WO2015098495A1

WO2015098495A1 - Hard coat film and information display device

Info

Publication number: WO2015098495A1
Application number: PCT/JP2014/082509
Authority: WO
Inventors: 佳美杉浦; 佑輔高橋; 大亮渡辺; 詩織高石; 茂年西澤
Original assignee: Dic株式会社
Priority date: 2013-12-24
Filing date: 2014-12-09
Publication date: 2015-07-02
Also published as: TW201531403A; JP5939449B2; JPWO2015098495A1

Abstract

The present invention addresses the problem of providing a hard coat film which exhibits excellent scratch resistance and has such a hardness that prevents the formation of a dent or the like even if a touch pen or the like is used for operation. The present invention relates to a hard coat film which is characterized by being obtained by sequentially laminating, on at least one surface of a transparent base, a first hard coat layer (A) containing a filler and a second hard coat layer (B) that is formed using a hard coat agent (b2) which contains an active energy ray-curable compound (b1) having a fluorine atom and a silicon atom.

Description

Hard coat film and information display device

The present invention relates to a hard coat film that can be used in fields such as manufacturing scenes of information display devices, for example.

Smaller electronic terminals such as mobile computers, electronic notebooks, and mobile phones are required to be further reduced in size and thickness. Accordingly, the information display device installed in the small electronic terminal is also required to be small and thin.

Among the information display devices, an information display device equipped with a so-called touch panel function is usually used for the purpose of preventing the information display unit from being damaged or damaged when operated using a touch pen or the like. In many cases, a hard coat film or the like is provided on the upper surface of the display portion.

Examples of the hard coat film include a polyfunctional (meth) acrylate (A) having two or more (meth) acryloyl groups in the molecule, and a urethane (meth) having two (meth) acryloyl groups in the molecule. An ultraviolet curable hard coat resin composition for a film containing acrylate (B-1) and / or epoxy (meth) acrylate (B-2) and colloidal silica (C) having a primary particle size of 1 nm to 200 nm is used. The hard coat film obtained by this is known (for example, refer patent document 1).

However, when the operation with the touch pen or the like is repeatedly performed, the information display unit may be dented or damaged.

JP 2009-24168 A

The problem to be solved by the present invention is, for example, provided with a level of hardness that does not cause dents or the like of the information display unit even when an operation using a touch pen or the like is repeated, and has excellent scratch resistance. It is to provide a hard coat film.

The present invention provides a hard coat containing a first hard coat layer (A) containing a filler and an active energy ray-curable compound (b1) having a fluorine atom and a silicon atom on at least one surface of a transparent substrate. The second hard coat layer (B) formed using the agent (b2) is laminated in order.

The hard coat film of the present invention has the above-described configuration, and has a hardness level that does not cause dents or the like in the information display portion even when the operation with a touch pen or the like is repeated, for example. Since it has scratch resistance, it can be used, for example, in the manufacture of information display devices constituting screen panels and electronic terminals.

Also, the hard coat film of the present invention can maintain excellent slipperiness and antifouling properties for a long period of time, and therefore can be used for manufacturing information display devices constituting screen panels and electronic terminals.

The hard coat film of the present invention comprises a first hard coat layer (A) containing a filler and an active energy ray-curable compound (b1) having a fluorine atom and a silicon atom on at least one surface of a transparent substrate. The second hard coat layer (B) formed using the hard coat agent (b2) contained therein is laminated in order.

As the transparent base material constituting the hard coat film, various resin film base materials generally used as the base material of the hard coat film can be used.

Examples of the resin film substrate include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, cellophane, diacetyl cellulose, triacetyl cellulose, acetyl cellulose butyrate, cellulose acetate propionate, cycloolefin polymer, cycloolefin Olefin copolymer, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polymethylpentene, polysulfone, polyetheretherketone, polyethersulfone, polyetherimide, polyimide, fluororesin, A resin film substrate obtained by using nylon, acrylic resin or the like can be used. Especially, as said resin film base material, it is preferable to use the resin film base material obtained using a polyethylene terephthalate, a triacetyl cellulose, a polycarbonate, and an acrylic resin.

As the transparent substrate, a substrate composed only of the resin film may be used. However, in order to further improve the adhesion with the first hard coat layer (A), the resin film substrate is used. It is preferable to use a transparent substrate having a primer layer on its surface.

Moreover, as said transparent base material, in order to improve the adhesiveness with said 1st hard-coat layer (A) further, uneven | corrugated processing, such as a sandblasting method and a solvent processing method, corona discharge processing, atmospheric pressure plasma It is preferable to use a transparent substrate that has been subjected to surface treatment such as treatment, chromic acid treatment, flame treatment, hot air treatment, ozone treatment, ultraviolet irradiation treatment, oxidation treatment, and the like.

The transparent substrate preferably has a thickness in the range of 50 μm to 200 μm, preferably has a thickness in the range of 75 μm to 150 μm, and has a thickness in the range of 90 μm to 130 μm. It is more preferable to use a thin film and to obtain a hard coat film that is thin and can prevent curling.

As the transparent substrate, for example, a material having excellent transparency at a level that can ensure good visibility when applied to a display of an information display device is used. As the transparent substrate, one having a total light transmittance of 85% or more is preferably used, more preferably 88% or more, and more preferably 90% or more. Is more preferable.

As the transparent substrate, a substrate having an elastic modulus in the range of 3 GPa to 7 GPa is preferably used, and a film substrate in the range of 3 GPa to 5 GPa is more preferable. By using a transparent substrate having an elastic modulus in the above range, cracks in the hard coat layer due to deformation of the film substrate can be suppressed, and a decrease in the surface hardness of the hard coat film can be suppressed. . Moreover, since a favorable softness | flexibility can be ensured by using the base material provided with the said elasticity modulus, it becomes possible to affix the hard coat film of this invention on a loose curved surface part.

[First hard coat layer (A)]
A 1st hard-coat layer (A) is a layer laminated | stacked on the at least one surface of the said transparent base material, and is a layer containing a filler.

The first hard coat layer (A) imparts high hardness to the hard coat film of the present invention.

The first hard coat layer (A) preferably has a thickness in the range of 5 μm to 30 μm, and a thickness in the range of 10 μm to 25 μm is preferable for obtaining a hard coat film with higher hardness. And more preferable.

The first hard coat layer (A) can be formed by using a hard coat agent (a1) containing a filler.

As the hard coat agent (a1), for example, a material containing a filler and an active energy ray-curable compound can be used.

Examples of the filler that can be used include silica, zirconia, titanium oxide, antimony pentoxide, magnesium carbonate, aluminum hydroxide, barium sulfate, and organic beads. Among these, it is preferable to use silica as the filler in order to further improve the hardness of the hard coat film.

As the silica, those generally called reactive silica and non-reactive silica can be used alone or in combination.

Examples of the reactive silica include those obtained by adding a reactive group such as a (meth) acryloyl group to the surface of silica particles.

As the reactive silica, in order to achieve both high transparency of the hard coat layer (A) and high hardness, it is preferable to use what is generally referred to as colloidal silica having an average particle size of nanometer order. It is more preferable to use those having an average particle size in the range of 5 nm to 200 nm, and it is more preferable to use those having an average particle size in the range of 5 nm to 100 nm.

Further, as the non-reactive silica, silica particles having no reactive group as described above can be used. Nonreactive functional groups may be introduced on the surface of the nonreactive silica.

As the non-reactive silica, in order to achieve both high transparency and high hardness of the hard coat layer (A) and to prevent curling of the hard coat film, it has an average particle size of nanometer order, Generally, what is called colloidal silica is preferably used, more preferably one having an average particle size in the range of 5 nm to 200 nm, more preferably one having an average particle size in the range of 5 nm to 100 nm. Further preferred.

As the filler, it is preferable to use a combination of the reactive silica and the non-reactive silica. The reactive silica and the non-reactive silica have a mass ratio of [reactive silica / non-reactive silica] of 0. It is preferable to use a combination so as to be in the range of 5 to 1.5, and it is preferable to use a combination so as to be in the range of 0.6 to 1, because the hardness of the first hard coat layer (A) Since the hardness of a coat film can be improved further, it is more preferable.

Moreover, as said hard-coat agent (a1) which can be used for formation of the said hard-coat layer (A), the urethane (meth) acrylate mentioned later which may be contained in the said hard-coat agent (a1), and three or more It is preferable to use a filler containing 100 to 300 parts by mass of filler with respect to a total of 100 parts by mass of the polyfunctional (meth) acrylate having a (meth) acryloyl group, and 150 to 280 parts by mass. It is more preferable to use those contained in the range of parts in order to obtain a hard coat film having higher hardness and more excellent scratch resistance.

As the hard coat agent (a1) that can be used for forming the hard coat layer (A), a material containing an active energy ray-curable compound in addition to the filler can be used.

As the active energy ray-curable compound, for example, urethane (meth) acrylate, polyfunctional (meth) acrylate having three or more (meth) acryloyl groups other than the urethane (meth) acrylate, and the like can be used. 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.

As the urethane (meth) acrylate, for example, those having four or more (meth) acryloyl groups obtained by reacting an aliphatic polyisocyanate and a (meth) acrylate having a hydroxyl group can be used.

Examples of the aliphatic polyisocyanate include aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, and lysine triisocyanate; norbornane diisocyanate, isophorone diisocyanate, methylenebis (4-cyclohexylisocyanate), 1,3-bis (isocyanatomethyl) Use cycloaliphatic polyisocyanates such as cyclohexane, 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl-1,5-diisocyanatocyclohexane, and their trimers (trimers) can do.

As the aliphatic polyisocyanate, it is possible to use at least one selected from the group consisting of hexamethylene diisocyanate, norbornane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate) and trimers thereof among the above-mentioned aliphatic polyisocyanates. It is preferable for further increasing the hardness of the hard coat layer (A) and the hard coat film.

As the (meth) acrylate having a hydroxyl group that can be reacted with the aliphatic polyisocyanate, for example, when producing a urethane (meth) acrylate having preferably 4 or more (meth) acryloyl groups, It is preferable to use those having two or more acryloyl groups.

Examples of the (meth) acrylate having a hydroxyl group 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. These can be used in combination.

Among the above-mentioned (meth) acrylates having a hydroxyl group, among them, pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate may be used. The hardness of the hard coat layer (A) and the present invention It is preferable for further increasing the hardness of the hard coat film.

The reaction between the aliphatic polyisocyanate and the (meth) acrylate having a hydroxyl group can be carried out by a conventional urethanization reaction. Moreover, in order to accelerate | stimulate progress of the said urethanation reaction, it is preferable to make them urethanize 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 hard coat agent (a1) usable in the present invention may be one containing one type of urethane (meth) acrylate as the urethane (meth) acrylate, or two or more types of urethane (meth). You may use what contains an acrylate. For example, as the hard coating agent (a1), urethane acrylate obtained by reacting hexamethylene diisocyanate with an acrylate having an arbitrary hydroxyl group, and a trimer of hexamethylene diisocyanate (trimerized product) and an arbitrary In order to further increase the hardness of the hard coat layer (A) and the hardness of the hard coat film of the present invention, it is preferable to use a combination of urethane acrylates obtained by reacting with an acrylate having a hydroxyl group.

The hard coating agent (a1) is preferably one containing the urethane (meth) acrylate in the range of 1% by mass to 80% by mass with respect to the total nonvolatile content. It is preferable to use what is contained in the range of mass%.

As said hard-coat agent (a1), what contains the polyfunctional (meth) acrylate which has a 3 or more (meth) acryloyl group as needed other than the above-mentioned filler and urethane (meth) acrylate. Can be used.

Examples of the polyfunctional (meth) acrylate include trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, and ditrimethylolpropane 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, dipentaerythritol The hexa (meth) acrylate, can be combined used alone or two or more.

Among the above-mentioned polyfunctional (meth) acrylates, in order to further increase the hardness of the hard coat layer (A) and the hard coat film, the (meth) 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. To 120 g / eq. It is more preferable to use the thing of the range. As the polyfunctional (meth) acrylate, it is preferable to use pentaerythritol tetraacrylate (acryloyl group equivalent: 88 g / eq.), Dipentaerythritol hexaacrylate (acryloyl group equivalent: 118 g / eq.), Or the like.

The urethane (meth) acrylate and the polyfunctional (meth) acrylate may be used in a mass ratio of [the urethane (meth) acrylate / the polyfunctional (meth) acrylate] in the range of 90/10 to 10/90. Preferably, it is used in the range of 80/20 to 20/80, more preferably in the range of 75/25 to 25/75.

As the hard coat agent (a1), in addition to those described above, if necessary, the (meth) acrylate having one (meth) acryloyl group and two ( You may use what contains other (meth) acrylates, such as (meth) acrylate which has a (meth) acryloyl group. When using other (meth) acrylate, the usage-amount of other (meth) acrylate is 40 mass parts or less with respect to a total of 100 mass parts of the said urethane (meth) acrylate and the said polyfunctional (meth) acrylate. It is preferable that it is 20 parts by mass or less.

As the hard coat agent (a1), in addition to the above-described ones, for example, a polymerization inhibitor, a surface conditioner, an antistatic agent, an antifoaming agent, and a viscosity adjuster as long as the effects of the present invention are not impaired. Agents, light-resistant stabilizers, weather-resistant stabilizers, heat-resistant stabilizers, ultraviolet absorbers, antioxidants, leveling agents, organic pigments, inorganic pigments, pigment dispersants and the like can be used alone or in combination.

On the other hand, since the second hard coat layer (B) to be described later is laminated on the surface of the first hard coat layer (A) formed using the hard coat agent (a1), the interlayer between these layers is laminated. It is preferable not to contain the component which reduces adhesiveness as much as possible. Specifically, it is preferable that the hard coating agent (a1) does not contain an active energy ray-curable compound (b1) having a fluorine atom and a silicon atom, which will be described later.

The first hard coat layer (A) is formed, for example, by applying the hard coat agent (a1) to one or both sides of the transparent base material, drying it, and then irradiating with active energy rays.

Examples of the active energy rays include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When ultraviolet rays are used as the active energy ray, it is preferable to use those containing a photopolymerization initiator or a photosensitizer as the hard coat agent (a1). On the other hand, when ionizing radiation such as electron beam, α ray, β ray, γ ray and the like is used as the active energy ray, a hard coating agent (a1) that does not contain a photopolymerization initiator or a photosensitizer is used. Also good.

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, the hydrogen abstraction type photopolymerization initiator includes, 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′-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, s-benzylisothuronium-p. -Sulfur compounds such as toluene sulfonate.

These photopolymerization initiators and photosensitizers are each 0.05 parts by mass with respect to a total of 100 parts by mass of urethane (meth) acrylate and polyfunctional (meth) acrylate contained in the hard coat agent (a1). It is preferably used in the range of ˜20 parts by mass, and more preferably in the range of 0.5 to 15 parts by mass.

[Second hard coat layer (B)]
The second hard coat layer (B) is a layer laminated on the surface of the first hard coat layer (A) constituting the hard coat film of the present invention.

The second hard coat layer (B) imparts excellent slipperiness to the hard coat film of the present invention, and as a result, imparts excellent scratch resistance.

The second hard coat layer (B) preferably has a thickness in the range of 500 nm to 15 μm, and the thickness in the range of 1 μm to 10 μm achieves both a reduction in thickness and excellent scratch resistance. It is more preferable for obtaining a hard coat film.

The second hard coat layer (B) can be formed by using a hard coat agent (b2) containing an active energy ray-curable compound (b1) having a fluorine atom and a silicon atom. By using the hard coat agent (b2), a hard coat film having both high hardness and excellent scratch resistance can be obtained.

As the hard coat agent (b2), one containing an active energy ray-curable compound (b1) having a fluorine atom and a silicon atom can be used. Thereby, it is possible to obtain a hard coat film that achieves both high hardness and excellent scratch resistance, and is excellent in stain resistance and fingerprint resistance.

As the active energy ray-curable compound (b1), for example, compounds having a fluorine atom and a silicon atom among compounds having a fluorocarbon chain, a siloxane chain, or a hydrocarbon chain can be used.

Specifically, it is preferable to use the active energy ray-curable compound (b1) having a poly (perfluoroalkylene ether) chain as a fluorocarbon chain and a cyclopolysiloxane structure. A structure in which a cyclopolysiloxane structure is bonded to both ends of a (perfluoroalkylene ether) chain via a divalent linking group, and a (meth) acryloyl group is bonded to the cyclopolysiloxane structure via a divalent linking group It is preferable to use the compound (b1-1) having

Examples of the poly (perfluoroalkylene ether) chain of the compound (b1-1) 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 fluorocarbon 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 used. Can be mentioned.

(In the above general formula (1), X is the following formulas (1-1) to (1-5), and X is 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 represents a repeating unit. Represents an integer of 2 to 200.)

Among the poly (perfluoroalkylene ether) chains, among the above, a perfluoromethylene group represented by the formula (1-1), a perfluoroethylene group represented by the formula (1-2), and It is preferable that the poly (perfluoroalkylene ether) chain is constituted by the following in order to further improve the antifouling property of the hard coat film.

The molar ratio of the perfluoromethylene group represented by the formula (1-1) to the perfluoroethylene group represented by the formula (1-2) [the perfluoromethylene represented by the formula (1-1) Methylene group / perfluoroethylene group represented by the formula (1-2)] is preferably in the range of 1/10 to 10/1. Further, the value of n in the general formula (1) is preferably in the range of 2 to 200, more preferably in the range of 10 to 100, and still more preferably in the range of 20 to 80.

Examples of the cyclopolysiloxane structure that the compound (b1-1) has include 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.)

The cyclopolysiloxane structure is preferably a cyclotetrasiloxane structure in which m in the general formula (2) is 3, among the above-described cyclopolysiloxane structures.

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.

(In the above 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.)

The compound (b1-1) can be produced, for example, through the following steps (1) to (3).
(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 the step (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 the step (1). .
(3) A step of introducing a (meth) acryloyl group by reacting the hydroxyl group added in the step (2) with a (meth) acrylate having an isocyanate group.

The active energy ray-curable compound (b1) such as the compound (b1-1) obtained by the above method is 0.05% by mass to 5% by mass with respect to the total nonvolatile content of the hard coat agent (b2). It is preferably included in the range, and more preferably in the range of 0.1% by mass to 2% by mass in order to achieve both excellent surface hardness and scratch resistance.

As a hard coat agent (b2) that can be used for forming the second hard coat layer (B), in addition to the active energy ray-curable compound (b1) having a fluorine atom and a silicon atom, if necessary, Other active energy ray-curable compounds can be used.

As the other active energy ray-curable compound, for example, urethane (meth) acrylate, polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups, and the like can be used.

As said urethane (meth) acrylate, the thing similar to the urethane (meth) acrylate illustrated as what can be used for the hard-coat agent (a1) which can be used for formation of said 1st hard-coat layer (A) is used. can do.

Moreover, as polyfunctional (meth) acrylate which has a 3 or more (meth) acryloyl group, it can be used for the hard-coat agent (a1) which can be used for formation of said 1st hard-coat layer (A). The thing similar to the polyfunctional (meth) acrylate which has three or more (meth) acryloyl groups illustrated can be used.

As the hard coat agent (b2), in addition to those described above, a polymerization inhibitor, a surface conditioner, an antistatic agent, an antifoaming agent, and a viscosity conditioner are added as necessary, as long as the effects of the present invention are not impaired. , A light-resistant stabilizer, a weather-resistant stabilizer, a heat-resistant stabilizer, an ultraviolet absorber, an antioxidant, and a leveling agent can be used alone or in combination of two or more.

The second hard coat layer (B) is applied to the hard coat agent (b2) on a part or all of the surface of the first hard coat layer (A) formed by the above method, and dried. It can be formed by irradiating active energy rays.

Examples of the active energy rays include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When ultraviolet rays are used as the active energy ray, it is preferable to use a hard coating agent (b2) containing a photopolymerization initiator or a photosensitizer. On the other hand, when ionizing radiation such as electron beam, α ray, β ray, γ ray and the like is used as the active energy ray, a hard coating agent (b2) containing no photopolymerization initiator or photosensitizer is used. Also good.

As the photopolymerization initiator and photosensitizer, those similar to those exemplified as those usable for the hard coat agent (a1) usable for the formation of the first hard coat layer (A) are used. can do. When 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 the photopolymerization initiator or photosensitizer.

The active energy ray used when the hard coat agent (b2) is cured and the light source thereof are the same as those exemplified as those that can be used when forming the first hard coat layer (A). Things can be used.

The hard coat film of the present invention is, for example, (i) a step of forming a first hard coat layer (A) on at least one surface of the transparent substrate using the hard coat agent (a1), (ii) It can manufacture by passing through the process of forming a 2nd hard-coat layer (B) on a part or all of the surface of the said hard-coat layer (A) using the said hard-coat agent (b2).

In addition, when using what contains an active energy ray hardening-type compound as said hard-coat agent (a1) and hard-coat agent (b2), on the surface of the hard-coat layer (A ') of an unhardened or semi-hardened state, After forming an uncured or semi-cured hard coat layer (B ′), the hard coat layer (A) and the hard coat layer (B) can be cured at once by irradiating with active energy rays. .

First, the step (i) will be described.

Specifically, in the method of forming the first hard coat layer (A) by the step (i), the hard coat agent (a1) is applied to a part or all of one side or both sides of the transparent substrate and The method of drying and hardening is mentioned.

Examples of the method for applying the hard coating agent to one or both sides of the transparent substrate 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.

As the curing method, for example, if the hard coat agent (a1) contains an active energy ray-curable compound, the hard coating agent (a1) is applied and dried on the coated surface. And then curing.

Examples of the active energy rays include ionizing radiation such as ultraviolet rays, electron rays, 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.

When producing the hard coat film of the present invention, the first hard coat layer (A) is formed on the surface of the transparent substrate by the above-described method, and then the second hard coat layer (B) is sequentially laminated. In order to obtain high adhesion at the interface between the hard coat layer (A) and the hard coat layer (B), the hard coat agent (a1) is applied to the surface of the transparent substrate. After drying, an active energy ray is not irradiated, or an active energy ray sufficient for complete curing is not irradiated to form an uncured or semi-cured hard coat layer (A ′), and then described later. The hard coat layer (B) may be laminated in order to produce a hard coat film. In this case, the hard coat layer (A ′) can be fully cured by active energy rays irradiated when the hard coat layer (B) is formed to form the hard coat layer (A).

The surface of the hard coat layer (A) may be subjected to corona treatment, plasma treatment or the like in order to further improve interlayer adhesion when laminated with the hard coat layer (B).

Next, the step (ii) will be described.

In the step (ii), the hard coat agent (b2) is applied to the surface of the hard coat layer (A) or the hard coat layer (A ′) formed in the step (i), dried and cured. It is.

Examples of the method for applying the hard coating agent (b2) include die coating, micro gravure coating, gravure coating, roll coating, comma coating, air knife coating, kiss coating, spray coating, transfer coating, dip coating, spinner coating, and wheeler coating. , Brush coating, silk screen solid coating, wire bar coating, flow coating, and the like.

As the curing method, for example, if the hard coat agent (b2) contains an active energy ray-curable compound, the hard coating agent (b2) is applied and dried on the coated surface with active energy rays. The method of hardening is mentioned.

In addition, when the hard coat agent (b2) is applied to the surface of the uncured or semi-cured hard coat layer (A ′), active energy rays are applied to the application surface of the hard coat agent (b2). By forming the hard coat layer (A) and the hard coat layer (B) by irradiation, the adhesion between the layers is further improved, and further excellent scratch resistance and excellent anti-resistance It is preferable in order to make it possible to maintain effects such as dirtiness for a long period of time.

As the hard cord film of the present invention, the other surface of the transparent base material constituting the hard cord film (on the opposite side of the surface on which the first hard coat layer (A) and the second hard coat layer (B) are laminated). In order to prevent curling, it is preferable to use a surface having a third hard coat layer.

The third hard coat layer preferably has a thickness in the range of 2 μm to 50 μm, more preferably in the range of 5 μm to 30 μm, in order to suppress the occurrence of curling.

The thickness of the third hard coat layer is about ± 50% of the total thickness of the first hard coat layer (A) and the second hard coat layer (B). It is preferable to suppress the occurrence of curling.

The third hard coat layer can be formed by applying, drying, and curing a third hard coat agent.
As said 3rd hard-coat agent, the thing similar to the hard-coat agent (a1) illustrated as what can be used for formation of said 1st hard-coat layer (A) can be used. Moreover, as said 3rd hard-coat agent, what does not contain a filler among the hard-coat agents (a1) illustrated as what can be used for formation of said 1st hard-coat layer (A) should be used. Can do.

The hard coat film of the present invention may have a decorative layer or an adhesive layer on part or all of one side or both sides. The hard coat film of the present invention provided with the decorative layer can be used as a decorative film. Moreover, the hard coat film of this invention provided with the said adhesive layer can be used as a protective film.

The decoration layer or the pressure-sensitive adhesive layer is preferably provided on a part or all of the surface of the third hard coat layer that can constitute the hard coat film.

Examples of the decorative layer include those composed of a frame-like border for the purpose of imparting concealment and design, as well as letters, figures and symbols.

[Decoration layer]
The hard coat film of the present invention may be used as a decorative film by providing a decorative layer. The decorative layer can be provided on the hard coat film by general printing. 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 that are visually recognized around the information display unit when used as an information display panel, or Examples thereof include a black border-shaped decorative layer provided in a frame shape on the information display section.

The thickness of the decoration layer is preferably 30 μm or less, more preferably 15 μm or less, and particularly preferably 10 μm or less. It becomes easy to obtain suitable designability by setting it as the decoration layer of the said thickness.

The decorative layer can be provided at any location on one or both sides of the hard coat film, but is usually provided at a location other than the information display section when used for a display of an information display device.

[Adhesive layer]
The hard coat film of the present invention may be used as a protective film by providing an adhesive layer. The pressure-sensitive adhesive layer can be provided by sticking a pressure-sensitive adhesive tape to the hard coat film or by directly applying a pressure-sensitive adhesive layer on the surface opposite to the hard coat layer (B) constituting the hard coat film.

The thickness of the pressure-sensitive adhesive layer 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.

For 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 these, it is preferable to use an acrylic pressure-sensitive adhesive containing an acrylic polymer in order to further improve interference fringe reduction, adhesion to a film substrate, transparency, weather resistance, and the like.

As the acrylic polymer, a polymer obtained by polymerizing a (meth) acrylic monomer can be used. Examples of the (meth) acrylic monomer include (meth) acrylate, and it is preferable to use a monomer containing (meth) acrylate having an alkyl group having 2 to 14 carbon atoms.

Examples of the (meth) acrylate having an alkyl group 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 meta Relate, n- octyl methacrylate, isooctyl methacrylate, 2-ethylhexyl methacrylate, isononyl methacrylate, isodecyl methacrylate, lauryl methacrylate.

Among the above-mentioned (meth) acrylates, it is preferable to use alkyl (meth) acrylates having an alkyl group having 4 to 9 carbon atoms, and alkyl acrylates having an alkyl group having 4 to 9 carbon atoms. More preferably, is used.

As the alkyl acrylate having an alkyl group having 4 to 9 carbon atoms, n-butyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, isononyl acrylate, and ethyl acrylate are more preferable because it is easy to ensure suitable adhesive strength. .

The (meth) acrylate having an alkyl group having 2 to 14 carbon atoms is preferably used in a range of 90% by mass to 99% by mass with respect to the total amount of the (meth) acrylic monomer. It is more preferable to use in the range of -96 mass% because it is easy to ensure a suitable adhesive force.

As the acrylic polymer, for example, a polymer having a polar group such as a hydroxyl group, a carboxyl group, and an amide group can be used.

The acrylic polymer can be produced by polymerizing a (meth) acrylic monomer containing a (meth) acrylic monomer having a polar group such as a hydroxyl group, a carboxyl group, or an amide group.

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. Of 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. Of these, N-vinyl-2-pyrrolidone, N-vinylcaprolactam, and acryloylmorpholine are preferably used.

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

The (meth) acrylic monomer having a polar group should be used in the range of 0.1% by mass to 20% by mass with respect to the total amount of the (meth) acrylic monomer used for the production of the acrylic polymer. It is preferable to use in the range of 1% by mass to 13% by mass, and it is preferable to use in the range of 1.5% by mass to 8% by weight to make the cohesive strength, holding power, and adhesiveness suitable. It is more preferable because it is easy to adjust.

The weight average molecular weight of the acrylic polymer is preferably 400,000 to 1,400,000, more preferably 600,000 to 1,200,000 because the adhesive force can be easily adjusted to a specific range.

The weight average molecular weight can be measured by gel permeation chromatograph (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 mass (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

As the pressure-sensitive adhesive, it is preferable to use a material containing a crosslinking agent in addition to the acrylic polymer in order to further increase the cohesive force.

Examples of the crosslinking agent include isocyanate crosslinking agents, epoxy crosslinking agents, chelate crosslinking agents, and the like.

The crosslinking agent is preferably used in a range where the gel fraction of the pressure-sensitive adhesive layer to be formed is 25% by mass to 80% by mass, and is used in a range where the gel fraction is 40% by mass to 75% by mass. More preferably, the use within the range of 50% by mass to 70% by mass can suppress a decrease in surface pencil hardness when the protective film is attached to the substrate, and has sufficient adhesiveness. 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.

As the pressure-sensitive adhesive, a material containing a tackifying resin can be used to further increase the adhesive strength.

The tackifying resin is preferably used in the range of 10 to 60 parts by mass with respect to 100 parts by mass of the acrylic polymer. Further, when importance is attached to adhesiveness, it is preferably added in the range of 20 to 50 parts by mass.

As the pressure-sensitive adhesive, those containing known and commonly used additives other than the above can be used.

As the additive, for example, a silane coupling agent is added in the range of 0.001 to 0.005 parts by mass with respect to 100 parts by mass of the pressure-sensitive adhesive in order to improve adhesion to the substrate. Is preferred. Furthermore, as necessary, plasticizers, softeners, fillers, pigments, flame retardants, and the like can be added as other additives.

[Embodiment]
The hard coat film of the present invention has suitable scratch resistance, slipperiness and antifouling properties and can be applied to various applications. Among them, information on information display devices such as liquid crystal displays (LCDs) and organic EL displays can be used. It can be suitably applied to a display unit. In particular, even if it is thin, it can realize suitable scratch resistance and slipperiness, so portable electronic devices that are highly demanded for miniaturization and thinning such as electronic notebooks, mobile phones, smartphones, portable audio players, mobile PCs, tablet terminals etc. It is suitable for the purpose of protecting the information display unit of the terminal information display device. In such an image display device, for example, 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 more specifically 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 part by weight of dibutyltin diacetate, 0.6 part by weight of dibutylhydroxytoluene, 0.1 part 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 the temperature reached 60 ° C., 90.9 parts by mass of hexamethylene diisocyanate was added, followed by reaction at 80 ° C. for 5 hours, and a non-volatile content containing urethane acrylate (A1-1) having 6 acryloyl groups in one molecule. % 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))
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 ”, a non-volatile content of 90% by mass, NCO%: 19.6% by mass, NCO equivalent: 214 g / eq.) A mixed solution of 107 parts by mass and methyl ethyl ketone 50 parts by mass was added dropwise over 2 hours. After completion of the dropwise addition, the mixture was reacted at 75 ° C. for 4 hours, and further reacted until the infrared absorption spectrum of 2250 cm ⁻¹ indicating the isocyanate group disappeared, and urethane acrylate (A1-2) having 9 acryloyl groups in one molecule was 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 (A1-2) in the nonvolatile content.

(Synthesis Example 3: Synthesis of urethane acrylate (A1-3))
A flask equipped with a stirrer, gas introduction tube, cooling tube and thermometer was charged with 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. 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 indicating the isocyanate group disappears, thereby obtaining urethane acrylate (A1-3) having 6 acryloyl groups in one molecule. A non-volatile content 80% by mass solution was obtained. This solution contains 19.5% by mass of PE4A in addition to urethane acrylate (A1-3) in the nonvolatile content.

(Synthesis Example 4: Synthesis of urethane acrylate (A1-4))
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 PE3A and PE4A (PE3A / PE4A = 75/25 (mass ratio)) was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was reacted at 70 ° C. for 3 hours, and further reacted until the infrared absorption spectrum of 2250 cm ⁻¹ indicating the isocyanate group disappeared, and urethane acrylate (A1-4) having 6 acryloyl groups in one molecule was obtained. A non-volatile content 80% by mass solution was obtained. This solution contains 19.9% by mass of PE4A in addition to urethane acrylate (A1-4) in the nonvolatile content.

(Synthesis Example 5: Synthesis of urethane acrylate (A1-5))
A flask equipped with a stirrer, gas introduction tube, cooling tube and thermometer was charged with 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. The temperature was raised to 70 ° C. while blowing air, and then 369 parts by weight of 369 parts by weight of bis (2-acryloyloxyethyl) hydroxyethyl isocyanurate and a mixture of PE3A and PE4A (PE3A / PE4A = 75/25 (mass ratio)). Were added dropwise over 1 hour. After completion of the 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 showing the isocyanate group disappears, and urethane acrylate having 4 to 6 acryloyl groups in one molecule (A1-5 ) Containing a non-volatile content of 80% by mass. This solution contains 10.1% by mass of PE4A in addition to urethane acrylate (A1-5) in the nonvolatile content.

(Synthesis Example 6: Synthesis of Fluorine Compound (B1-1))
In a flask equipped with a stirrer and a condenser, in a dry nitrogen atmosphere, 500 parts by mass of perfluoropolyether having allyl groups 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. 0.442 parts by mass of a toluene solution of a chloroplatinic acid / vinylsiloxane complex (containing 1.1 × 10 ⁻⁶ mol as a simple substance of Pt) was added thereto, and the mixture was 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. A perfluoropolyether compound (1) 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.)

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 treated with activated carbon to obtain the following formula (7) A perfluoropolyether compound (2), which is a pale yellow transparent liquid represented by

In 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 (B1-1) 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)) was added to this fluorine compound (B1-1), and a fluorine compound (B1-1) solution having a nonvolatile content of 20% by mass Was prepared.

(Preparation 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 2 18.3 parts by mass of a solution containing urethane acrylate (A1-2) (8.9 parts by mass of urethane acrylate (A1-2) and 3.5 parts by mass of PE4A), a mixture of PE4A and PE3A (PE4A / PE3A = 60/40 (mass ratio)) 38 parts by mass, 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, “reactive silica (C1-1) ) ") 287.5 parts by mass (115 parts by mass as reactive silica (C1-1)), non-reactive colloidal silica (Nissan Chemical Industries Ltd.) "MEK-ST40", 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 (as non-reactive silica (C2-1)) 125 parts by mass), photopolymerization initiator (“Irgacure 184” manufactured by BASF Japan Ltd., 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., oxyphenylacetic acid 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester and oxyphenylacetic acid 2- (2-hydroxyethoxy) ethyl ester) Mixture; hereinafter abbreviated as “photopolymerization initiator (D-2).”) After 1.6 parts by mass of the mixture were uniformly stirred, methyl ethyl The hard coat agent (a1-1) having a nonvolatile content of 40% by mass was prepared by diluting with ruketone.

(Preparation Example 2)
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 Preparation Example 1 is 287.5 parts by mass to 200 parts by mass (reactive silica (C1-1) as 200 parts by mass). The hard coat agent (a1-2) having a nonvolatile content of 40% by mass was prepared in the same manner as in Preparation Example 1, except that the non-reactive silica (C2-1) was not blended.

(Preparation Example 3)
The blending amount of the non-reactive silica (C2-1) methyl ethyl ketone dispersion having a nonvolatile content of 40% by mass used in Preparation Example 1 is from 312.5 parts by mass to 500 parts by mass (200 as non-reactive silica (C2-1)). The hard coat agent (a1-3) having a nonvolatile content of 40% by mass was prepared in the same manner as in Preparation Example 1, except that the reactive silica (C1-1) was not blended.

(Preparation 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 Preparation Example 1 is 287.5 parts by mass to 312.5 parts by mass (125% as reactive silica (C1-1)). The non-reactive silica (C2-1) is mixed in a methyl ethyl ketone dispersion having a nonvolatile content of 40% by mass from 312.5 parts by mass to 287.5 parts by mass (non-reactive silica (C2-1)). The hard coat agent (a1-4) having a nonvolatile content of 40% by mass was prepared in the same manner as in Preparation Example 1 except that the content was changed to 115 parts by mass).

(Preparation Example 5)
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 Preparation Example 1 is 287.5 parts by mass to 187.5 parts by mass (75 as reactive silica (C1-1)). A hard coat agent (a1-5) having a nonvolatile content of 40% by mass was prepared in the same manner as in Preparation Example 1, except that the content was changed to (parts by mass).

(Preparation Example 6)
The hard coat agent (a1) having a nonvolatile content of 40% by mass was the same as in Preparation Example 1 except that the reactive silica (C1-1) and the non-reactive silica (C2-1) used in Preparation Example 1 were not blended. -6) was prepared.

(Preparation Example 7)
31.3 parts by mass of the solution containing urethane acrylate (A1-3) obtained in Synthesis Example 3 (including 20.1 parts by mass of urethane acrylate (A1-3) and 4.9 parts by mass of PE4A), Synthesis Example 4 31.3 parts by mass of the solution containing urethane acrylate (A1-4) obtained in the above (including 20 parts by mass of urethane acrylate (A1-4) and 5 parts by mass of PE4A), the urethane acrylate obtained in Synthesis Example 5 ( 25 parts by mass of a solution containing A1-5) (including 18 parts by mass of urethane acrylate (A1-5) and 2 parts by mass of PE4A), dipentaerythritol hexaacrylate (hereinafter abbreviated as “DPHA”), and dipentaeri. 30 parts by mass of a mixture (DPHA / DPPA = 60/40 (mass ratio)) of thrisitol pentaacrylate (hereinafter abbreviated as “DPPA”), 1.5 parts by mass of a 20% by mass solution of the fluorine compound (B1-1) obtained in Example 6 (0.3 parts by mass as the fluorine compound (B1-1)) and a photopolymerization initiator (D-1) 4 After uniformly stirring 5 parts by mass, it was diluted with ethyl acetate to prepare a hard coat agent (b1-1) having a nonvolatile content of 40% by mass.

(Preparation Example 8)
Instead of the 20 mass% solution of the fluorine compound (B1-1) used in Preparation Example 7, 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 Preparation Example 7, a hard coat agent (b1-2) having a nonvolatile content of 40% by mass was prepared.

(Preparation Example 9)
A hard coat agent (b1-3) having a nonvolatile content of 40% by mass was prepared in the same manner as in Preparation Example 7, except that the fluorine compound (B1-1) used in Preparation Example 7 was not blended.

Example 1
The hard coat agent (a1-1) obtained above was applied to one side of a polyethylene terephthalate film (“Cosmo Shine A4300” manufactured by Toyobo Co., Ltd., thickness 100 μm) using a wire bar (# 40), After drying at 60 ° C. 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) in an air atmosphere, the irradiation light quantity is 0.1 J / cm. ² was irradiated with ultraviolet rays to obtain a hard coat film (X-1a) having a cured coating film (hard coat layer) having a thickness of 15 μm.

Next, a hard coat agent (a1-1) is applied to the other surface of the base material, and a first hard coat layer having a thickness of 15 μm is formed in the same manner as in the above (X-1a). A film (X-1b) was obtained.

The hard coat agent (b1-1) is applied to one surface of the first hard coat layer using a wire bar, dried at 60 ° C. for 1 minute, and then irradiated with ultraviolet rays in an atmosphere having an oxygen concentration of 5000 ppm or less. Using a device (“MIDN-042-C1” manufactured by Eye Graphics Co., Ltd., lamp: 120 W / cm, high-pressure mercury lamp), ultraviolet light was irradiated with an irradiation light amount of 0.3 J / cm ² , and a second of 5 μm thickness A hard coat film (X-1) was obtained by forming a hard coat layer.

(Example 2)
A hard coat film (X-2) was produced in the same manner as in Example 1 except that the hard coat agent (a1-1) was changed to the hard coat agent (a1-2).

Example 3
A hard coat film (X-3) was produced in the same manner as in Example 1 except that the hard coat agent (a1-1) was changed to the hard coat agent (a1-3).

Example 4
A hard coat film (X-4) was produced in the same manner as in Example 1 except that the hard coat agent (a1-1) was changed to the hard coat agent (a1-4).

(Example 5)
A hard coat film (X-5) was produced in the same manner as in Example 1 except that the hard coat agent (a1-1) was changed to the hard coat agent (a1-5).

(Example 6)
A hard coat film (X-6) was produced in the same manner as in Example 1 except that the thickness of the first hard coat layer was changed from 15 μm to 10 μm.

(Example 7)
The hard coat agent (a1-1) obtained above was applied to one side of a polyethylene terephthalate film (“Cosmo Shine A4300” manufactured by Toyobo Co., Ltd., thickness 100 μm) using a wire bar (# 40). After drying for 1 minute at a temperature of 0.1 J / cm ^{2 in} an air atmosphere, an ultraviolet irradiation device (“MIDN-042-C1” manufactured by Eye Graphics Co., Ltd., lamp: 120 W / cm, high-pressure mercury lamp) is used. The hard coat film (X-1a) having a cured coating film (first hard coat layer) having a thickness of 15 μm was obtained.

The hard coat agent (b1-1) was applied to the surface of the first hard coat layer constituting the hard coat film (X-1a) using a wire bar, dried at 60 ° C. for 1 minute, and then oxygenated. Irradiation of ultraviolet rays with an irradiation light quantity of 0.3 J / cm ² using an ultraviolet irradiation device (“MIDN-042-C1” manufactured by Eye Graphics Co., Ltd., lamp: 120 W / cm, high-pressure mercury lamp) in an atmosphere having a concentration of 5000 ppm or less Thus, a hard coat film (X-7) on which a second hard coat layer having a thickness of 5 μm was formed was obtained.

(Comparative Example 1)
A hard coat film (X′-1) was produced in the same manner as in Example 1 except that the thickness of the first hard coat layer was changed from 15 μm to 20 μm and the second hard coat layer was not formed. .

(Comparative Example 2)
The hard coat agent (a1-1) obtained above was applied to one side of a polyethylene terephthalate film (“Cosmo Shine A4300” manufactured by Toyobo Co., Ltd., thickness 100 μm) using a wire bar (# 40), After drying at 60 ° C. 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) in an air atmosphere, the irradiation light quantity is 0.1 J / cm. ² was irradiated with ultraviolet rays to form a cured coating film (third hard coat layer) having a thickness of 15 μm.

Next, the hard coat agent (b1-1) is applied to the other surface of the polyethylene terephthalate film (the surface opposite to the surface on which the third hard coat layer is formed) using a wire bar. After coating and drying at 60 ° C. 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) in an atmosphere with an oxygen concentration of 5000 ppm or less, A hard coat film (X′-2) on which a second hard coat layer having a thickness of 5 μm was formed was obtained by irradiating ultraviolet rays with an irradiation light amount of 0.3 J / cm ² .

(Comparative Example 3)
A hard coat film (X′-3) was produced in the same manner as in Example 1 except that the hard coat agent (a1-1) was changed to the hard coat agent (a1-6).

(Comparative Example 4)
A hard coat film (X′-4) was produced in the same manner as in Example 1 except that the hard coat agent (b1-1) was changed to the hard coat agent (b1-2).

(Comparative Example 5)
A hard coat film (X′-5) was produced in the same manner as in Example 1 except that the hard coat agent (b1-1) was changed to the hard coat agent (b1-3).

[Measurement of pencil hardness]
The hard coat film obtained above was cut into 10 cm squares, placed on a glass plate so that the second hard coat layer was on the top, and the four corners were fixed with cellophane tape. The pencil hardness of the surface of the second hard coat layer was determined using a pencil scratch tester (manual type) for coating film manufactured by Imoto Seisakusho Co., Ltd. based on the provisions of JIS K 5600-5-4 (1999 edition). It was measured.

The hardness of the hardest pencil that did not cause scars was evaluated as the pencil hardness of the surface of the hard coat layer. A hard coat film having a surface hardness of 3H or more was determined to be excellent in surface hardness. In addition, about the hard coat film obtained in the comparative example 1 which has not provided the 2nd hard coat layer, pencil hardness was evaluated by making the 1st hard coat layer into the outermost surface.

[Evaluation of scratch resistance]
A sample obtained by cutting the hard coat film obtained above into a 30 cm × 2 cm rectangle was used as a test piece. The test piece is fixed to a flat friction tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.) using a jig so that the second hard coat layer constituting the test piece is the upper surface, and steel wool # 0000 is used. The surface was abraded at a load of 0.5 kg / cm ² , a stroke of 100 mm, and a speed of 30 times / min.

The scratched state of the scratched portion of the test piece was visually observed, and the scratch resistance was evaluated according to the following criteria. It was determined that the hard coat film that was evaluated as O had excellent scratch resistance. In addition, about the hard coat film obtained by the comparative example 1 which does not provide the 2nd hard coat layer, scratch resistance was evaluated so that a 1st hard coat layer might become an upper surface.

○: No scratches were observed even after 10,000 round trips.
Δ: The surface was scratched by carrying out 10,000 round trips, but was not scratched by 2000 round trips.
×: Scratched by 2000 reciprocations.

[Measurement of water contact angle]
A sample obtained by cutting the hard coat film obtained above into a 1 cm × 5 cm rectangle was used as a test piece. The test piece was fixed to the glass plate with double-sided tape so that the second hard coat layer constituting the test piece was on the upper surface.

The contact angle of water on the surface of the test piece was contacted with 3 to 3.5 μL of purified water using an automatic contact angle meter “DM-501” manufactured by Kyowa Interface Science Co., Ltd., and contacted after 1 second. The corner was measured. In addition, about the hard coat film obtained in the comparative example 1 which has not provided the 2nd hard coat layer, the water contact angle of the surface of a 1st hard coat layer was evaluated.

[Evaluation of antifouling properties]
A circle was drawn on the surface of the second hard coat layer constituting the hard coat film obtained above using a marker “Uni Mediax (black)” manufactured by Mitsubishi Pencil Co., Ltd. At that time, the repelling degree of the marker ink on the surface of the hard coat layer was visually observed. In addition, about the hard coat film obtained in the comparative example 1 which does not provide the 2nd hard coat layer, the antifouling property of the surface of the 1st hard coat layer was evaluated.

A: The ink repelled in a dot shape.
◯: The ink repelled in the form of dots and lines.
Δ: The ink repelled linearly.
X: Ink did not repel and a linear circle was drawn.

[Evaluation of slipperiness]
The slipperiness was evaluated based on the slipperiness when the surface of the second hardcoat layer of the hardcoat film obtained above was rubbed with Bencott (manufactured by Asahi Kasei Fibers Co., Ltd.). In addition, about the hard coat film obtained by the comparative example 1 which is not providing the 2nd hard coat layer, the slip property of the surface of a 1st hard coat layer was evaluated.

A: Glide well.
○: Slip.
Δ: Not slippery
×: Does not slip.

[Curl evaluation method]
The hard coat film was cut into a 10 cm square, allowed to stand in a 25 ° C. environment for 1 day, and then placed on a smooth surface.

The height of the four corners of the hard coat film was measured with respect to the smooth surface, and the average value was taken as the curl height. Evaluation was performed according to the following evaluation criteria based on the average value.

◎: curl height (average value) of 4 corners is less than 2 mm ○: curl height (average value) of 4 corners is 2 mm or more and less than 5 mm ×: curl height (average value) of 4 corners is 5 mm or more

The table shows the composition and evaluation results of the hard coat agent that forms the hard coat films obtained in Examples 1 to 7 and Comparative Examples 1 to 5.

Claims

A hard coat agent (b2) containing a first hard coat layer (A) containing a filler and an active energy ray-curable compound (b1) having a fluorine atom and a silicon atom on at least one surface of the transparent substrate. A hard coat film comprising a second hard coat layer (B) formed using
The first hard coat layer (A) comprises a hard coat agent (a1) containing urethane (meth) acrylate, a polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups, and a filler. A layer formed by using the filler, wherein the filler is contained in an amount of 100 to 300 parts by mass with respect to a total of 100 parts by mass of the urethane (meth) acrylate and the polyfunctional (meth) acrylate. The hard coat film according to 1.
The urethane (meth) acrylate is a urethane (meth) acrylate having 4 or more (meth) acryloyl groups in one molecule obtained by reacting an aliphatic polyisocyanate and a (meth) acrylate having a hydroxyl group. The hard coat film according to claim 2.
The hard coat film according to claim 3, wherein the aliphatic polyisocyanate is at least one selected from the group consisting of hexamethylene diisocyanate, norbornane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), and trimers thereof. .
The hard coat film according to any one of claims 1 to 4, wherein the filler contains reactive silica and non-reactive silica.
The hard coat film according to claim 5, wherein a mass ratio of the reactive silica to the non-reactive silica is [reactive silica / non-reactive silica] = 0.5 to 1.5.
The hard coat film according to any one of claims 1 to 6, wherein the surface of the second hard coat layer (B) has a water contact angle of 95 ° or more.
The active energy ray-curable compound (b1) having a fluorine atom and a silicon atom has a cyclopolysiloxane structure bonded to both ends of a poly (perfluoroalkylene ether) chain via a divalent linking group. The hard coat film according to any one of claims 1 to 7, which is a compound (b1-1) having a structure in which a (meth) acryloyl group is bonded to a siloxane structure via a divalent linking group.
9. An information display device, wherein the hard coat film according to claim 1 is used for protecting an information display unit.