JP2015016683A - Hard coat film, decorative film, protective film and image display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hard coat film excellent in antifouling properties, slipperiness and durability.SOLUTION: There is provided a hard coat film in which an antifouling layer (II) is laminated on at least one surface of a hard coat film (I), where the antifouling layer (II) is composed of a cured product of an active energy ray-curable composition containing a fluorine atom-containing compound (II-1) having a polymerizable unsaturated double bond and the fluorine atom-containing compound (II-1) is contained in an amount of 10 mass% or more based on the total amount of the solid content of the active energy ray-curable composition.

Description

  The present invention relates to a hard coat film suitably used for protective films for various touch panel displays such as smartphones and tablet terminals.

  As image display units provided in portable electronic devices such as smartphones and tablet terminals, and image display units provided in televisions, personal computers, and the like, those equipped with a touch panel function are becoming widespread. Since the touch panel is usually operated with a finger or a touch pen, the hard coat film affixed to the surface is required to have excellent antifouling properties (fingerprint resistance) and durability.

  As the hard coat film having excellent antifouling properties and durability, for example, a fluorine-based additive is previously added to the active energy ray-curable composition, applied to a film substrate, and then cured by ultraviolet irradiation. A hard coat film excellent in dirtiness and surface hardness has been proposed. (For example, refer to Patent Document 1.)

  However, in recent years, the high-definition of the image display device and the response speed of the touch panel have been improved, and the improvement in operability corresponding to the response speed has been an issue, the hard coat film improves the operability. In some cases, it was not sufficient in terms of the contributed surface slipperiness. Moreover, the antifouling property and durability requested | required of the hard coat film used for a touch panel etc. may not be enough.

JP 2010-168419 A

  The problem to be solved by the present invention is to provide a hard coat film excellent in antifouling property, slipperiness and durability.

  As a result of intensive studies to solve the above problems, the present inventors have found that a hard coat film in which a specific antifouling layer is laminated on at least one side of the hard coat film has excellent antifouling properties, surface slipperiness and durability. As a result, the present invention was completed.

  That is, the present invention is a hard coat film in which an antifouling layer (II) is laminated on at least one side of the hard coat film (I), and the antifouling layer (II) has a polymerizable unsaturated double bond. It consists of the hardened | cured material of the active energy ray-curable composition containing a fluorine atom containing compound (II-1), and the said fluorine atom containing compound (II-1) is the total amount of solid content of the said active energy ray curable composition. In contrast, the present invention relates to a hard coat film characterized by being contained in an amount of 10% by mass or more.

  Since the hard coat film of the present invention is excellent in antifouling property, surface slipperiness and durability, for example, in an image display unit provided in a portable electronic device such as a smartphone or a tablet terminal, and in a television or a personal computer. It can be suitably used for a protective film, a decorative film and the like provided on the surface of the provided image display unit.

  The hard coat film of the present invention is a fluorine atom in which the antifouling layer (II) has a polymerizable unsaturated double bond among the antifouling layers (II) laminated on at least one side of the hard coat film (I). It consists of hardened | cured material of the active energy ray-curable composition containing containing compound (II-1), and the said fluorine atom containing compound (II-1) is with respect to the total amount of solid content of the said active energy ray-curable composition. 10% by mass or more is contained. The hard coat film of the present invention having the above structure is superior in terms of antifouling property, slipperiness and durability as compared with a conventional hard coat film in which a hard coat layer is simply provided on a transparent film substrate.

  As for the hard coat film of this invention, it is preferable that a part or all of the surface is comprised by the said antifouling layer (II), and a part or all of the surface layer of the one side is constituted by the said antifouling layer (II) More preferably, it is configured.

  Moreover, the hard coat film of this invention may have a decorating layer and an adhesive layer in part or all of the single side | surface or both surfaces. The hard coat film of the present invention in which the decorative layer is provided in part or in whole can be used as a decorative film. In addition, the hard coat film of the present invention in which the pressure-sensitive adhesive layer is partially or entirely provided can be used as a protective film.

  Examples of the decorative layer include those composed of letters, figures, symbols, and frame-like borders for concealment.

  The hard coat film of the present invention preferably has a thickness of 300 μm or less, more preferably has a thickness of 10 μm to 200 μm, and has a thickness of 50 μm to 150 μm. It is more preferable to use a material having a thickness of 80 μm to 140 μm, and it is particularly preferable to use a material having a thickness of 100 μm to 135 μm. If the hard coat film having the thickness in the above range is used for display of various image display devices, for example, it can contribute to thinning of the image display device. In addition, the hard coat film of the present invention can achieve excellent antifouling properties, slipperiness and durability even with a thin thickness within the above range.

  As the hard coat film of the present invention, a hard coat film (I) having a thickness of 180 μm or less and an antifouling layer (II) having a thickness of 50 nm or less may be used. preferable.

  As the hard coat film of the present invention, it is preferable to use a highly transparent film because it can ensure good visibility when applied to a display of an image display device. The total light transmittance of the hard coat film of the present invention is preferably 85% or more, more preferably 88% or more, and particularly preferably 90% or more.

  In the hard coat film of the present invention, the initial water contact angle of the surface layer (antifouling layer (II)) is preferably 95 ° or more, and more preferably 100 ° or more. A high water contact angle makes it easy to obtain suitable antifouling properties.

  The pencil hardness of the hard coat film of the present invention is preferably 2H or more, and preferably 3H or more in order to prevent the surface from being scratched even when, for example, a finger or a touch pen comes into contact. Further preferred.

[Hard coat film (I)]
As the hard coat film (I) constituting the hard coat film of the present invention, those conventionally known can be used, for example, a plastic substrate (I-1) and a hard coat layer (I-2) are laminated. Can be used.

  As the hard coat film (I), a film having a thickness of 180 μm or less is preferably used, and a film having a thickness in the range of 75 μm to 150 μm is more preferable.

  As the hard coat film (I), a hard coat layer (I-2) constituting the hard coat film (I-2) preferably has a surface hardness of 2H or more, more preferably 3H or more. It is preferable to use a film having a hardness of 4H or more because the surface hardness of the finally obtained hard coat film of the present invention can be increased, and as a result, the scratch resistance can be further improved.

Further, the hard coat film (I) has a Martens hardness of 280 N measured by pushing a Vickers indenter with a corner angle of 136 ° into the surface of the hard coat layer (I-2) constituting the hard coat film (I-2) with a load of 15 mN. / ^mm it is preferable to use those having ² ~500N / mm 2 hardness ^hard coat film is finally obtained present invention using a range of 300N / mm ² ~400N / mm 2 The surface hardness can be increased, and as a result, the scratch resistance can be further improved.

[Plastic substrate (I-1)]
As the plastic substrate (I-1) constituting the hard coat film (I), for example, a polyester film, a triacetyl cellulose film, an acrylic resin film, an alicyclic structure-containing thermoplastic resin film, a polycarbonate film, or the like is used. be able to.

  The plastic substrate (I-1) may be a substrate composed only of the resin film mentioned above, but the plastic substrate (I-1) and the hard coat layer (I-2) For the purpose of improving adhesiveness, a base material in which a primer layer is laminated on the surface of the resin film may be used. Further, the surface of the plastic substrate (I-1) is subjected to an unevenness treatment by, for example, a sand blast method, a solvent treatment method or the like for the purpose of further improving the adhesion with the hard coat layer (I-2). Further, treatment by corona discharge treatment, atmospheric pressure plasma treatment, chromic acid treatment, flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, oxidation treatment, or the like may be performed.

  As said plastic base material (I-1), in order to obtain the hard coat film of this invention excellent in transparency, it is preferable to use what has a total light transmittance of 88% or more, and 90% or more. It is preferable to use one having a total light transmittance.

  As said plastic base material (I-1), it is preferable to use what has the thickness of the range of 50 micrometers-150 micrometers, It is preferable to use what has the thickness of the range of 80 micrometers-150 micrometers, 90 micrometers- Even when the hard coat layer (I-2) is provided on one side of the plastic substrate (I-1), it is possible to use the one having a thickness in the range of 130 μm and the hard coat film (I) and It is preferable because curling of the hard coat film of the present invention obtained using the same can be suppressed.

[Hard coat layer (I-2)]
The hard coat layer (I-2) laminated on the plastic substrate (I-1) is a conventionally known hard coat layer.

  The hard coat layer (I-2) may be appropriately selected according to the application to be used, but preferably has a thickness of 5 μm to 25 μm, and preferably has a thickness of 10 μm to 15 μm. For example, it is more preferable to obtain a hard coat film that is excellent in properties and slipperiness and that can be used in, for example, an image display device that is highly required to be thin.

  As said hard-coat layer (I-2), it is preferable to use the surface whose water contact angle is 80 degrees or less, and it is more preferable to use what is 75 degrees or less. By using a hard coat layer having a water contact angle in the above range, the adhesion between the hard coat layer (I-2) and the antifouling layer (II) can be further improved, and the durability is excellent. The hard coat film of the present invention can be obtained.

  Examples of the hard coat layer (I-2) include a layer formed using a conventionally known hard coat agent. Specifically, examples of the hard coat layer (I-2) include a hard coat layer made of a cured product of the active energy ray-curable composition.

  As the active energy ray-curable composition that can be used for forming the hard coat layer (I-2), those conventionally known can be used. Among them, it is preferable to use an active energy ray-curable composition containing (meth) acrylate because it is easy to obtain and handle and easily controls the properties of the resulting hard coat layer, and has a suitable surface hardness. It is more preferable to use an active energy ray-curable composition containing urethane (meth) acrylate since it is easy to obtain durability.

  As urethane (meth) acrylate, various urethane (meth) acrylates that are conventionally known for use in the formation of hard coat layers can be used, and in particular, 4 or more (meth) acryloyl in the molecule. It is preferable to use a urethane (meth) acrylate (A) having a group and a polyfunctional (meth) acrylate (B) having three or more (meth) acryloyl groups in the molecule.

  Examples of the urethane (meth) acrylate (A) include four or more (meth) acryloyl in a molecule obtained by reacting, for example, an aliphatic polyisocyanate (a1) and a (meth) acrylate (a2) having a hydroxyl group. It is preferable to use one having a group.

  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 -Use alicyclic polyisocyanates (a1-2) such as bis (isocyanatomethyl) cyclohexane, 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl-1,5-diisocyanatocyclohexane, etc. be able to. Moreover, as said aliphatic polyisocyanate (a1), the trimerization which trimerized the said aliphatic polyisocyanate (a1-1) or the alicyclic polyisocyanate (a1-2) can also be used. As the aliphatic polyisocyanate (a1), use of hexamethylene diisocyanate, which is a diisocyanate of a linear aliphatic hydrocarbon, norbornane diisocyanate, which is an alicyclic diisocyanate, or isophorone diisocyanate, provides excellent scratch resistance. It is preferable for obtaining a hard coat film.

  As said (meth) acrylate (a2), in order to provide four or more (meth) acryloyl groups to said urethane (meth) acrylate (A), what has two or more (meth) acryloyl groups should be used. Is preferred.

  Examples of the (meth) acrylate (a2) include trimethylolpropane di (meth) acrylate, ethylene oxide modified trimethylolpropane di (meth) acrylate, propylene oxide modified trimethylolpropane di (meth) acrylate, and glycerin di (meth). ) Acrylate, bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. it can. As the (meth) acrylate (a2), it is preferable to use pentaerythritol tri (meth) acrylate or dipentaerythritol penta (meth) acrylate for obtaining the hard coat film of the present invention having excellent scratch resistance. .

  The said (meth) acrylate (a2) can be used 1 type with respect to 1 type of the said aliphatic polyisocyanate (a1), or can also use 2 or more types together.

  The reaction between the aliphatic polyisocyanate (a1) and the (meth) acrylate (a2) can be carried out by a conventional urethanization reaction. The urethanization reaction is preferably performed in the 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 urethane (meth) acrylate (A) obtained by the urethanization reaction may be used alone or in combination of two or more. When two or more kinds are used as the urethane (meth) acrylate (A), urethane acrylate obtained using norbornane diisocyanate as the aliphatic polyisocyanate (a1) and isophorone diisocyanate as the aliphatic polyisocyanate (a1). It is preferable to use the urethane acrylate obtained in combination in combination in order to obtain the hard coat film of the present invention having excellent scratch resistance.

  Examples of the polyfunctional (meth) acrylate (B) having 3 or more (meth) acryloyl groups in the molecule that can be used in combination with the urethane (meth) acrylate (A) include trimethylolpropane tri (meth) acrylate, Ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, tris (2- (meth) acryloyl Oxyethyl) isocyanurate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaeryth Ritorutetora (meth) acrylate, dipentaerythritol penta (meth) acrylate, may be used dipentaerythritol hexa (meth) acrylate. The polyfunctional (meth) acrylate (B) can be used alone or in combination of two or more.

  As the polyfunctional (meth) acrylate (B), in order to further improve the scratch resistance of the hard coat layer (I-2) comprising the cured product of the active energy ray-curable composition, the (meth) The acryloyl group equivalent is 50 g / eq. -200 g / eq. In the range of 70 g / eq. -150 g / eq. In the range of 80 g / eq. -120 g / eq. The thing of the range is more preferable. The (meth) acryloyl group equivalent is 80 g / eq. -200 g / eq. Specific examples of the polyfunctional (meth) acrylate (B) in the range are pentaerythritol tetraacrylate (acroyl group equivalent: 88 g / eq.), Dipentaerythritol hexa (meth) acrylate (acroyl group equivalent: 118 g / eq). .) And the like.

  The mass ratio [(A) / (B)] of the urethane (meth) acrylate (A) and the polyfunctional (meth) acrylate (B) further increases the scratch resistance of the hard coat layer (I-2). In improving, it is preferably in the range of 90/10 to 10/90, more preferably in the range of 80/20 to 20/80, and further preferably in the range of 75/25 to 25/75. preferable.

  As the active energy ray-curable composition that can be used for forming the hard coat layer (I-2), in addition to those described above, one (meth) in the molecule is within the range not impairing the effects of the present invention. Those containing other (meth) acrylates such as mono (meth) acrylate having an acryloyl group and di (meth) acrylate having two (meth) acryloyl groups in the molecule can be used.

  When using the said other (meth) acrylate, the usage-amount is 40 mass parts or less with respect to a total of 100 mass parts of the said urethane (meth) acrylate (A) and the said polyfunctional (meth) acrylate (B). It is preferable that it is 20 parts by mass or less.

  As said active energy ray curable composition, what contains the photoinitiator which can start hardening reaction by irradiating an active energy ray can be used.

  Examples of the photopolymerization initiator 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, examples of the hydrogen abstraction type photopolymerization initiator include 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′-diethyl Aminobenzophenone compounds such as minobenzophenone; 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 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 the photopolymerization initiator and the 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. More preferably, it is 5 to 10 parts by mass. In the case where ionizing radiation such as electron beam, α ray, β ray, and γ ray is used as the active energy ray, it is not necessary to use a photopolymerization initiator or a photosensitizer.

  Further, the active energy ray curable composition, if necessary, a polymerization inhibitor, a surface conditioner, an antistatic agent, an antifoaming agent, a viscosity modifier, a light resistance stabilizer, a weather resistance stabilizer, a heat resistance stabilizer, Additives such as UV absorbers, antioxidants, leveling agents, organic pigments, inorganic pigments, pigment dispersants, silica beads, and organic beads; inorganic fillers such as silicon oxide, aluminum oxide, titanium oxide, zirconia, and antimony pentoxide An agent or the like can be blended. These other blends can be used alone or in combination of two or more.

  As a method for producing the hard coat film (I) in which the plastic substrate (I-1) and the hard coat layer (I-2) are laminated, for example, on one side or both sides of the plastic substrate (I-1), A method of applying a hard coat agent comprising the active energy ray-curable composition, drying, and then irradiating the application surface with active energy rays to form a hard coat layer (I-2) comprising the cured layer Is mentioned.

  Examples of the method for applying the active energy ray-curable composition to the plastic substrate (I-1) include die coating, micro gravure coating, gravure coating, roll coating, comma coating, air knife coating, kiss coating, spray coating, and coating. Examples include transfer coating, dip coating, spinner coating, wheeler coating, brush coating, silk screen solid coating, wire bar coating, and flow coating.

  Examples of active energy rays applied to the hard coating agent application surface include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. As an apparatus for irradiating the active energy ray, for example, in the case of ultraviolet rays, the generation source thereof is a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, an electrodeless lamp (fusion lamp), a chemical lamp, a black light. Lamps, mercury-xenon lamps, short arc lamps, helium / cadmium lasers, argon lasers, sunlight, LEDs and the like can be mentioned.

[Anti-fouling layer (II)]
The antifouling layer (II) constituting the hard coat film of the present invention is laminated on at least one side of the hard coat film (I). The antifouling layer (II) imparts excellent antifouling properties and slipperiness to the hard coat film of the present invention.

  The antifouling layer (II) preferably has a thickness of 50 nm or less in order to suppress generation of interference fringes and the like without reducing visibility. The antifouling layer (II) preferably has a thickness in the range of 1 nm to 30 nm in order to further improve the durability of the hard coat film of the present invention.

  The antifouling layer (II) constituting the hard coat film of the present invention comprises a cured product of an active energy ray-curable composition containing a fluorine atom-containing compound (II-1) having a polymerizable unsaturated double bond. The fluorine atom-containing compound (II-1) is contained in an amount of 10% by mass or more based on the total solid content of the active energy ray-curable composition.

  The antifouling layer (II) is an active energy ray containing a fluorine atom-containing compound (II-1) having a polymerizable unsaturated double bond on at least a part or all of one side of the hard coat film (I). It can be formed by applying and curing a curable composition.

  As the active energy ray-curable composition that can be used for forming the antifouling layer (II), for example, the fluorine atom-containing compound (II-1) having a polymerizable unsaturated double bond is used as the active energy ray-curable composition. What contains 10 mass% or more with respect to solid content of a composition can be used.

  The fluorine atom-containing compound (II-1) is in a range of 10% by mass to 95% by mass with respect to the total solid content of the active energy ray-curable composition used for forming the antifouling layer (II). It is preferable that it is contained, and it is more preferable that it is contained in the range of 70% by mass to 95% by mass for imparting excellent antifouling properties to the hard coat film of the present invention.

  As the fluorine atom-containing compound (II-1), for example, a fluorine atom-containing compound having a poly (perfluoroalkylene ether) chain can be used. It is preferable that the number of the polymerizable unsaturated double bonds which the said fluorine atom containing compound (II-1) has is 2-6, More preferably, it is 4-6. By using a fluorine atom-containing compound having a polymerizable unsaturated double bond within the above range, an antifouling layer (II) having excellent durability and antifouling properties can be formed.

  Examples of the poly (perfluoroalkylene ether) chain include those having a structure in which divalent fluorocarbon groups 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.

In the general formula (1), X is the following formulas (1-1) to (1-5). X may be one of the following formulas (1-1) to (1-5), or two or more of the following formulas (1-1) to (1-5). You may have. For example, the structure having two or more of the following formulas (1-1) to (1-5) as X is represented by — (CF ₂ CF ₂ —O) n— (CF ₂ —O) n—. Such a structure is mentioned. In the case where two or more types of structures represented by the formulas (1-1) to (1-5) are included as X, it has a random structure or a block structure composed of structural units of — (X—O) —. Also good. N is an integer of 2 to 200 representing a repeating unit.

  Among the poly (perfluoroalkylene ether) chains, in order to further improve the antifouling property of the hard coat film of the present invention, the perfluoromethylene group represented by the formula (1-1) and the formula ( A poly (perfluoroalkylene ether) chain having a perfluoroethylene group represented by 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 the fluorine atom-containing compound (II-1), it is particularly preferable to use a compound having a cyclopolysiloxane structure.

  Examples of the fluorine atom-containing compound (II-1) include compounds having a structure represented by the following general formula (2).

(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.)

  As the fluorine atom-containing compound (II-1), among the cyclopolysiloxane structures, those having a cyclotetrasiloxane structure in which m in the general formula (2) is 3 are preferably used.

The divalent linking group (R ³ ) that bonds 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 following general formula (3 ).

(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.

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

  Specifically, as the fluorine atom-containing compound (II-1), a compound represented by the following formula (5) is preferably used.

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

The fluorine atom-containing compound (II-1) is obtained by, for example, reacting a compound having an allyl group at both ends of a poly (perfluoroalkylene ether) chain with a cyclopolysiloxane compound having a hydrosilyl group in the presence of a platinum-based catalyst, A step of obtaining a compound having a cyclopolysiloxane structure at both ends of a poly (perfluoroalkylene ether) chain (step [1]),
The step of reacting the compound obtained in step [1] with allyloxyalkanol (step [2]), the reaction product obtained in step [2], and the (meth) acrylate having an isocyanate group are reacted. It can be manufactured through the steps (step [3]).

  Moreover, as said fluorine atom containing compound (II-1), what has an isocyanurate frame | skeleton as shown, for example by following formula 6 other than what has the said cyclopolysiloxane structure can also be used.

  (N in the formula (6) represents an integer of 1 or more.)

  As the active energy ray-curable composition for forming the antifouling layer (II), in addition to the fluorine atom-containing compound (II-1), a silicon atom-containing compound having a polymerizable unsaturated double bond (II- It is preferable to use a material containing 2) in order to obtain a hard coat film excellent in antifouling property and slipperiness.

  As the silicon atom-containing compound (II-2), a conventionally known compound can be used, but it is particularly preferable to use a compound having excellent slipperiness, for example, a silicon atom-containing compound having a dimethylsiloxane chain. It is preferable to do.

  It is preferable that the number of the polymerizable unsaturated double bonds which the said silicon atom containing compound (II-2) has is 1-6. By using the silicon atom-containing compound having a polymerizable unsaturated double bond within the above range, the antifouling layer (II) having excellent durability and slipperiness can be formed.

  As the silicon atom-containing compound (II-2), specifically, compounds as shown below can be used.

  (N in the formula (7) represents an integer of 1 or more.)

  As the silicon atom-containing compound (II-2), use of a silicon atom-containing compound having a dimethylsiloxane chain having a number average molecular weight of 100 to 50,000 is more preferable for obtaining a hard coat film having excellent slipperiness. preferable.

  Examples of the silicon atom-containing compound having a dimethylsiloxane chain include Kyoeisha Chemical Co., Ltd. Polyflow Series (silicone surface conditioner), BYK Japan Japan BYK series (silicone surface conditioner), Enomoto Kasei Co., Ltd. DISPARLON series (silicone slip agent) manufactured by Shin-Etsu Chemical Co., Ltd., silicone paint additive, etc. can be used.

  It is preferable that the said silicon atom containing compound (II-2) is contained in the range of 10 mass parts-1000 mass parts with respect to 100 mass parts of the said fluorine atom containing compound (II-1), and 100 mass parts-500. Inclusion in the range of parts by mass further improves the slipperiness of the antifouling layer (II) constituting the hard coat film, and the appearance due to repelling or the like when forming the antifouling layer (II) It is more preferable in preventing defects.

  As the active energy ray-curable composition for forming the antifouling layer (II), in addition to the above, (meth) acrylate (II-3) having two or more (meth) acryloyl groups as necessary. In order to further improve the durability, it is preferable to use a material that contains.

  Examples of the (meth) acrylate (II-3) include trimethylolpropane di (meth) acrylate, ethylene oxide modified trimethylolpropane di (meth) acrylate, propylene oxide modified trimethylolpropane di (meth) acrylate, and glycerin di. (Meth) acrylate, bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol Hexa (meth) acrylate or the like can be used.

  Said (meth) acrylate (II-3) is 0.1 mass part-50 masses with respect to 100 mass parts of total mass of the said fluorine atom containing compound (II-1) and the said silicon atom containing compound (II-2). It is preferably included in the range of parts.

  The active energy ray-curable composition used for forming the antifouling layer (II) contains a photopolymerization initiator capable of initiating a curing reaction by irradiation with active energy rays, a photosensitizer, and the like. Things can be used.

  Examples of the photopolymerization initiator 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. Among them, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one is preferable for the thin film such as the antifouling layer of the present invention from the viewpoint of curability.

  On the other hand, examples of the hydrogen abstraction type photopolymerization initiator include 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′-diethyl Aminobenzophenone compounds such as minobenzophenone; 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 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 the photopolymerization initiator and the 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. More preferably, it is 5 to 10 parts by mass. In the case where ionizing radiation such as electron beam, α ray, β ray, and γ ray is used as the active energy ray, it is not necessary to use a photopolymerization initiator or a photosensitizer.

  Further, the active energy ray curable composition, if necessary, a polymerization inhibitor, a surface conditioner, an antistatic agent, an antifoaming agent, a viscosity modifier, a light resistance stabilizer, a weather resistance stabilizer, a heat resistance stabilizer, Additives such as UV absorbers, antioxidants, leveling agents, organic pigments, inorganic pigments, pigment dispersants, silica beads, and organic beads; inorganic fillers such as silicon oxide, aluminum oxide, titanium oxide, zirconia, and antimony pentoxide An agent or the like can be blended. These other blends can be used alone or in combination of two or more.

  Examples of the method for forming the antifouling layer (II) include a hard coat comprising the active energy ray-curable composition on a part or all of the hard coat layer (I-2) of the hard coat film (I). Examples include a method of applying an agent, drying, and then irradiating the application surface with an active energy ray to form an antifouling layer (II) comprising a cured layer thereof.

  Examples of the method for applying the hard coat agent comprising the active energy ray-curable composition to the hard coat layer (I-2) of the hard coat film (I) include microgravure coat, gravure coat, roll coat, Examples include kiss coat, spray coat, transfer coat, dip coat, spinner coat, brush coat, wire bar coat, and flow coat.

  Examples of the active energy rays applied to the application surface of the active energy ray-curable composition include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. As an apparatus for irradiating the active energy ray, for example, in the case of ultraviolet rays, the generation source thereof is a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, an electrodeless lamp (fusion lamp), a chemical lamp, a black light. Lamps, mercury-xenon lamps, short arc lamps, helium / cadmium lasers, argon lasers, sunlight, LEDs and the like can be mentioned.

[Decoration layer]
The hard coat film of the present invention can be used as a decorative film by providing a decorative layer on one side or part of both sides.

  The said decoration layer can be provided by printing on the surface by a general printing method. Examples of the printing method include silk printing, screen printing, thermal transfer printing, and gravure printing.

  The decorative layer is not particularly limited as long as it imparts various design properties to the hard coat film, for example, characters and figures visually recognized around the image display unit when used as an image display panel, or Examples thereof include a black bordered decorative layer provided in a frame shape on the image display unit.

  The thickness of the decorative layer is preferably 30 μm or less, more preferably 1 μm to 15 μm, and particularly preferably 2 μm to 10 μm. By setting it as the decorating layer of the said thickness, it is hard to produce a suitable color omission and a printing defect, and it becomes easy to obtain suitable designability.

  The decorative layer can be provided at any location on one or both sides of the hard coat film, but when it is provided on the surface of the antifouling layer (II), a part of the antifouling layer (II) is exposed on the surface. It is provided as follows. Moreover, when using it for the display of an image display apparatus, it is normally provided in places other than an image display part.

[Adhesive layer]
The hard coat film of the present invention can be used as a protective film by providing an adhesive layer on one side or part of both sides.

  The pressure-sensitive adhesive layer is formed by a method of applying a pressure-sensitive adhesive directly on the surface opposite to the antifouling layer (II) constituting the hard-coated film, or a method of attaching a pressure-sensitive adhesive tape to the surface opposite to the hard-coated film. A pressure-sensitive adhesive layer can be provided.

  The thickness of the pressure-sensitive adhesive layer constituting the protective film of the present invention is preferably in the range of 5 μm to 50 μm, more preferably in the range of 8 μm to 30 μm, and still more preferably in the range of 10 μm 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, or 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 (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% by mass to 99% by mass. 90 mass% to 96 mass% is more preferable. 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, and 2- (perhydrophthalimide-N. -Yl) ethyl acrylate 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% by mass to 20% by mass of the monomer component constituting the acrylic copolymer, and preferably 1% by mass to 13% by mass. Is more preferable, and it is more preferable that it is 1.5 mass%-8 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. As addition amount of a crosslinking agent, it is preferable to adjust so that the gel fraction of an adhesive layer may be 25 mass%-80 mass%, and it is more preferable to adjust so that it may become 40 mass%-75 mass%, 50 It is most preferable to adjust so that it may become mass%-70 mass%. By adjusting the gel fraction to the above range, it is possible to suppress a decrease in surface pencil hardness when the protective film of the present invention is applied to, for example, a display of an image display device, and the adhesiveness is sufficient. Can do. 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 the addition amount of the tackifier resin, when the adhesive resin is an acrylic copolymer, it is preferably added in the range of 10 parts by mass to 60 parts by mass with respect to 100 parts by mass of the acrylic copolymer. . Furthermore, when importance is attached to adhesiveness, it is preferable to add in the range of 20 mass parts-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 the 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.

[Embodiment]
Since the hard coat film, decorative film and protective film of the present invention are excellent in antifouling property, slipperiness and durability, they are suitable for an image display unit of an image display device such as a liquid crystal display (LCD) or an organic EL display. Applicable to. 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 apparatus, it is effective to prevent damage and to prevent scattering when the transparent panel is damaged by being attached to the surface of the transparent panel.

Hereinafter, the present invention will be described more specifically with reference to examples.
(Synthesis Example 1: Synthesis of fluorine atom-containing compound (II-1-1))

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 (11), 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. Here, 0.442 parts by mass of a toluene solution of chloroplatinic acid / vinylsiloxane complex (containing 1.1 × 10 ⁻⁶ mol as platinum alone) 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 (12). A perfluoropolyether compound which was a colorless and transparent liquid was obtained.

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

(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 represented by the formula (12), 7.05 parts by mass of 2-allyloxyethanol, 50 parts by mass of m-xylene hexafluoride, and chloroplatinic acid / vinyl 0.0442 parts by mass of a siloxane complex toluene solution (containing 1.1 × 10 ⁻⁷ mol as platinum 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, followed by activated carbon treatment, whereby the following formula (13) A perfluoropolyether compound which is a pale yellow transparent liquid represented by

(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 represented by the formula (13), 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 atom-containing compound (II-1-1), which is a pale yellow paste represented by the following formula (14), 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 atom-containing compound (II-1-1), and a fluorine atom-containing compound having a nonvolatile content of 20% by mass (II-1-1) A solution was prepared.

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

(Fluorine atom-containing compound (II-1-2))
Daikin Industries, Ltd. OPTOOL DAC-HP (nonvolatile content 20 mass%) was used as the fluorine atom-containing compound (II-1-2) solution.

(Synthesis Example 2: Synthesis of urethane acrylate (a1-1))
A flask equipped with a stirrer, gas introduction tube, cooling tube and thermometer was charged with 250 parts by mass of butyl acetate, 206 parts by mass of norbornane diisocyanate, 0.5 parts by mass of p-methoxyphenol and 0.5 parts by mass of dibutyltin diacetate. The temperature was raised to 70 ° C. while blowing air, and then 795 parts by mass of a mixture of pentaerythritol triacrylate (PE3A) and pentaerythritol tetraacrylate (PE4A) (PE3A / PE4A = 75/25 (mass ratio)) for 1 hour. It was dripped over. After completion of the dropwise addition, the mixture is reacted at 70 ° C. for 3 hours, and further reacted until the infrared absorption spectrum of 2250 cm ⁻¹ showing the isocyanate group disappears, whereby urethane acrylate (a1-1) having 6 acryloyl groups in the molecule is obtained. A butyl acetate solution having a nonvolatile content of 80% by mass was obtained. This solution contained 19.9% by mass of PE4A in addition to urethane acrylate (a1-1) in the nonvolatile content.

(Synthesis Example 3: 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 the dropwise addition, the mixture is reacted at 70 ° C. for 3 hours, and further reacted until the infrared absorption spectrum of 2250 cm ⁻¹ showing the isocyanate group disappears, whereby urethane acrylate (a1-2) having 6 acryloyl groups in the molecule is obtained. A non-volatile content 80% by mass solution was obtained. This solution contained 19.5% by mass of PE4A in addition to urethane acrylate (a1-2) in the nonvolatile content.

(Synthesis Example 4: Synthesis of urethane acrylate (a1-3))
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 369 mass parts of 369 parts by mass of bis (2-acryloyloxyethyl) hydroxyethyl isocyanurate and PE3A / PE4A (PE3A / PE4A = 75/25 (mass ratio)). Were added dropwise over 1 hour. After completion of the dropwise addition, 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 showing the isocyanate group disappears, and the urethane acrylate having 4 to 6 acryloyl groups in the molecule (a1-3 ) Containing a non-volatile content of 80% by mass. This solution contained 10.1% by mass of PE4A in addition to urethane acrylate (a1-3) in the nonvolatile content.

(Preparation Example 1: Preparation of silicon atom-containing compound (II-2-1) solution)
20 parts by mass of a compound having a polydimethylsiloxane skeleton represented by the following formula (15) having a number average molecular weight of 1000 as a silicon atom-containing compound (II-2-1) having a polymerizable unsaturated double bond, and ethyl acetate as a diluent solvent 80 parts by mass was mixed and stirred for 10 minutes to obtain a silicon atom-containing compound (II-2-1) solution having a nonvolatile content of 20% by mass.

(In the formula, n is 6 to 12.)

(Preparation Example 2: Preparation of silicon atom-containing compound (II-2-2) solution)
20 parts by mass of a compound having a polydimethylsiloxane skeleton represented by the following formula (16) having a number average molecular weight of 5000 as a silicon atom-containing compound (II-2-2) having a polymerizable unsaturated double bond, and ethyl acetate as a diluent solvent By mixing 80 parts by mass and stirring for 10 minutes, a silicon atom-containing compound (II-2-2) solution having a nonvolatile content of 20% by mass was obtained.

(In the formula, n is 60 to 80.)

(Preparation Example 3: Preparation of silicon atom-containing compound (II-2-3) solution)
20 parts by mass of a compound having a polydimethylsiloxane skeleton represented by the following formula (17) having a number average molecular weight of 1000 as a silicon atom-containing compound (II-2-3) having a polymerizable unsaturated double bond and ethyl acetate as a diluent solvent By mixing 80 parts by mass and stirring for 10 minutes, a silicon atom-containing compound (II-2-3) solution having a nonvolatile content of 20% by mass was obtained.

(In the formula, n is 6 to 12.)

(Preparation Example 4: Preparation of silicon atom-containing compound (II-2-4) solution)
20 parts by mass of a compound having a polydimethylsiloxane skeleton represented by the following formula (18) having a number average molecular weight of 5000 as a silicon atom-containing compound (II-2-4) having a polymerizable unsaturated double bond, and ethyl acetate as a diluent solvent By mixing 80 parts by mass and stirring for 10 minutes, a silicon atom-containing compound (II-2-4) solution having a nonvolatile content of 20% by mass was obtained.

(In the formula, n is 60 to 80.)

(Preparation Example 5: Preparation of silicon atom-containing compound (II-2-5) solution)
20 parts by mass of a compound having a polydimethylsiloxane skeleton represented by the following formula (19) having a number average molecular weight of 14,000 as a silicon atom-containing compound (II-2-5) having a polymerizable unsaturated double bond and ethyl acetate as a diluting solvent By mixing 80 parts by mass and stirring for 10 minutes, a silicon atom-containing compound (II-2-5) solution having a nonvolatile content of 20% by mass was obtained.

(In the formula, n is 170 to 200.)

  Urethane acrylates (a1-1) to (a1-3) obtained above and fluorine atom-containing compound solutions (II-1-1) and (II-1-2), silicon atom-containing compound solutions (II-2- An active energy ray-curable composition was prepared using 1) to (II-2-5) as follows.

Example 1
31.3 parts by mass of the solution containing urethane acrylate (a1-1) obtained in Synthesis Example 2 (including 20 parts by mass of urethane acrylate (a1-1) and 5 parts by mass of PE4A), obtained in Synthesis Example 3. 31.3 parts by mass of a solution containing urethane acrylate (a1-2) (including 20.1 parts by mass of urethane acrylate (a1-2) and 4.9 parts by mass of PE4A), urethane acrylate obtained in Synthesis Example 4 ( a mixture of 25 parts by mass (including 18 parts by mass of urethane acrylate (a1-3) and 2 parts by mass of PE4A), dipentaerythritol hexaacrylate (DPHA) and dipentaerythritol pentaacrylate (DPPA). (DPHA / DPPA = 60/40 (mass ratio)) 30 parts by mass, and photopolymerization initiator (BASF Japan Ltd.) Irgacure 184 ", 1-hydroxycyclohexyl phenyl ketone) 4.5 parts by mass is uniformly stirred and then diluted with ethyl acetate to form an active energy ray-curable composition for forming a hard coat layer having a nonvolatile content of 40% by mass (1 ) Was prepared.

The hard-coat layer-forming active energy ray-curable composition (1) is applied on a polyester film (Toyobo Cosmo Shine A4300, thickness 100 μm) using a wire bar (# 40) at 60 ° C. After drying for 1 minute, using an ultraviolet irradiation device (“MIDN-042-C1” manufactured by Eye Graphics Co., Ltd., lamp: 120 W / cm, high-pressure mercury lamp) under an air atmosphere, the ultraviolet ray is irradiated at an irradiation light amount of 0.1 J / cm ² . Was applied to obtain a hard coat film (Ia) having a hard coat layer having a thickness of 10 μm.

The hard coat film (Ia) is placed on a glass plate having a thickness of 1 mm so that the hard coat layer is on the upper surface, and a Fischer Scope H100CXY manufactured by Fisher Instruments Co., Ltd. is used. Martens hardness was measured with a Vickers indenter at a maximum indentation depth of 1 μm, a maximum load of 15 mN, and a load time of 15 seconds. As a result, the Martens hardness of the hard coat film (Ia) was 310 N / mm ² .

  Next, the fluorine atom-containing compound (II-1-1) solution obtained in Synthesis Example 1 is 100 parts by mass in solids, the silicon atom-containing compound (II-2-1) solution is 10 parts by mass in solids, DPHA And 3 parts by mass of a mixture of DPPA (DPHA / DPPA = 60/40 (mass ratio)) and a photopolymerization initiator (“Irgacure I907” manufactured by BASF Japan Ltd., 2-methyl-1- (4-methylthiophenyl)- 2-Morpholinopropan-1-one) is stirred uniformly and then diluted with ethyl acetate to form an antifouling layer-forming active energy ray-curable composition having a nonvolatile content of 0.1% by mass ( 2) was prepared.

The anti-stain layer forming active energy ray-curable composition (2) is formed on the hard coat layer constituting the hard coat film (Ia) so that the anti-stain layer has a thickness of 10 nm. Apply using a bar, dry at 60 ° C. for 1 minute, and then irradiate with UV light in an atmosphere with an oxygen concentration of 1000 ppm or less (“MIDN-042-C1” manufactured by Eye Graphics Co., Ltd., lamp: 120 W / cm, high-pressure mercury lamp) Was used to obtain an antifouling hard coat film having an antifouling layer by irradiating ultraviolet rays at an irradiation light amount of 0.3 J / cm ² .

  Hereinafter, according to the compounding quantity of Table 1, Examples 2-20 and the antifouling hard coat film of Comparative Examples 1 and 2 were created.

(Example 2)
The antifouling hard coat film was prepared in the same manner as in Example 1 except that the amount (solid content) of the mixture containing DPHA and DPPA contained in the antifouling layer was changed from 3 parts by mass to 10 parts by mass. Produced.

Example 3
The antifouling hard coat film was prepared in the same manner as in Example 1 except that the amount (solid content) of the mixture containing DPHA and DPPA contained in the antifouling layer was changed from 3 parts by mass to 15 parts by mass. Produced.

Example 4
The antifouling hard coat film was prepared in the same manner as in Example 1 except that the amount (solid content) of the mixture containing DPHA and DPPA contained in the antifouling layer was changed from 3 parts by mass to 30 parts by mass. Produced.

(Example 5)
The antifouling hard coat film was prepared in the same manner as in Example 1 except that the amount (solid content) of the mixture containing DPHA and DPPA contained in the antifouling layer was changed from 3 parts by mass to 50 parts by mass. Produced.

(Example 6)
An antifouling hard coat film was produced in the same manner as in Example 1 except that the amount of the silicon atom-containing compound (II-2-1) solution was changed from 10 parts by mass to 100 parts by mass in terms of solid content. .

(Example 7)
The amount of the silicon atom-containing compound (II-2-1) solution used is changed from 10 parts by mass to 100 parts by mass in terms of solid content, and the amount of the mixture containing DPHA and DPPA contained in the antifouling layer (solid The antifouling hard coat film was produced in the same manner as in Example 1 except that the component (min) was changed from 3 parts by mass to 10 parts by mass.

(Example 8)
The usage amount of the fluorine atom-containing compound (II-1-1) solution was changed from 100 parts by mass to 80 parts by mass in terms of solid content, and the usage amount of the silicon atom-containing compound (II-2-1) solution was changed to 10 in terms of solid content. Example 1 except that the amount used (solid content) of the mixture containing DPHA and DPPA contained in the antifouling layer was changed from 3 parts by weight to 10 parts by weight from 30 parts by weight to 30 parts by weight. An antifouling hard coat film was prepared in the same manner as described above.

Example 9
Antifouling was carried out in the same manner as in Example 1 except that 100 parts by mass of the silicon atom-containing compound (II-2-2) solution was used in solid content instead of the silicon atom-containing compound (II-2-1) solution. A hard coat film was produced.

(Example 10)
Antifouling was conducted in the same manner as in Example 1 except that 500 parts by mass of the silicon atom-containing compound (II-2-2) solution was used in solid content instead of the silicon atom-containing compound (II-2-1) solution. A hard coat film was produced.

(Example 11)
Antifouling was carried out in the same manner as in Example 1 except that 100 parts by mass of the silicon atom-containing compound (II-2-3) solution was used in solid content instead of the silicon atom-containing compound (II-2-1) solution. A hard coat film was produced.

(Example 12)
Antifouling was carried out in the same manner as in Example 1 except that 100 parts by mass of the silicon atom-containing compound (II-2-4) solution was used in solid content instead of the silicon atom-containing compound (II-2-1) solution. A hard coat film was produced.

(Example 13)
Antifouling was conducted in the same manner as in Example 1 except that 500 parts by mass of the silicon atom-containing compound (II-2-4) solution was used as a solid content instead of the silicon atom-containing compound (II-2-1) solution. A hard coat film was produced.

(Example 14)
Antifouling was conducted in the same manner as in Example 1 except that 100 parts by mass of the silicon atom-containing compound (II-2-5) solution was used in solid content instead of the silicon atom-containing compound (II-2-1) solution. A hard coat film was produced.

(Example 15)
Antifouling was conducted in the same manner as in Example 1 except that 500 parts by mass of the silicon atom-containing compound (II-2-5) solution was used as a solid content instead of the silicon atom-containing compound (II-2-1) solution. A hard coat film was produced.

(Example 16)
Antifouling was conducted in the same manner as in Example 1 except that 100 parts by mass of the fluorine atom-containing compound (II-1-2) solution was used in solid content instead of the fluorine atom-containing compound (II-1-1) solution. A hard coat film was produced.

(Example 17)
Instead of the fluorine atom-containing compound (II-1-1) solution, 100 parts by mass of the fluorine atom-containing compound (II-1-2) solution is used in solid content, and contains DPHA and DPPA contained in the antifouling layer An antifouling hard coat film was produced in the same manner as in Example 1 except that the amount of the mixture used (solid content) was changed from 3 parts by mass to 10 parts by mass.

(Example 18)
Instead of the fluorine atom-containing compound (II-1-1) solution, 100 parts by mass of the fluorine atom-containing compound (II-1-2) solution is used as a solid content, and the silicon atom-containing compound (II-2-1) An antifouling hard coat film was produced in the same manner as in Example 1 except that the amount of the solution used was changed from 10 parts by mass to 100 parts by mass in terms of solid content.

(Example 19)
An antifouling hard coat film was produced in the same manner as in Example 1 except that the silicon atom-containing compound (II-2-1) solution was not used.

(Example 20)
Without using the silicon atom-containing compound (II-2-1) solution, the amount (solid content) of the mixture containing DPHA and DPPA contained in the antifouling layer is changed from 3 parts by mass to 10 parts by mass. Except for this, an antifouling hard coat film was produced in the same manner as in Example 1.

(Comparative Example 1)
An antifouling hard coat film was produced in the same manner as in Example 1 except that the amount of the silicon atom-containing compound (II-2-1) solution used was 10 to 1400 parts by mass in terms of solid content.

(Comparative Example 2)
Without using the fluorine atom-containing compound (II-1-1) solution, the amount of use (solid content) of the mixture containing DPHA and DPPA contained in the antifouling layer is changed from 3 parts by mass to 10 parts by mass. Except for this, an antifouling hard coat film was produced in the same manner as in Example 1.

(Comparative Example 3)
31.3 parts by mass of the solution containing urethane acrylate (a1-1) obtained in Synthesis Example 2 (including 20 parts by mass of urethane acrylate (a1-1) and 5 parts by mass of PE4A), obtained in Synthesis Example 3. 31.3 parts by mass of a solution containing urethane acrylate (a1-2) (including 20.1 parts by mass of urethane acrylate (a1-2) and 4.9 parts by mass of PE4A), urethane acrylate obtained in Synthesis Example 4 ( 25 parts by mass of a solution containing a1-3) (including 18 parts by mass of urethane acrylate (a1-3) and 2 parts by mass of PE4A), a mixture of DPHA and DPPA (DPHA / DPPA = 60/40 (mass ratio)) 30 Parts by mass, 1.5 parts by mass of a 20% by mass solution of the fluorine atom-containing compound solution (II-1-1) (0.3 parts by mass as the fluorine atom-containing compound (II-1-1)), and photopolymerization Initiator (“Irgacure 184” manufactured by BASF Japan Ltd., 1-hydroxycyclohexyl phenyl ketone) is uniformly stirred and then diluted with ethyl acetate to form a hard coat layer having a nonvolatile content of 40% by mass. An active energy ray-curable composition was prepared.

The active energy ray-curable composition for forming a hard coat layer is applied to a polyester film (Toyobo Cosmo Shine A4300, thickness 100 μm) using a wire bar (# 40) and dried at 60 ° C. for 1 minute. Thereafter, using an ultraviolet irradiation device (“MIDN-042-C1” manufactured by Eye Graphics Co., Ltd., lamp: 120 W / cm, high-pressure mercury lamp) under an atmosphere having an oxygen concentration of 1000 ppm or less at an irradiation light amount of 0.5 J / cm ² . A hard coat film having a hard coat layer having a thickness of 10 μm was obtained by irradiation with ultraviolet rays.

(Comparative Example 4)
A hard coat layer was produced in the same manner as in Comparative Example 3 except that the fluorine atom-containing compound (II-1-2) solution was used instead of the fluorine atom-containing compound (II-1-1) solution used in Comparative Example 3. A hard coat film having was obtained.

(Comparative Example 5)
In the same manner as in Comparative Example 3 except that the silicon atom-containing compound (II-2-1) solution was used instead of the fluorine atom-containing compound (II-1-2) solution used in Comparative Example 3, the hard coat layer was used. A hard coat film having was obtained.

[Evaluation of repellency of hard coat film surface]
The surface of the outermost layer (antifouling layer) constituting the hard coat film obtained in the examples and comparative examples was observed under a three-wavelength fluorescent lamp to confirm the presence or absence of repelling. In addition, about the hard coat film obtained in Comparative Examples 3-5 which has not provided the antifouling layer, the presence or absence of the repellency of the outermost surface was evaluated. Moreover, since it was clear that the hard coat film in which the repellency was confirmed was insufficient in slipping property, antifouling property and durability, the following evaluation was not performed. In addition, repellency means that when an antifouling layer is applied, the active energy ray-curable composition solution for forming the antifouling layer is locally concentrated on the hard coat layer to form a non-uniform coating film.

[Slidability Evaluation Method 1 (Evaluation by Dynamic Friction Coefficient)]
The surface of the outermost layer (antifouling layer) constituting the hard coat film obtained in the examples and comparative examples was adhered to both ends with a cotton canvas # 11 on the tip of a 10 mm diameter stainless steel round bar (weight approximately 82 g). The load at the time of rubbing at a speed of 1000 mm / min with a friction element fixed with a tape was measured, and the dynamic friction coefficient was calculated. In addition, about the hard coat film obtained in Comparative Examples 3-5 which has not provided the antifouling layer, the slip property of the outermost surface was evaluated.

[Evaluation method 2 of slipperiness]
From the slipperiness when rubbing the surface of the outermost layer (antifouling layer) constituting the hard coat film obtained in Examples and Comparative Examples with Bencott (manufactured by Asahi Kasei Fibers Co., Ltd.), the slipperiness according to the following criteria Evaluated. In addition, about the hard coat film obtained in Comparative Examples 3-5 which has not provided the antifouling layer, the slip property of the outermost surface was evaluated.

  A: Glide very well.

  ○: Slip well.

  Δ: It is difficult to slip.

  X: It does not slip so much.

[Anti-fouling evaluation method (fingerprint resistance)]
From the number of times of wiping when the index finger was pressed on the surface of the outermost surface (antifouling layer) of the hard coat film obtained in Examples and Comparative Examples for 10 seconds under a load of 500 g and wiped with Bencott (Asahi Kasei Fibers Corporation), Fingerprint resistance was evaluated according to the following criteria. In addition, about the hard coat film obtained in Comparative Examples 3-5 which has not provided the antifouling layer, the antifouling property of the outermost surface was evaluated.

  A: Fingerprints can be wiped out 5 times or less.

  ○: The fingerprint can be wiped off 6 to 10 times.

  Δ: The fingerprint can be wiped off in less than 11 to 20 times.

  X: It takes 21 times or more to wipe off the fingerprint.

[Durability Evaluation Method (Abrasion Resistance)]
The outermost surface (antifouling layer) of the hard coat film obtained in Examples and Comparative Examples was fixed to a flat friction tester (Imoto Seisakusho Co., Ltd.) with a jig, and a load of 500 g / cm using steel wool # 0000. ^2. The scratched state of the test piece after a stroke of 100 mm, a speed of 30 times / min, and a reciprocating 3000 times was visually observed, and the scratch resistance was evaluated according to the following criteria. In addition, about the hard coat film obtained in Comparative Examples 3-5 which has not provided the antifouling layer, the durability of the outermost surface was evaluated.

  A: Not scratched.

  ○: Less than 10 scratches are attached.

  X: Ten or more scratches are attached.

Claims (11)

A hard coat film in which an antifouling layer (II) is laminated on at least one side of the hard coat film (I), wherein the antifouling layer (II) is a fluorine atom-containing compound (II) having a polymerizable unsaturated double bond -1) comprising a cured product of an active energy ray-curable composition, wherein the fluorine atom-containing compound (II-1) is 10% by mass or more based on the total amount of solid content of the active energy ray-curable composition. A hard coat film characterized by being included. The hard coat film according to claim 1, wherein the thickness of the hard coat film (I) is 180 µm or less and the thickness of the antifouling layer (II) is 50 nm or less. The hard coat film according to claim 1 or 2, wherein the hard coat film (I) is obtained by laminating a hard coat layer (I-2) on a surface of a plastic substrate (I-1). The Martens hardness measured by pushing a Vickers indenter with a corner angle of 136 ° into the surface of the hard coat layer (I-2) constituting the hard coat film (I) with a load of 15 mN is 280 N / mm ^{2 to} 500 N / the hard coat film according to claim 3 in the range of mm ^2. The hard coat film according to claim 3 or 4, wherein the plastic substrate (I-1) has a thickness of 50 µm to 150 µm, and the hard coat layer (I-2) has a thickness of 5 µm to 25 µm. . The antifouling layer (II) contains a fluorine atom-containing compound (II-1) having a polymerizable unsaturated double bond and a silicon atom-containing compound (II-2) having a polymerizable unsaturated double bond. The hard coat film according to claim 1, comprising a cured product of the energy beam curable composition. The hard coat film according to claim 6, wherein the silicon atom-containing compound (II-2) is contained in a range of 10 parts by mass to 1000 parts by mass with respect to 100 parts by mass of the fluorine atom-containing compound (II-1). The antifouling layer (II) is a fluorine atom-containing compound (II-1) having a polymerizable unsaturated double bond, a silicon atom-containing compound (II-2) having a polymerizable unsaturated double bond, and 2 It consists of hardened | cured material of the active energy ray-curable composition containing the (meth) acrylate (II-3) which has a 1 or more (meth) acryloyl group, The any one of Claims 1-5. Hard coat film. A decorative film having a decorative layer on a part or all of one side or both sides of the hard coat film according to claim 1. A protective film comprising a pressure-sensitive adhesive layer on one or both sides of the hard coat film according to claim 1 or the decorative film according to claim 9. An image display device in which the decorative film according to claim 9 or the protective film according to claim 10 and an image display module are laminated.