether) chain of a combination of a group and a perfluoroethylene group represented by the formula (1-2) is preferred. Here, the molar ratio of the perfluoromethylene group represented by the formula (1-1) and the perfluoroethylene group represented by the formula (1-2) [(1-1) / (1-2 )] Is preferably in the range of 1/10 to 10/1. Moreover, the value of n in the said General formula (1) has the preferable range of 2-200, The range of 10-100 is more preferable, The range of 20-80 is further more preferable.

  As a cyclopolysiloxane structure which the said fluorine compound (B) has, the structure represented by following General formula (2) is mentioned, for example.

（上記一般式（２）中、Ｒ^１はメチル基であり、Ｒ^３はポリ（パーフルオロアルキレンエーテル）鎖と結合する２価の有機基であり、Ｒ^４は（メタ）アクリロイル基を有する１価の有機基である。また、ｍは２〜５の整数である。）

(In the 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 a 1 having a (meth) acryloyl group. And m is an integer of 2 to 5.)

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

  The divalent linking group that connects the poly (perfluoroalkylene ether) chain and the cyclopolysiloxane structure is not particularly limited as long as it is a divalent organic group. For example, the divalent linking group is represented by the following general formula (3). Can be mentioned.

（上記一般式（３）中、Ｙは炭素原子数１〜６のアルキレン基である。）

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

  In addition, the divalent linking group that bonds the cyclopolysiloxane structure and the (meth) acryloyl group is not particularly limited as long as it is a divalent organic group. For example, it is represented by the following general formula (4). Things.

（上記一般式（４）中、Ｚ^１、Ｚ^２及びＺ^３は、それぞれ独立に炭素原子数１〜６のアルキレン基である。）

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

As a manufacturing method of the said fluorine compound (B), the method of manufacturing through the following (1)-(3) process is mentioned, for example.
(1) A compound having an allyl group at both ends of a poly (perfluoroalkylene ether) chain and a cyclopolysiloxane compound having a hydrosilyl group are reacted in the presence of a platinum-based catalyst to form both poly (perfluoroalkylene ether) chains. A step of obtaining a compound having a cyclopolysiloxane structure at the terminal.
(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 portion of the compound obtained in (1).
(3) A step of reacting a hydroxyl group added in (2) with a (meth) acrylate having an isocyanate group to introduce a (meth) acryloyl group.

  The blending amount of the fluorine compound (B) in the active energy ray-curable composition of the present invention can impart higher pencil hardness to the cured coating film surface of the active energy ray-curable composition of the present invention, and scratch resistance. In addition, since the antifouling property and slipperiness can be further improved, the urethane (meth) acrylate (A1), the polyfunctional (meth) acrylate (A2), and other (meth) acrylates optionally blended in a total of 100 parts by mass On the other hand, the range of 0.05-5 mass parts is preferable, and the range of 0.1-2 mass parts is more preferable.

  The reactive silica (C1) is obtained by introducing a reactive group such as a (meth) acryloyl group to the surface of silica particles by surface modification. The reactive silica (C1) is preferably nanometer-sized, since it can further improve the transparency of the cured coating film of the active energy ray-curable composition of the present invention and the pencil hardness of the surface. Silica is preferred. In a specific average particle diameter, a range of 5 to 200 nm is preferable, and a range of 5 to 100 nm is more preferable.

  The non-reactive silica (C2) does not have a reactive group on the surface of the silica particles, but may be surface-modified with a non-reactive organic group. Further, the non-reactive silica (C2) can further improve the transparency of the cured coating film and the pencil hardness of the surface of the active energy ray-curable composition of the present invention, and can further improve the curl resistance. An order size is preferable, and colloidal silica is preferable. In a specific average particle diameter, a range of 5 to 200 nm is preferable, and a range of 5 to 100 nm is more preferable.

The use ratio [(C1) / (C2)] of the reactive silica (C1) and the non-reactive silica (C2) is the pencil hardness of the cured coating film surface of the active energy ray-curable composition of the present invention. because it can further improve, but in the range of 0.5 to 1.5, the range of 0.6 to 1 is good preferable.

  The total amount of the reactive silica (C1) and the non-reactive silica (C2) in the active energy ray-curable composition of the present invention is the amount of the cured coating film surface of the active energy ray-curable composition of the present invention. Since the pencil hardness, scratch resistance, antifouling property and slipperiness can be further improved, the urethane (meth) acrylate (A1), the polyfunctional (meth) acrylate (A2), and other (meth) acrylates optionally blended The range of 100-300 mass parts is preferable with respect to a total of 100 mass parts, and the range of 150-280 mass parts is more preferable.

  Moreover, the active energy ray curable composition of this invention can be made into a cured coating film by irradiating an active energy ray after apply | coating to a base material. The active energy rays refer to ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When irradiating ultraviolet rays as active energy rays to form a cured coating film, it is preferable to add a photopolymerization initiator (D) to the active energy ray curable composition of the present invention to improve curability. Further, if necessary, a photosensitizer can be further added to improve curability. On the other hand, when ionizing radiation such as electron beam, α-ray, β-ray, γ-ray, etc. is used, it is hardened quickly without using a photopolymerization initiator (D) or a photosensitizer, so that photopolymerization is particularly initiated. It is not necessary to add an agent (D) or a photosensitizer.

  Examples of the photopolymerization initiator (D) include intramolecular cleavage type photopolymerization initiators and hydrogen abstraction type photopolymerization initiators. Examples of the intramolecular cleavage type photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, oligo [2-hydroxy-2-methyl-1- [4- ( 1-methylvinyl) phenyl] propanone], benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy -2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) -Acetophenone compounds such as butanone; benzoin, benzoin methyl ether, benzo Benzoin such as isopropyl ether; acylphosphine oxide compounds such as 2,4,6-trimethylbenzoin diphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; benzyl, methylphenylglyoxyester, etc. Is mentioned.

  On the other hand, as the hydrogen abstraction type photopolymerization initiator, for example, benzophenone, methyl 4-phenylbenzophenone, o-benzoylbenzoate, 4,4′-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4′-methyl-diphenyl sulfide Acrylated benzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone Benzophenone compounds such as 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, etc .; Michler-ketone, 4,4′-diethyla Aminobenzophenone compounds such as nobenzophenone; 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, 1- [4- (4-benzoylphenylsulfanyl) phenyl ] -2-methyl-2- (4-methylphenylsulfonyl) propan-1-one and the like. These photopolymerization initiators (D) can be used alone or in combination of two or more.

  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-benzylisothuronium-p. -Sulfur compounds, such as toluene sulfonate, etc. are mentioned.

  The amount of these photopolymerization initiator and photosensitizer used is preferably 0.05 to 20 parts by mass with respect to 100 parts by mass of the non-volatile component in the active energy ray-curable composition of the present invention. -15 mass% is more preferable.

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

  The method for applying the active energy ray-curable composition of the present invention to the substrate varies depending on the application, but includes, for example, die coating, microgravure coating, gravure coating, roll coating, comma coating, air knife coating, kiss coating, spray coating, Examples include dip coating, spinner coating, wheeler coating, brush coating, full surface coating with silk screen, wire bar coating, and flow coating.

  As described above, the active energy rays for curing 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. When ultraviolet rays are used as a device for irradiating rays, the sources of ultraviolet rays are low pressure mercury lamps, high pressure mercury lamps, ultrahigh pressure mercury lamps, metal halide lamps, electrodeless lamps, chemical lamps, black light lamps, mercury-xenon. Examples include lamps, short arc lamps, helium / cadmium lasers, argon lasers, sunlight, and LEDs. In addition, when the substrate on which the active energy ray-curable composition of the present invention is applied is a film substrate, the influence of heat on the film substrate can be reduced by using a flashing xenon-flash lamp. Therefore, it is preferable. On the other hand, when an electron beam is used, examples of the generation source of the electron beam include a scanning electron beam accelerator and a curtain type electron beam accelerator.

  In addition, when the active energy ray-curable composition of the present invention is irradiated with ultraviolet rays to form a cured coating film, it may be performed in an air atmosphere, but a cured coating film having higher pencil hardness is obtained, Furthermore, it is preferable to carry out in an atmosphere having an oxygen concentration of 5,000 ppm or less because a cured coating film having excellent scratch resistance and slipperiness can be obtained.

  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 slipperiness, the active energy ray-curable composition of the present invention is variously used. By applying and curing on the surface of an article, high pencil hardness can be imparted to the surface of various articles, and excellent antifouling properties, scratch resistance and slipperiness can also be imparted. 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, antifouling property and the like to the surface of various articles.

  Articles to which the active energy ray-curable composition of the present invention can be applied include housings for home appliances such as televisions, refrigerators, washing machines, and air conditioners; electronic devices such as personal computers, smartphones, mobile phones, digital cameras, and game machines. Enclosures; Interior materials for various vehicles such as automobiles and railway vehicles; Various building materials such as decorative panels; Woodwork materials such as furniture; Artificial and synthetic leather; FRP bathtubs; Liquid crystal displays (LCD) such as triacetylcellulose (TAC) films Optical film; Prism sheet or diffusion sheet as backlight member of LCD; Various display screens (hard coat layer, antireflection layer) such as plasma display (PDP) and organic EL display; Touch panel; Electronics such as mobile phones and smartphones Terminal screen; Color filter for liquid crystal display (hereinafter referred to as “CF”) ) Transparent protective film; optical recording media such as CD, DVD, Blu-ray disc; transfer film for insert mold (IMD, IMF); rubber roller for OA equipment such as copiers and printers; OA equipment such as copiers and scanners Glass surface of reading unit; Optical lens such as camera, video camera, glasses, etc .; Windshield of watches such as watches, glass surface; Windows of various vehicles such as automobiles and railway vehicles; Cover glass or film for solar cells; Various building materials; residential window glass; woodwork materials such as furniture.

  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 surface of a film substrate. As the film substrate, various commonly used resin film substrates can be used, for example, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, cellophane, diacetylcellulose, triacetylcellulose, acetylcellulose butyrate. , Cellulose acetate propionate, cycloolefin polymer, cycloolefin copolymer, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polymethylpentene, polysulfone, polyether ether ketone, poly List resin films such as ether sulfone, polyether imide, polyimide, fluororesin, nylon, acrylic resin It can be. In particular, resin films of polyethylene terephthalate, triacetyl cellulose, and acrylic resin are excellent in transparency and processability, and thus can be suitably used.

  The film substrate may be a substrate composed only of the resin film mentioned above, but in order to improve the adhesion with the active energy ray-curable composition of the present invention, the resin film It may be a film substrate provided with a primer layer. Examples of the primer layer include those made of polyester resin, urethane resin, acrylic resin, and the like. In addition, for the purpose of improving the adhesion with the hard coat layer, the surface of the resin film is subjected to surface concavo-convex treatment by sandblasting method, solvent treatment method, corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, ozone The treatment can also be performed by ultraviolet irradiation treatment, oxidation treatment or the like.

  The thickness of the film base is preferably in the range of 50 to 200 μm, more preferably in the range of 80 to 150 μm, and still more preferably in the range of 90 to 130 μm. In the present invention, by setting the thickness of the film substrate within the range, curling can be easily suppressed even when a hard coat layer is provided on one side of the film substrate.

  Furthermore, it is preferable to use a film substrate having an elastic modulus in the range of 3 to 7 GPa as the film substrate, and it is particularly preferable to use a film substrate in the range of 3 to 5 GPa. When the elastic modulus is within this range, deformation of the film substrate is less likely to occur when a protective film is formed, and cracking of the hard coat layer can be suppressed, and a decrease in hardness of the hard coat film surface can be easily suppressed. Moreover, since the flexibility of the film base material can be ensured, it is easy to follow a gentle curved surface when a protective film described later is attached.

  The protective film of the present invention has an adhesive layer on one surface of the hard coat film. The pressure-sensitive adhesive layer can be provided by attaching a pressure-sensitive adhesive tape to the film base material, or by directly applying a pressure-sensitive adhesive layer to the surface opposite to the hard coat surface of the film base material.

  The thickness of the pressure-sensitive adhesive layer of the protective film of the present invention is preferably in the range of 5 to 50 μm, more preferably in the range of 8 to 30 μm, and still more preferably in the range of 10 to 25 μm. In this invention, by making the thickness of an adhesive layer into the said range, it is excellent in adhesive reliability, and can maintain the surface hardness of a hard coat film not remarkably impaired.

  As the pressure-sensitive adhesive used in the pressure-sensitive adhesive layer used in the present invention, known acrylic, rubber-based, silicone-based pressure-sensitive resins can be used. Among them, an acrylic copolymer obtained by polymerizing a (meth) acrylate monomer having an alkyl group having 2 to 14 carbon atoms as a repeating unit as a main component has adhesiveness with a film substrate, transparency, It is preferable from the point of weather resistance.

  Examples of the (meth) acrylate monomer having 2 to 14 carbon atoms include ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, and n-hexyl acrylate. , Cyclohexyl acrylate, n-octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, isononyl acrylate, isodecyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, sec- Butyl methacrylate, t-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, n Octyl methacrylate, isooctyl methacrylate, 2-ethylhexyl methacrylate, isononyl 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 preferable, and an alkyl acrylate having an alkyl group having 4 to 9 carbon atoms is more preferable. preferable. Of the alkyl acrylates, n-butyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, isononyl acrylate, and ethyl acrylate are particularly preferable. By using an alkyl (meth) acrylate having an alkyl group having the number of carbon atoms in the range, it is easy to ensure a suitable adhesive force.

  The content of the (meth) acrylate having 2 to 14 carbon atoms in the monomer constituting the acrylic copolymer used in the pressure-sensitive adhesive layer of the present invention is preferably 90 to 99% by mass, 90 More preferably, it is made -96 mass%. By setting the content of the (meth) acrylate in this range, it is easy to ensure a suitable adhesive force.

  For acrylic copolymers, (meth) acrylate monomers having polar groups such as hydroxyl, carboxyl and amide groups and vinyl monomers having other polar groups should be used as monomer components. Is preferred.

  Examples of the (meth) acrylate monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, hydroxypropyl (meth) acrylate, Examples include caprolactone-modified (meth) acrylate, polyethylene glycol mono (meth) acrylate, and polypropylene glycol mono (meth) acrylate. 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, acrylic acid or methacrylic acid dimer, ethylene oxide-modified succinic acid acrylate, and the like. Can be mentioned. Among these, it is preferable to use acrylic acid.

  Examples of the (meth) acrylate monomer having an amide group include N-vinyl-2-pyrrolidone, N-vinylcaprolactam, acryloylmorpholine, acrylamide, N, N-dimethylacrylamide, N-acryloyloxyethyl-3, 4,5,6-tetrahydrophthalimide and the like. Among these, it is preferable to use N-vinyl-2-pyrrolidone, N-vinylcaprolactam, and acryloylmorpholine.

  Examples of the other vinyl monomers having a polar group include vinyl acetate, acrylonitrile, maleic anhydride, itaconic anhydride and the like.

  The content of the monomer having a polar group is preferably 0.1 to 20% by mass, more preferably 1 to 13% by mass of the monomer component constituting the acrylic copolymer. More preferably, it is 1.5 to 8% by weight. By containing a monomer having a polar group within this range, it is easy to adjust the cohesive strength, holding power, and adhesiveness of the pressure-sensitive adhesive within a suitable range.

  The weight average molecular weight Mw of the acrylic copolymer used for the pressure-sensitive adhesive layer is preferably 400,000 to 1,400,000, and more preferably 600,000 to 1,200,000. When the weight average molecular weight Mw of the acrylic copolymer is within the 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, as a GPC measurement device, “SC8020” manufactured by Tosoh Corporation can be used to measure and obtain the following GPC measurement conditions based on polystyrene conversion values.
(GPC measurement conditions)
Sample concentration: 0.5% by weight (tetrahydrofuran solution)
Sample injection volume: 100 μL
・ Eluent: Tetrahydrofuran (THF)
・ Flow rate: 1.0 mL / min
Column temperature (measurement temperature): 40 ° C
Column: “TSKgel GMHHR-H” manufactured by Tosoh Corporation
・ Detector: Differential refraction

  Further, in order to increase the cohesive strength of the pressure-sensitive adhesive layer, it is preferable to add a crosslinking agent in the pressure-sensitive adhesive. As a crosslinking agent, an isocyanate type crosslinking agent, an epoxy type crosslinking agent, a chelate type crosslinking agent etc. are mentioned, for example. The addition amount of the crosslinking agent is preferably adjusted so that the gel fraction of the pressure-sensitive adhesive layer is 25 to 80% by mass, more preferably adjusted to be 40 to 75% by mass, and 50 to 70% by mass. It is most preferable to adjust so that. By adjusting the gel fraction within this range, it is possible to suppress a decrease in surface pencil hardness when the protective film is attached to the substrate, and the adhesiveness can be sufficient. The gel fraction in the present invention is expressed as a percentage of the original mass by immersing the cured pressure-sensitive adhesive layer in toluene, measuring the mass after drying of the insoluble matter remaining after standing for 24 hours, and the original mass. Is.

  Furthermore, in order to improve the adhesive strength of the pressure-sensitive adhesive layer, a tackifier resin may be added. As addition amount of tackifying resin, when an adhesive resin is an acrylic copolymer, it is preferable to add in 10-60 mass parts with respect to 100 mass parts of acrylic copolymers. Furthermore, when importance is attached to adhesiveness, it is preferable to add in the range of 20-50 mass parts.

  Moreover, a well-known and usual additive other than the above can be added to an adhesive. For example, in order to improve the adhesion to the glass substrate, it is preferable to add a silane coupling agent in the range of 0.001 to 0.005 parts by mass with respect to 100 parts by mass of the pressure-sensitive adhesive. Furthermore, a plasticizer, a softening agent, a filler, a pigment, a flame retardant, etc. can also be added as other additives as needed.

  The protective film of the present invention can be applied to various uses because it has suitable scratch resistance and slipperiness, and is particularly suitable for an image display unit of an image display device such as a liquid crystal display (LCD) or an organic EL display. Applicable. In particular, since it is possible to realize suitable scratch resistance and slipperiness even when it is thin, portable electronic devices that are highly demanded for miniaturization and thinning of electronic notebooks, mobile phones, smartphones, portable audio players, mobile personal computers, tablet terminals, etc. It is suitable as a protective film for the image display unit of the terminal image display device. In such an image display device, for example, a configuration in which an image display module such as an LCD module or an organic EL module is included in the configuration, and a transparent panel for protecting the image display module is provided above the image display module. In this image display device, it is effective to prevent scratches and to prevent scattering when the transparent panel is damaged by being attached to the front or back surface of the transparent panel.

  Hereinafter, the present invention will be described in more detail with reference to examples.

(Synthesis Example 1: Synthesis of urethane acrylate (A1-1))
In a flask equipped with a stirrer, a gas introduction tube, a cooling tube, and a thermometer, pentaerythritol triacrylate (hereinafter abbreviated as “PE3A”) and pentaerythritol tetraacrylate (hereinafter abbreviated as “PE4A”). 549.1 parts by weight of the mixture (PE3A / PE4A = 60/40 (mass ratio)), 0.1 parts by weight of dibutyltin diacetate, 0.6 parts by weight of dibutylhydroxytoluene, 0.1 parts by weight of p-methoxyphenol and acetic acid 160 parts by mass of butyl was added, air was blown in, and the temperature was gradually raised while mixing uniformly. When 90.9 parts by mass of hexamethylene diisocyanate was added when the temperature reached 60 ° C., the mixture was reacted at 80 ° C. for 5 hours, and a non-volatile content containing urethane acrylate (A1-1) having 6 acryloyl groups in one molecule was obtained. % Solution was obtained. This solution contains 34.3% by mass of PE4A in addition to urethane acrylate (A1-1) in the nonvolatile content.

(Synthesis Example 2: Synthesis of urethane acrylate (A1-2))
254 parts by mass of butyl acetate, 222 parts by mass of isophorone diisocyanate, 0.5 parts by mass of p-methoxyphenol and 0.5 parts by mass of dibutyltin diacetate are charged in a flask equipped with a stirrer, a gas introduction pipe, a cooling pipe and a thermometer. The temperature was raised to 70 ° C. while blowing air, and then 795 parts by mass of a mixture of PE3A and PE4A (PE3A / PE4A = 75/25 (mass ratio)) was added dropwise over 1 hour. After completion of dropping, the reaction is carried out at 70 ° C. for 3 hours, and further, the reaction is carried out until the infrared absorption spectrum of 2250 cm ⁻¹ indicating the isocyanate group disappears, and urethane acrylate (A1-2) having 6 acryloyl groups in one molecule is obtained. A non-volatile content 80% by mass solution was obtained. This solution contains 19.5% by mass of PE4A in addition to urethane acrylate (A1-2) in the nonvolatile content.

(Synthesis Example 3: Synthesis of urethane acrylate (A1-3))
In a flask equipped with a stirrer, a gas introduction tube, a cooling tube and a thermometer, 242 parts by mass of a mixture of PE3A and PE4A (PE3A / PE4A = 60/40 (mass ratio)), 0.23 parts by mass of p-methoxyphenol, dibutyl After charging 0.13 parts by mass of tin dilaurate and 100 parts by mass of methyl ethyl ketone and raising the temperature to 75 ° C. while blowing air, a trimerized hexamethylene diisocyanate (isocyanurate) (manufactured by Sumika Bayer Urethane Co., Ltd.) Module N3390BA ”, 90% by mass of non-volatile content, NCO%: 19.6, NCO equivalent: 214 g / eq.) 107 parts by mass and 50 parts by mass of methyl ethyl ketone were added dropwise over 2 hours. After completion of the dropwise addition, the mixture is reacted at 75 ° C. for 4 hours, and further reacted until the infrared absorption spectrum of 2250 cm ⁻¹ showing the isocyanate group disappears, and urethane acrylate (A1-3) having 9 acryloyl groups in one molecule is obtained. A 67.8 mass% solution with a nonvolatile content was obtained. This solution contains 28.6% by mass of PE4A in addition to urethane 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 condenser, in a dry nitrogen atmosphere, 500 parts by mass of perfluoropolyether having an allyl group at both ends represented by the following formula (5), 700 parts by mass of m-xylene hexafluoride, 361 parts by mass of tetramethylcyclotetrasiloxane was charged, and the temperature was raised to 90 ° C. while stirring. To this, 0.442 parts by mass of a toluene solution of chloroplatinic acid / vinylsiloxane complex (containing 1.1 × 10 ⁻⁶ mol as a Pt simple substance) was added and stirred for 4 hours while maintaining the internal temperature at 90 ° C. or higher. After confirming disappearance of the allyl group of the raw material by ¹ H-NMR spectrum, the solvent and excess tetramethylcyclotetrasiloxane are distilled off under reduced pressure, and activated carbon treatment is performed, thereby being represented by the following formula (6). A perfluoropolyether compound (1) which was a colorless and transparent liquid was obtained.

（式中、ｍ／ｎは０．９であり、ｍ及びｎの合計は平均で４５である。）

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

Under a dry air atmosphere, 50 parts by mass of the perfluoropolyether compound (1) obtained above, 7.05 parts by mass of 2-allyloxyethanol, 50 parts by mass of m-xylene hexafluoride and chloroplatinic acid / vinylsiloxane 0.0442 parts by mass of a toluene solution of the complex (containing 1.1 × 10 ⁻⁷ mol as Pt alone) 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 the activated carbon treatment was performed, whereby the following formula (7) A perfluoropolyether compound (2), which is a pale yellow transparent liquid represented by

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

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

Example 1
62 parts by mass of the solution containing urethane acrylate (A1-1) obtained in Synthesis Example 1 (including 32.6 parts by mass of urethane acrylate (A1-1) and 17 parts by mass of PE4A), obtained in Synthesis Example 3 18.3 parts by mass of a solution containing urethane acrylate (A1-3) (8.9 parts by mass of urethane acrylate (A1-3), 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 compound (B-1) obtained in Synthesis Example 4 (1.5 parts by mass as the fluorine compound (B-1)) ), Reactive colloidal silica ("MEK-AC-2140Z" manufactured by Nissan Chemical Industries, Ltd., methyl ethyl ketone dispersion having a nonvolatile content of 40% by mass; hereinafter abbreviated as "reactive silica (C1-1)") .) 287.5 parts by mass (115 parts by mass as reactive silica (C1-1)), non-reactive colloidal silica (“MEK-ST40” manufactured by Nissan Chemical Industries, Ltd., methyl ethyl ketone dispersion having a nonvolatile content of 40% by mass; Hereinafter, abbreviated as “non-reactive silica (C2-1).” 312.5 parts by mass (125 parts by mass as non-reactive silica (C2-1)), photopolymerization initiator (“Irgacure” manufactured by BASF Japan Ltd.) 184 ", 1-hydroxycyclohexyl phenyl ketone; hereinafter abbreviated as" photopolymerization initiator (D-1) ") 10.9 parts by mass and photopolymerization initiator (" Irgacure 754 "manufactured by BASF Japan Ltd., oxy Phenylacetic acid 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester and oxyphenylacetic acid 2- (2-hydroxyethoxy) Mixture with ethyl ester; hereinafter abbreviated as “photopolymerization initiator (D-2)”.) 1.6 parts by mass of the mixture was uniformly stirred and then diluted with methyl ethyl ketone to obtain an active energy having a nonvolatile content of 40% by mass. A linear curable composition (1) was prepared.

[Evaluation of coating appearance]
In order to judge whether the active energy ray-curable composition (1) obtained above can be used as a coating, the appearance was visually observed, and the coating appearance was evaluated according to the following criteria.
○: There is no cloudiness or component separation.
X: There is cloudiness or component separation.

[Preparation of test piece film]
The active energy ray-curable composition (1) obtained above is coated with a wire bar (# 40) on the easy-adhesion treated surface of a polyethylene terephthalate film (“Cosmo Shine A4100” manufactured by Toyobo Co., Ltd., thickness 100 μm). Applied, dried at 60 ° C. for 1 minute, and then irradiated with an ultraviolet ray in an atmosphere having an oxygen concentration of 5,000 ppm or less (“MIDN-042-C1” manufactured by Eye Graphics Co., Ltd., lamp: 120 W / cm, high pressure mercury lamp ) Was irradiated with ultraviolet rays at an irradiation light amount of 0.5 J / cm ² to obtain a test piece film having a cured coating film (hard coat layer) having a thickness of 15 μm.

[Evaluation of appearance of cured coating film]
The surface of the cured coating film of the test piece film obtained above was visually observed, and the cured coating film appearance was evaluated according to the following criteria.
○: There are no coating unevenness, coating streaks, and irregularities.
X: There are coating unevenness, coating stripes or irregularities.

  The test piece film obtained above was evaluated or measured for the following curls, pencil hardness, scratch resistance, water contact angle, antifouling property, and slipperiness.

[Evaluation of curling resistance]
The film for evaluation obtained above was cut into a 10 cm square, allowed to stand overnight at 23 ° C. and 50% RH, then measured for lifting from the bottom of the curled corners, and evaluated for curl resistance according to the following criteria. did.
(Double-circle): The average value of lifting of four corners is less than 10 mm.
○: The average value of lifting at the four corners is 10 mm or more and less than 25 mm.
X: The average value of lifting of four corners is 25 mm or more.

[Measurement of pencil hardness]
The hardest pencil which did not produce a scar in accordance with JIS K 5600-5-4: 1999, using the pencil specified in JIS S 6006: 2007 for the cured coating film surface of the evaluation film obtained above. Was measured as pencil hardness.

[Evaluation of scratch resistance]
The test piece film obtained above is cut into a 30 cm × 2 cm rectangle, fixed to a flat friction tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.) with a jig, a load of 1 kg / cm ² using steel wool # 0000, a stroke The scratched state of the test piece after 10 cm, speed 20 cm / sec, and reciprocating 200 times was visually observed, and scratch resistance was evaluated according to the following criteria.
A: Not scratched.
A: Less than 5 scratches are attached.
Δ: 5 or more scratches are attached, but the entire test piece film is not damaged.
X: The test piece film is scratched.

[Measurement of water contact angle]
The test piece film obtained above was cut into a 1 × 5 cm rectangle, and the cured film of the test piece film was fixed to the glass plate with a double-sided tape, and an automatic contact angle meter “DROMPAMSTER500” manufactured by Kyowa Interface Science Co., Ltd. was used. The contact angle of 4 to 4.5 μL of purified water was measured.

[Evaluation of antifouling properties]
On the cured coating film of the test piece film obtained above, ink was applied in a circular shape with “Uni Mediax (black)” manufactured by Mitsubishi Pencil Co., Ltd., and the degree of ink repelling was visually observed. From the observation results, antifouling properties were evaluated according to the following criteria.
5: The ink is repelled.
4: The ink is repelled by dots and lines.
3: The ink is repelled linearly.
2: Slightly repel ink.
1: Does not repel ink.

[Evaluation of slipperiness]
From the slipperiness when the surface of the cured coating film of the test piece film obtained above was rubbed with Bencott (manufactured by Asahi Kasei Fibers Corporation), the slipperiness was evaluated according to the following criteria.
A: Glide well.
○: Slip.
Δ: Not slippery
×: Does not slip.

(Example 2)
The non-volatile content was 40 as in Example 1 except that the 20% by mass solution of the fluorine compound (B-1) used in Example 1 was changed to 5 parts by mass (1 part by mass as the fluorine compound (B-1)). A mass% active energy ray-curable composition (2) was prepared. Using the obtained active energy ray-curable composition (2), in the same manner as in Example 1, evaluation or measurement was performed after preparing a test piece film.

Example 3
Instead of the mixture of PE4A and PE3A used in Example 1 (PE4A / PE3A = 60/40 (mass ratio)), 23.8 parts by mass of the solution containing urethane acrylate (A1-2) obtained in Synthesis Example 2 (Including urethane acrylate (A1-2) 15.3 parts by mass, PE4A 3.7 parts by mass), and DPHA and DPPA mixture (DPHA / DPPA = 60/40 (mass ratio)) except 19 parts by mass Prepared an active energy ray-curable composition (3) having a nonvolatile content of 40% by mass in the same manner as in Example 1. Using the obtained active energy ray-curable composition (3), in the same manner as in Example 1, evaluation or measurement was performed after preparing a test piece film.

Example 4
The compounding amount of the methyl ethyl ketone dispersion having a nonvolatile content of 40% by mass of the reactive silica (C1-1) used in Example 1 is 287.5 parts by mass to 187.5 parts by mass (75 as reactive silica (C1-1)). 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 content was changed to (parts by mass). Using the obtained active energy ray-curable composition (4), in the same manner as in Example 1, evaluation or measurement was performed after preparing a test piece film.

(Comparative Example 1)
Active energy ray curability having a nonvolatile content of 40% by mass, as in Example 1, except that the reactive silica (C1-1) and the non-reactive silica (C2-1) used in Example 1 were not blended. Composition (R1) was prepared. Using the obtained active energy ray-curable composition (R1), in the same manner as in Example 1, evaluation or measurement was performed after producing a test piece film.

(Comparative Example 2)
Instead of the 20% by mass solution of the fluorine compound (B-1) used in Example 1, a fluorine compound having an acryloyl group at one end of the poly (perfluoroalkylene ether) chain ("OPTOOL DAC-" manufactured by Daikin Industries, Ltd.) HP ”, 20 parts by mass of nonvolatile content; hereinafter abbreviated as“ fluorine compound (RB-1). ”Except for using 7.5 parts by mass (1.5 parts by mass as fluorine compound (RB-1)). 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), in the same manner as in Example 1, evaluation or measurement was performed after preparing a test piece film.

(Comparative Example 3)
The compounding amount of the methyl ethyl ketone dispersion having a nonvolatile content of 40% by mass of the reactive silica (C1-1) used in Example 1 is 287.5 parts by mass to 200 parts by mass (reactive silica (C1-1) as 200 parts by mass). The active energy ray-curable composition (R3) having a nonvolatile content of 40% by mass was prepared in the same manner as in Example 1 except that the non-reactive silica (C2-1) was not blended. Using the obtained active energy ray-curable composition (R3), in the same manner as in Example 1, evaluation or measurement was performed after preparing a test piece film.

(Comparative Example 4)
The blending amount of the methyl ethyl ketone dispersion having a nonvolatile content of 40% by mass of the non-reactive silica (C2-1) used in Example 1 is from 312.5 parts by mass to 200 parts by mass (200 as non-reactive silica (C2-1) The active energy ray-curable composition (R4) having a nonvolatile content of 40% by mass was prepared in the same manner as in Example 1 except that the reactive silica (C1-1) was not blended. Using the obtained active energy ray-curable composition (R4), in the same manner as in Example 1, evaluation or measurement was performed after producing a test piece film.

  Table 1 shows the compositions 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 non-volatile content, and the urethane acrylates (A1-1) to (A1-3) describe the blending amounts including PE4A.

  From the evaluation results shown in Table 1, the active energy ray-curable compositions of the present invention of Examples 1 to 4 have no problem in appearance as a coating agent, and there is no problem in the appearance of the cured coating film. I was able to confirm. It was also confirmed that the active energy ray-curable composition of the present invention has low curl after curing and high curl resistance. Furthermore, it was confirmed that the cured coating film surface of the active energy ray-curable composition of the present invention has high pencil hardness and excellent scratch resistance, pencil hardness, antifouling property and slipperiness.

  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 the non-reactive silica (C2) used in the present invention, but the pencil hardness is not sufficient. Was confirmed.

  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, but it can be confirmed that pencil hardness, scratch resistance, and slipperiness are not sufficient. It was.

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

  Comparative Example 4 is an example of an active energy ray-curable composition that did not use the reactive silica (C1) used in the present invention, but it was confirmed that the pencil hardness and scratch resistance were not sufficient.

Claims (13)

A cyclopolysiloxane structure is bonded to both ends of the active energy ray-curable compound (A) and the poly (perfluoroalkylene ether) chain via a divalent linking group, and a divalent linking group is bonded to the cyclopolysiloxane structure. An active energy ray-curable composition comprising a fluorine compound (B) having a structure in which a (meth) acryloyl group is bonded thereto, reactive silica (C1), and non-reactive silica (C2), Active energy ray curability, wherein the ratio [(C1) / (C2)] of the reactive silica (C1) and the non-reactive silica (C2) is in the range of 0.5 to 1.5 Composition.   The active energy ray-curable compound (A) is obtained by reacting an aliphatic polyisocyanate (a1) with a (meth) acrylate (a2) having a hydroxyl group, and four or more (meth) acryloyl groups in one molecule. The active energy ray-curable composition according to claim 1, which is a urethane (meth) acrylate (A1) having a group and a polyfunctional (meth) acrylate (A2) having three or more (meth) acryloyl groups in one molecule. object.   3. The aliphatic polyisocyanate (a1) is at least one polyisocyanate selected from the group consisting of hexamethylene diisocyanate, norbornane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate) and trimers thereof. The active energy ray-curable composition described.   The active energy according to claim 2, wherein the (meth) acrylate (a2) is at least one (meth) acrylate selected from the group consisting of dipentaerythritol penta (meth) acrylate and pentaerythritol tri (meth) acrylate. A linear curable composition.   The (meth) acryloyl group equivalent of the polyfunctional (meth) acrylate (A2) is 50 to 200 g / eq. The active energy ray-curable composition according to claim 2, which is in the range of   The polyfunctional (meth) acrylate (A2) is selected from the group consisting of dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate and pentaerythritol tri (meth) acrylate. The active energy ray-curable composition according to claim 2, which is one or more polyfunctional (meth) acrylates. Hardened | cured material of the active energy ray curable composition of any one of Claims 1-6 . An article having a cured coating film of the active energy ray-curable composition according to any one of claims 1 to 6 . A hard coat layer comprising a hard coat layer on at least one surface of a film substrate, wherein the hard coat layer comprises a cured product of the active energy ray-curable composition according to any one of claims 1 to 6. the film. The hard coat film according to claim 9 , wherein the hard coat layer has a thickness of 1 to 20 μm and the base material has a thickness of 50 to 200 μm. A protective film comprising an adhesive layer on one surface of the hard coat film according to claim 9 . Protective film of claim 1 1, wherein the thickness of the adhesive layer is 5 to 50 [mu] m. Protective film of claim 1 1, wherein used for the protection of the image display unit of the mobile electronic terminal.