JP2016112834A - Hard coat film and information display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hard coat film which has scratch resistance at a level capable of preventing occurrence of a dent or a scratch even when repeatedly pressed and scratched for example with a stylus or the like, and which can maintain surface functions such as antifouling property for a long period of time.SOLUTION: A hard coat film is constituted of a hard coat layer and a surface layer sequentially laminated on at least one surface of a substrate, in which the hard coat layer is a layer formed by using a hard coat agent containing: a compound (x1) having a hydrolyzable silyl group or a silanol group and a radical-polymerizable functional group; a radical-polymerizable compound (x2) other than the compound (x1); and a polymerization initiator. The hard coat film includes the compound (x1) of 2.9 mass% or more, and has plastic hardness of the surface layer of 1,000 N/mmor more.SELECTED DRAWING: None

Description

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

2. Description of the Related Art As portable electronic devices such as smartphones and tablet terminals, and image display devices such as televisions and personal computers, those equipped with a display with a touch panel function are widespread.
An image display device equipped with the touch panel is usually operated by bringing a finger, a touch pen, or the like into contact with the display surface and pressing the surface. Therefore, the surface of the display has a high level of scratch resistance capable of preventing dents and scratches even when repeatedly pressed and scratched with a relatively strong force by the touch pen or the like, and is antifouling. It is required that surface functions such as properties can be maintained for a long time.

  In addition to the above, the information display device is required to have various characteristics as its functionality increases. For example, the surface of the information display device may require a surface function such as antifouling property capable of preventing adhesion of fingerprints and dirt in the atmosphere, and antifogging performance with the spread of touch panel functions. is there.

  Among the surface functions, for example, as a hard coat film imparted with antifouling properties, a fluorine-based additive is added in advance to the active energy ray-curable composition, applied to the film substrate, and then cured by irradiation with ultraviolet rays. The hard coat film obtained by this is known (for example, refer patent document 1).

  However, the conventional hard coat film may not be sufficient in terms of surface functions such as antifouling property and slipperiness.

JP 2010-168419 A

  The problem to be solved by the present invention is, for example, a level of scratch resistance capable of preventing the occurrence of dents and scratches even when repeatedly pressed and scratched with a touch pen or the like, and has antifouling properties, etc. It is to provide a hard coat film capable of maintaining the surface function for a long time.

The present inventors are a hard coat film in which a hard coat layer (X) and a surface layer (Y) are sequentially laminated on at least one surface of a base material, and the hard coat layer (X) is hydrolyzed. A hard coat agent containing a compound (x1) having a reactive silyl group or silanol group and a radical polymerizable functional group, a radical polymerizable compound (x2) other than the compound (x1), and a polymerization initiator. 2.9% by mass or more of the compound (x1) with respect to the total of the radical polymerizable compound (x2) and the polymerization initiator, and the surface layer (Y) of the hard coat film The above problems have been solved by a hard coat film characterized in that the plastic hardness of the side surface is 1000 N / mm ² or more.

  Even if the hard coat film of the present invention is repeatedly pressed and rubbed with, for example, a touch pen, etc., it can prevent the occurrence of dents and scratches and has surface functions such as antifouling properties and anti-fogging properties. Since it can last for a long period of time, it can be suitably used as a hard coat film for protecting the surface of a display mounted on a portable electronic device such as a smartphone or a tablet terminal, or an image display device such as a television or a personal computer. .

The hard coat film of the present invention is a hard coat film in which a hard coat layer (X) and a surface layer (Y) are sequentially laminated on at least one surface of a substrate, and the hard coat layer (X) is Using a hard coat agent containing a compound (x1) having a hydrolyzable silyl group or silanol group and a radical polymerizable functional group, a radical polymerizable compound (x2) other than the compound (x1), and a polymerization initiator 2.9% by mass or more of the compound (x1) with respect to the total of the radical polymerizable compound (x2) and the polymerization initiator, and the surface layer of the hard coat film ( The plastic hardness of the surface on the Y) side is 1000 N / mm ² or more. The hard coat film of the present invention having the above structure is simply a case where it is repeatedly pressed and scratched with a touch pen or the like, compared with a hard coat film in which a hard coat layer and a surface layer are laminated on the surface of a substrate. However, it is possible to prevent the occurrence of dents and scratches and to maintain surface functions such as antifouling properties and anti-fogging properties over a long period of time.

  As an embodiment of the hard coat film of this invention, what has the structure by which the said hard-coat layer (X) and the surface layer (Y) were laminated | stacked in order is mentioned on the one surface side of the said base material.

  The hard coat film of the present invention may have no layer on the other surface side of the substrate, and the hard coat layer (X) and the surface layer on the other surface side of the substrate. (Y) may have a structure in which the layers are sequentially laminated, and the hard coat layer (X), the surface layer (Y), or other layers are used alone or in combination of two or more on the other surface side of the base material. It may be a thing.

  As a preferred embodiment of the hard coat film of the present invention, the hard coat layer (X) and the surface layer (Y) are sequentially laminated on one surface of the base material, and the other of the base materials. Those having the hard coat layer (X) on the surface side of the substrate directly or via another layer. The hard coat film having the above-described configuration can further improve the surface hardness. Moreover, the hard coat film which consists of the said structure can suppress the curvature of the hard coat film resulting from the cure shrinkage at the time of forming the said hard coat layer (X).

  On the other hand, when a hard coat film having no hard coat layer (X) on the other side of the substrate is used in a mode in which an adhesive layer is provided on the other side, good pasting workability and post-processing It is preferable because the production cost can be suppressed.

  As the hard coat film, a film having a thickness of 75 μm to 500 μm is preferably used, a film having a thickness of 100 μm to 400 μm is more preferable, and a film having a thickness of 100 μm to 350 μm is used. Is more preferable, and it is particularly preferable to use a material having a thickness of 100 μm to 300 μm. The hard coat film having the thickness in the above range can contribute to thinning of a portable electronic terminal or an image display device provided with the display, for example, when used for an application to be installed on the surface of various displays. Moreover, by setting the thickness of the hard coat film within the above range, it is possible to easily obtain the surface hardness necessary for protecting the display or the like, and to suppress warping to the extent that the workability is not impaired.

  Moreover, as the hard coat film, a film in which the hard coat layer (X) and the surface layer (Y) form a bond (xy) is used. Thereby, the effect of surface functions, such as antifouling property, can be obtained for a hard coat film sustainable for a long time.

  Examples of the bond (xy) that may be formed between the hard coat layer (X) and the surface layer (Y) include, for example, a bond composed of a silicon atom and an oxygen atom or a titanium atom and an oxygen atom. Can be mentioned. Specifically, the bond (xy) was used for forming the hydrolyzable silyl group or silanol group of the compound (x1) contained in the hard coat layer (X) and the surface layer (Y). A bond formed by a reaction with a functional group of the compound (y1) is preferable.

  As the bond (xy), a hydrolyzable silyl group or silanol group such as an alkoxysilyl group or silanol group derived from the compound (x1) which is one of the components forming the hard coat layer (X), and Examples include a bond formed by a reaction with an alkoxysilyl group, a silanol group, a titanol group, a hydroxyl group, or the like, which is derived from a component forming the surface layer (Y).

  Since the hard coat film having the bond (xy) is excellent in interlayer adhesion between the hard coat layer (X) and the surface layer (Y), even when repeatedly pressed and rubbed with a touch pen or the like, for example. In addition, the occurrence of dents and scratches can be prevented, and surface functions such as antifouling properties and anti-fogging properties can be maintained for a long period of time.

  In addition, it is preferable to use a highly transparent film as the hard coat film, because even if it is installed on the surface of a display, good visibility can be secured. The total light transmittance of the hard coat film is preferably 85% or more, more preferably 88% or more, and particularly preferably 90% or more.

  The hard coat film has a pencil hardness of 2H or more, for example, even when repeatedly pressed and rubbed with a touch pen or the like, can prevent the occurrence of dents and scratches, and This is preferable because surface functions such as antifouling property and anti-fogging property can be maintained for a long period of time.

[Base material]
As a base material which comprises the hard coat film of this invention, it is highly transparent and what is generally used as a base material of the optical hard coat film can be selected suitably, and can be used.

  As said base material, a polyester resin film, a triacetyl cellulose film, an acrylic resin film, an alicyclic structure containing thermoplastic resin film, a polycarbonate resin film etc. can be used, for example.

  As the substrate, a substrate composed only of the resin film mentioned above can be used, but for the purpose of further improving the adhesion with the hard coat layer (X), the surface of the resin film is used. It is also possible to use a substrate having an easy adhesion layer.

  In addition, as the base material, the surface of the resin film is subjected to a roughening process by a sandblasting method, a solvent processing method, or the like for the purpose of further improving the adhesion to the hard coat layer (X). Discharge treatment, atmospheric pressure plasma treatment, chromic acid treatment, flame treatment, hot air treatment, ozone treatment, ultraviolet irradiation treatment, oxidation treatment, or the like can be used.

  Moreover, it is preferable to use the transparent base material whose total light transmittance is 88% or more as said base material, and it is more preferable to use the transparent base material which is 90% or more. In the present invention, by setting the total light transmittance within the above range, even when the hard coat layer (X) is provided on one or both sides of the transparent substrate, the transmittance is excellent, and good visual recognition when applied to an image display device. Sex can be obtained.

  As the substrate, it is preferable to use a material having a thickness in the range of 5 μm to 450 μm, more preferably a material in the range of 50 μm to 400 μm, and a material in the range of 75 μm to 300 μm. It is further preferable for suppressing the occurrence of warpage of the hard coat film.

[Hard coat layer (X)]
The hard coat layer (X) constituting the hard coat film of the present invention includes a compound (x1) having a hydrolyzable silyl group or silanol group and a radical polymerizable functional group, and other than the compound (x1). The layer formed using the hard-coat agent containing a radically polymerizable compound (x2) is used. Here, the hydrolyzable silyl group refers to, for example, a functional group in which an alkoxy group is bonded to a silicon atom, and specifically includes an alkoxysilyl group. The silanol group refers to a functional group in which a hydroxyl group is bonded to a silicon atom.

  Part or all of the hydrolyzable silyl group or silanol group possessed by the compound (x1) reacts with the functional group possessed by the compound (y1) used for the formation of the surface layer (Y) described later, and the bond ( It is preferable to contribute to the formation of xy).

  Moreover, as a radically polymerizable functional group which the said compound (x1) has, a (meth) acryloyl group is mentioned. The radical polymerizable functional group is preferably radically polymerized with, for example, a (meth) acryloyl group of the radical polymerizable compound (x2) described later in order to obtain a hard coat film having further excellent scratch resistance and the like.

The compound (x1) is used in an amount of 2.9% by mass or more based on the total amount (nonvolatile content) of the radical polymerizable compound (x2) other than the compound (x1) contained in the hard coat agent and the polymerization initiator. It is preferable to use 3.9% by mass or more, and it is preferable to use 4.9% by mass or more even when the surface layer (Y) is repeatedly pressed and rubbed by, for example, a touch pen. Is particularly preferable for obtaining a hard coat film that can maintain surface functions such as antifouling property and anti-fogging property over a long period of time.
The upper limit of the amount of the compound (x1) used is preferably 100% by mass or less, more preferably 80% by mass or less, and 60% by mass or less hardly lowering the hardness of the hard coat layer. It is particularly preferable for obtaining a hard coat film having excellent scratch resistance.

  Examples of the compound (x1) include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and 2-hydroxyethyltrimethoxy. Silane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxy Silane, vinyltriacetoxysilane, allyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxytrimethoxysilane, 3-methacryloxy Propylmethyldiethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3- Glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (Meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxyoctyltrimethoxysilane, 3- (meth) acryloxyocty Triethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyl dimethoxysilane, it may be used diethyl diethoxy silane.

  As the compound (x1), a silane compound having a functional group capable of dehydration condensation such as the hydrolyzable silyl group or silanol group and a radical polymerizable functional group such as a (meth) acryloyl group is used. However, a bond (xy) can be formed between the hard coat layer (X) and the surface layer (Y). As a result, it has high hardness, excellent durability such as scratch resistance, and antifouling properties. It is preferable because a hard coat film that can sustain the effect for a long time can be obtained.

  Among them, as the silane compound, a compound (x1-1) represented by the following general formula (1) or a compound having a structure represented by the following general formula (2) and general formula (3) (x1-2) It is preferable to use at least one compound (x1) selected from the group consisting of a) in order to obtain a hard coat film having higher durability and sustainable effects such as antifouling properties for a long period of time.

(R ₁ , R ₂ and R _{3 in the} general formula (1) each independently represent a hydrogen atom or an alkyl group, R ₄ represents an alkylene group having 3 to 10 carbon atoms, and R ₅ represents a hydrogen atom or Represents a methyl group.)

(R ₁ , R ₂ and R _{3 in} general formula (2) each independently represent a hydrogen atom or an alkyl group, and R _{5 in} general formula (3) represents a hydrogen atom or a methyl group.)
Specific examples of the compound (x1-1) represented by the general formula (1) include 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) Examples include meth) acryloxyoctyltrimethoxysilane and 3- (meth) acryloxyoctyltriethoxysilane.

  As the compound (x1-2), specifically, compounds having structures represented by the general formula (2) and the general formula (3) can be used. Moreover, as the compound (x1-2), “X-12-1048”, “X-12-1050”, and the like manufactured by Shin-Etsu Chemical Co., Ltd. can be used.

  Especially, as the compound (x1-2), the molar ratio of the structure represented by the general formula (2) to the structure represented by the general formula (3) [structure / general formula represented by the general formula (2) It is preferable to use the compound (x1-2-1) in which the structure represented by (3) is 5/1 to 1/5, and it is preferable to use the compound having 3/1 to 1/3. It is possible to suppress a decrease in the crosslink density inside the hard coat layer (X) and to form a bond (xy) between the hard coat layer (X) and the surface layer (Y). It is preferable because a hard coat film having excellent durability such as scratch resistance and capable of maintaining the effect of the surface function for a long period of time can be obtained.

  Moreover, as a hard-coat agent which can be used for formation of the said hard-coat layer (X), what contains radically polymerizable compounds (x2) other than the said compound (x1) other than the said compound (x1) is used. To do.

  As the radical polymerizable compound (x2), it is preferable to use (meth) acrylate because it is easy to obtain and handle and it is easy to control the characteristics of the hard coat layer (X) depending on the application. .

  The (meth) acrylate is a urethane that suppresses curing shrinkage when the hard coat layer (X) is formed, and forms a hard coat layer having high surface hardness and excellent durability. It is more preferable to use (meth) acrylate.

  As the urethane (meth) acrylate, various urethane (meth) acrylates can be used, and among them, it is preferable to use a urethane (meth) acrylate having 4 or more (meth) acryloyl groups in the molecule. .

  As the urethane (meth) acrylate having 4 or more (meth) acryloyl groups in the molecule, it is preferable to use, for example, those obtained by reacting polyisocyanate and (meth) acrylate having a hydroxyl group.

  Examples of the polyisocyanate include aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, and lysine triisocyanate; norbornane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), 1,3-bis (isocyanatomethyl) cyclohexane, Alicyclic polyisocyanates such as 2-methyl-1,3-diisocyanatocyclohexane and 2-methyl-1,5-diisocyanatocyclohexane can be used.

  As said polyisocyanate, the trimer of the said aliphatic polyisocyanate or alicyclic polyisocyanate can also be used.

  As the polyisocyanate, hexamethylene diisocyanate, which is an aliphatic diisocyanate, norbornane diisocyanate, which is an alicyclic diisocyanate, or isophorone diisocyanate can be used to obtain a hard coat film with further excellent durability such as scratch resistance. Is preferable.

  Examples of the (meth) acrylate having a hydroxyl group that can be used in the production of the urethane (meth) acrylate include trimethylolpropane di (meth) acrylate, ethylene oxide-modified trimethylolpropane di (meth) acrylate, and propylene oxide-modified trimethylol. Propane di (meth) acrylate, glycerin di (meth) acrylate, bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol Penta (meth) acrylate or the like can be used alone or in combination of two or more.

  As the (meth) acrylate having a hydroxyl group, it is possible to use pentaerythritol tri (meth) acrylate or dipentaerythritol penta (meth) acrylate to obtain a hard coat film excellent in durability such as scratch resistance. preferable.

  The urethane (meth) acrylate can be produced by subjecting the polyisocyanate and the (meth) acrylate having a hydroxyl group to a urethanization reaction in a conventional manner 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, and 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 obtained by the above method can be used alone or in combination of two or more.

  As the urethane (meth) acrylate, it is preferable to use a combination of a urethane acrylate obtained using norbornane diisocyanate as the polyisocyanate and a urethane acrylate obtained using isophorone diisocyanate as the polyisocyanate. By setting it as such a combination, the hard coat film excellent in high surface hardness and durability can be obtained, suppressing the curvature of the hard coat film by the cure shrinkage at the time of hardening.

  As a hard-coat agent which can be used for formation of the said hard-coat layer (X), what contains other (meth) acrylates other than the said urethane (meth) acrylate can be used.

  Examples of the other (meth) acrylates include polyfunctional (meth) acrylates having 3 or more (meth) acryloyl groups in the molecule.

  Examples of the polyfunctional (meth) acrylate other than the urethane (meth) acrylate include trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, and propylene oxide modified trimethylolpropane tri (meth). Acrylate, 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 hexa (meth) acrylate may be used singly or in combination.

  The polyfunctional (meth) acrylate has a (meth) acryloyl group equivalent of 50 g / eq. For further improving durability such as scratch resistance of the hard coat layer (X). -200 g / eq. In the range of 70 g / eq. -150 g / eq. In the range of 80 g / eq. -120 g / eq. It is more preferable to use the thing of the range. Examples of the polyfunctional (meth) acrylate having a (meth) acryloyl group equivalent within the above range include pentaerythritol tetraacrylate (acryloyl group equivalent: 88 g / eq.), Dipentaerythritol hexa (meth) acrylate (acryloyl group equivalent: 118 g / eq.) and the like.

  The polyfunctional (meth) acrylate is preferably used in combination with the urethane (meth) acrylate.

  The mass ratio of the urethane (meth) acrylate and the polyfunctional (meth) acrylate [the urethane (meth) acrylate / the polyfunctional (meth) acrylate] further improves the durability of the hard coat film such as scratch resistance. 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.

  The total amount of the urethane acrylate and the polyfunctional (meth) acrylate used is preferably 10 parts by mass to 99.95 parts by mass with respect to 100 parts by mass of the nonvolatile content of the hard coating agent, and 20 parts by mass to It is preferably 99.5 parts by mass, particularly preferably 50 parts by mass to 99 parts by mass.

  As a hard coat agent that can be used for forming the hard coat layer (X), in addition to those described above, mono ((meth) acryloyl groups having one (meth) acryloyl group in the molecule are used as long as the effects of the present invention are not impaired. Those containing other (meth) acrylates such as (meth) acrylate and di (meth) acrylate having two (meth) acryloyl groups in the molecule can be used. They are preferably used at 40 parts by mass or less, more preferably at 20 parts by mass or less, with respect to 100 parts by mass in total of the urethane (meth) acrylate and the polyfunctional (meth) acrylate.

  As a hard coat agent that can be used for forming the hard coat layer (X), a hard coat agent containing a polymerization initiator such as a photopolymerization initiator capable of initiating a curing reaction by irradiating active energy rays is used. Can do.

  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, ben Benzoin such as inisopropyl 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′-die Aminobenzophenone compounds such as ruaminobenzophenone; 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 can be used alone or in combination of two or more.

  Moreover, as the hard coat agent, one containing a photosensitizer can be used.

  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-toluene. And sulfur compounds such as sulfonate.

  The amount of the photopolymerization initiator and photosensitizer used is preferably 0.05 parts by mass to 20 parts by mass, and 0.5 parts by mass to 100 parts by mass of the nonvolatile component of the hard coat agent. It is more preferable that it is 10 mass parts. 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.

  As the hard coat agent, one diluted with an appropriate solvent can be used.

  Examples of the solvent include acetone, isobutyl alcohol, 2-propanol, isopentyl alcohol, ethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol mono-normal-butyl ether, ethylene glycol monomethyl ether, ortho -Dichlorobenzene, xylene, cresol, chlorobenzene, isobutyl acetate, isopropyl acetate, isopentyl acetate, ethyl acetate, normal-butyl acetate, normal-propyl acetate, normal-pentyl acetate, methyl acetate, cyclohexanol, cyclohexanone, 1,4 -Dioxane, dichloromethane, N, N-dimethylformamide, styrene, tetrachloroethylene, tetrahydrofuran, 1,1,1 Trichloroethane, toluene, normal hexane, 1-butanol, 2-butanol, methanol, methyl isobutyl ketone, methyl ethyl ketone, methyl cyclohexanol, methyl cyclohexanone, methyl-normal-butyl ketone, etc. may be used alone or in combination of two or more. it can.

  Further, as the hard coat agent, if necessary, a polymerization inhibitor, a surface conditioner, an antistatic agent, an antifoaming agent, a viscosity adjuster, a light resistance stabilizer, a weather resistance stabilizer, a heat resistance stabilizer, an ultraviolet absorber, Additives such as antioxidants, leveling agents, organic pigments, inorganic pigments, pigment dispersants, silica beads, organic beads; inorganic fillers such as silicon oxide, aluminum oxide, titanium oxide, zirconia, antimony pentoxide, etc. You can use what you want.

  The hard coat layer (X) formed using the hard coat agent preferably has a thickness of 3 μm to 25 μm, preferably 5 μm to 15 μm, and has durability such as scratch resistance and the like. For example, it is more preferable to obtain a hard coat film that is excellent in slipperiness and that can be used in, for example, an image display device that is highly demanded to be thin.

  Moreover, as said hard-coat layer (X), it is preferable to use what the water contact angle of the surface is 85 degrees or less, and it is more preferable to use what is 75 degrees or less. By using the hard coat layer (X) having a water contact angle in the above range, the adhesion between the hard coat layer (X) and the surface layer (Y) can be further improved, and the surface function can be improved for a long time. Sustainable hard coat film can be obtained.

  The hard coat layer (X) preferably has a pencil hardness of 2H or more when laminated on one side of the substrate, and more preferably 3H or more because of durability such as scratch resistance. It is more preferable when obtaining a more excellent hard coat film.

[Surface layer (Y)]
The surface layer (Y) constituting the hard coat film of the present invention is a layer laminated on the surface of the hard coat layer (X) and imparts various surface functions to the hard coat film.

  The surface layer (Y) forms a bond (xy) with the hard coat layer (X). Thereby, the adhesion between the layers increases, and the effect of the surface function can be maintained for a long time.

  Examples of the surface function provided by the surface layer (Y) include antifouling properties and anti-fogging properties that can prevent adhesion of dirt due to fingerprints and the like.

  The surface layer (Y) can be formed using a surface layer (Y) forming coating agent. As the surface layer (Y) forming coating agent, a coating agent containing a compound having a functional group capable of reacting with a hydrolyzable silyl group or silanol group of the compound (x1) contained in the hard coat agent is used. It is preferable for forming a bond (xy) and obtaining a hard coat film having more excellent scratch resistance and the like.

  As the compound (y1), for example, in the case of forming the antifouling surface layer (antifouling layer), it can react with the functional group of the compound (x1) to form a bond (xy). Fluorine compounds having various functional groups can be used.

  As the fluorine compound, a fluorine compound having a hydrolyzable silyl group or silanol group as a functional group capable of reacting with the hydrolyzable silyl group or silanol group of the compound (x1) to form a bond (xy). Is preferably used. Here, the hydrolyzable silyl group refers to a functional group in which an alkoxy group is bonded to a silicon atom, and specifically includes an alkoxysilyl group. Silanol group refers to a functional group in which a hydroxyl group is bonded to a silicon atom.

  As a fluorine-based compound having the hydrolyzable silyl group or silanol group, for example, in order to give a higher slip by the hard coat film of the present invention, for example, having a hydrolyzable silyl group or silanol group at the terminal, It is preferable to use a fluorine-based compound having a polyperfluoropolyether chain.

  Examples of the polyperfluoropolyether chain include those having a structure in which a divalent fluorinated alkylene group having 1 to 6 carbon atoms and oxygen atoms are alternately connected.

  Examples of the polyperfluoropolyether chain include those represented by the following general formula (4).

In the general formula (4), X is the following formulas (4-1) to (4-3). X may be one of the following formulas (4-1) to (4-3), or two or more of the following formulas (4-1) to (4-3). You may have. For example, the structure having two or more of the following formulas (4-1) to (4-3) as the _{X, - (CF 2 CF 2} -O) n- (CF 2 -O) n- at the indicated Such a structure is mentioned. In the case where two or more types of structures represented by the formulas (4-1) to (4-3) are included as X, it has a random structure or block structure composed of structural units of — (X—O) — Also good. N is an integer of 2 to 200 representing a repeating unit.

(In the formula, a is an integer of 1 to 6.)

  As the fluorine-based compound, it is possible to use a compound having a hydrolyzable silyl group or silanol group together with a fluorine chain such as the perfluoropolyether chain, so that the hard coat layer (X) and the surface layer (Y) A bond (xy) can be formed between them, and as a result, a hard coat film that has excellent scratch resistance, slipperiness and antifouling properties and excellent antifouling properties for a long period of time can be obtained. Examples of the bond (xy) include a bond composed of a silicon atom and an oxygen atom, such as a —Si—O—Si— bond.

  Specific examples of the fluorine compound capable of forming the bond (xy) include OPTOOL DSX manufactured by Daikin Industries, Ltd. and trade names “KY-164” and “KY-130” manufactured by Shin-Etsu Chemical Co., Ltd. "KY-108", "X-71-190" etc. are mentioned.

  As content of the said compound (y1), such as the said fluorine-type compound, 80 mass parts-with respect to 100 mass parts of non volatile matters of the coating agent for surface layer (Y) formation used for formation of the said surface layer (Y) 100 parts by mass is preferable, 90 parts by mass to 100 parts by mass is more preferable, and 95 parts by mass to 100 parts by mass is still more preferable.

  The surface layer (Y) preferably has a water contact angle of 110 ° or more, more preferably 112 ° or more, and still more preferably 113 ° or more. In addition, the said water contact angle represents the contact angle measured 1 second after a 3 microliter water droplet is made to contact the surface layer (Y) which comprises a hard coat film.

  The hard coat film of the present invention includes, for example, (i) a step of forming a hard coat layer (X) on the at least one surface of the substrate using the hard coat agent, and (ii) the hard coat layer (X). It can manufacture by passing through the process of forming a surface layer (Y) on the surface of this using the said surface layer (Y) formation coating agent.

  The surface layer (Y) is formed on the surface of the uncured or semi-cured hard coat layer (X ′) using the coating agent for forming the surface layer (Y), and the hard coat layer is formed by heat curing or the like. It is preferable that after the bond (xy) is formed at the interface between (X ′) and the surface layer (Y), the hard coat layer (X) is completely cured by irradiation with active energy rays. Thereby, sufficient bond (xy) can be formed between the hard coat layer (X) and the surface layer (Y), and the effects of various surface functions can be maintained for a long time.

  First, the step (i) will be described.

  Specifically, the method of forming the hard coat layer (X) by the step (i) is a method in which the hard coat agent is applied to and dried on a part or all of one side or both sides of the substrate. Can be mentioned.

  Examples of the method for applying the hard coating agent to one or both sides of the substrate include die coating, micro gravure coating, gravure coating, roll coating, comma coating, air knife coating, kiss coating, spray coating, and delivery. Examples of the method include coating, dip coating, spinner coating, wheeler coating, brush coating, solid coating by silk screen, wire bar coating, and flow coating.

  As the curing method, for example, if the hard coating agent contains an active energy ray-curable composition, a method of applying the hard coating agent and irradiating the dried application surface with an active energy ray and curing it may be mentioned. It is done.

  Examples of the active energy rays 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. Examples include lamps, mercury-xenon lamps, short arc lamps, helium / cadmium lasers, argon lasers, sunlight, and LEDs.

  When manufacturing the hard coat film of the present invention, the step of laminating the surface layer (Y) described later may be performed after the hard coat layer (X) is formed on the surface of the substrate by the above-described method. However, from the viewpoint of obtaining high adhesion at the interface between the hard coat layer (X) and the surface layer (Y), after applying the hard coat agent on the surface of the substrate and drying, do not irradiate active energy rays, or By not irradiating a sufficient amount of active energy rays for complete curing, an uncured or semi-cured hard coat layer (X ′) is formed, and then a surface layer (Y) described later is laminated to produce a hard coat film. May be. In this case, the hard coat layer (X ′) is a hard coat layer that has been fully cured by irradiating with active energy rays after forming a sufficient bond (xy) with the surface layer (Y). (X) is formed. Thereby, sufficient bond (xy) can be formed between the hard coat layer (X) and the surface layer (Y), and the effects of various surface functions can be maintained for a long time.

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

  Next, the step (ii) will be described.

  In the step (ii), the surface layer (Y) is formed by applying and drying the coating agent on the surface of the hard coat layer (X) or hard coat layer (X ′) formed in the step (i). It is a process of forming.

  As a method of laminating the surface layer (Y) on the surface of the hard coat layer (X) or the hard coat layer (X ′), for example, the surface of the hard coat layer (X) or the hard coat layer (X ′) A method of forming a surface layer (Y) by applying a coating agent or the like and drying to remove the solvent, followed by heat treatment. As the processing temperature at this time, 20 ° C. or more is sufficient, but the bond (xy) is promptly bonded to the interface between the hard coat layer (X) or the hard coat layer (X ′) and the surface layer (Y). For the purpose of forming, it is also possible to process at a higher temperature. For example, the temperature is preferably treated in an environment of 40 ° C. or higher, and more preferably in an environment of 60 ° C. or higher.

  Examples of the method of applying the coating agent on the surface of the hard coat layer (X) or hard coat layer (X ′) include die coating, micro gravure coating, gravure coating, roll coating, comma coating, air knife coating, kiss coating, Examples thereof include spray coating, transfer coating, dip coating, spinner coating, wheeler coating, brush coating, silk screen solid coating, wire bar coating, flow coating, and vacuum deposition.

  Further, the hydrolyzable silyl group contained in the coating agent or the like can be hydrolyzed in advance. Silanol groups generated by hydrolysis are dehydrated and condensed between a plurality of molecules to generate Si-O-Si. Dehydration condensation proceeds quickly and oligomers are produced. It may be cured after hydrolysis so that the dehydration condensation proceeds sufficiently. By using such hydrolyzed and partially condensed oligomer, the curing time until the coating agent is cured to form the surface layer (Y) can be shortened.

  In addition, a surface layer (Y) formed by applying the coating agent on the surface of the hard coat layer (X) or hard coat layer (X ′) can be used in a water vapor atmosphere or an atmosphere in which a small amount of moisture exists. It is possible to form a silanol group by hydrolyzing a hydrolyzable silyl group that may be contained in the hard coat layer (X) or the hard coat layer (X ′) and the surface layer (Y), As a result, a bond (xy) such as a bond composed of a silicon atom and an oxygen atom can be efficiently formed between the silanol groups or between the silanol group and the hydrolyzable silyl group.

  When the hard coat film of the present invention is produced by a so-called roll-to-roll method, it is preferable to use a material having a high water vapor transmission rate as a slip sheet. Specifically, after applying a hard coating agent on the surface of the base material and drying it, the surface obtained by applying the coating agent on the surface and drying it is wound up in a roll shape through a slip sheet. After that, the material wound up in the form of a roll is cured in the form of a roll.

  Even when the slip sheet is wound up in a roll shape, moisture can permeate from the end to the vicinity of the center of the roll. Therefore, even if it is in the state wound in the roll shape, the hydrolyzable silyl group that may be contained in the primer layer (Y) and the surface layer (Y) is hydrolyzed, and the primer layer (Y ) And the silanol groups present in the surface layer (Y) or between the silanol groups and the hydrolyzable silyl groups, and as a result, bonds (xy) such as bonds constituted by silicon atoms and oxygen atoms are formed. It can be formed efficiently.

  Moreover, since the contact between the surface on which the surface layer (Y) is formed and the back surface of the base material can be avoided by using the slip sheet, blocking or the like at the interface can be prevented. .

Examples of the interleaving paper include resin films such as polystyrene film, cellophane, polypropylene, polyethylene, polyester resin film, triacetyl cellulose film, acrylic resin film, alicyclic structure-containing thermoplastic resin film, and polycarbonate resin film. be able to. Among them, it is preferable that water vapor permeability is to use more than 10g ^/ m 2 · day, and more preferable to use more than 20g ^/ m 2 · day. Examples of the slip sheet having a high water vapor transmission rate include polystyrene film, cellophane, and polyester resin film.

  As the interleaving paper, one having a thickness in the range of 5 μm to 250 μm can be used. In order to ensure workability when winding the manufactured hard coat film, the thickness is preferably in the range of 5 μm to 200 μm, more preferably in the range of 10 μm to 100 μm, and more preferably in the range of 10 μm to 80 μm. It is more preferable to use those in the range.

  As the interleaving paper, one having an arbitrary layer can be used as appropriate. For example, a slip sheet having a fine pressure-sensitive adhesive layer on the surface of the resin film protects the surface layer (Y) by using the fine pressure-sensitive adhesive layer bonded to the surface of the surface layer (Y). It can also be used as a film. In addition, by using the slip sheet having the slightly adhesive layer, it is possible to prevent the surface layer in an uncured state from partially falling off.

  The hard coat film of the present invention obtained by the above method may be any structure as long as the surface layer (Y) is exposed on at least a part of the surface layer, and has an appropriate layer in addition to the above structure. Also good.

  The hard coat film of the present invention may have a decorative layer or an adhesive layer on a part or all of one side or both sides. 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 characters, graphics, symbols, and frame-like borders for the purpose of providing concealment and design.

[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 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.

  As thickness of a decoration layer, 30 micrometers or less are preferable, 15 micrometers or less are more preferable, and 10 micrometers or less are especially preferable. It becomes easy to obtain suitable designability by setting it as the decoration layer of the said thickness.

  Although a decoration layer can be provided in the arbitrary location of the single side | surface or both surfaces of a hard coat film, when providing on a surface layer (Y), it is provided so that a part of surface layer (Y) may be exposed. 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]
When the surface layer (Y) is provided only on one side or one side of the hard coat film of the present invention, an adhesive layer may be provided on the other side and used as a protective film. The pressure-sensitive adhesive layer can be provided by attaching a pressure-sensitive adhesive tape to the hard coat film or by directly applying a pressure-sensitive adhesive layer to the surface opposite to the surface layer (Y) of the hard coat film.

  The thickness of the pressure-sensitive adhesive layer is preferably in the range of 5 μm to 200 μm, more preferably in the range of 8 μm to 175 μm, and still more preferably in the range of 10 μm to 100 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, or silicone-based pressure-sensitive resins can be used. Among them, the use of an acrylic pressure-sensitive adhesive or a silicone pressure-sensitive adhesive containing an acrylic polymer reduces interference fringes and further improves the adhesion to the substrate, transparency, weather resistance, and the like. It is preferable for improvement.

  As said acrylic polymer, what is obtained by superposing | polymerizing a (meth) acryl monomer can be used. As said (meth) acryl monomer, (meth) acrylate is mentioned, for example, It is preferable to use what contains the (meth) acrylate which has a C2-C14 alkyl group.

  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 methacrylate Rate, n- octyl methacrylate, isooctyl methacrylate, 2-ethylhexyl methacrylate, isononyl methacrylate, isodecyl methacrylate, lauryl methacrylate.

  Among the above (meth) acrylates, it is preferable to use an alkyl (meth) acrylate having an alkyl group having 4 to 9 carbon atoms, and an alkyl acrylate 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, and is 90% by mass. It is more preferable to use in the range of ˜96% by mass because it is easy to secure a suitable adhesive force.

  As said acrylic polymer, what has polar groups, such as a hydroxyl group, a carboxyl group, an amide group, can be used, for example.

  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. 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 (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 to use in the range of 1.5% by mass to 8% by weight makes the cohesive strength, holding power, and adhesiveness within suitable ranges. It is more preferable because it is easy to adjust.

  The acrylic polymer preferably has a weight average molecular weight of 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 the 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 the range where the gel fraction is 40% by mass to 75% by mass. It is more preferable that use in 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 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.

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

  The tackifier resin is preferably used in the range of 10 parts by mass to 60 parts by mass with respect to 100 parts by mass of the acrylic polymer. Furthermore, when importance is attached to adhesiveness, it is preferable to add in the range of 20 mass parts-50 mass parts.

  As said adhesive, what contains a well-known and usual additive other than the above can be used.

  As said additive, in order to improve the adhesiveness to a glass base material, for example, a silane coupling agent is added in 0.001 mass part-0.005 mass part with respect to 100 mass parts of adhesives. It is preferable. Furthermore, as necessary, plasticizers, softeners, fillers, pigments, flame retardants, and the like can be added as other additives.

  Further, as the pressure-sensitive adhesive layer, a silicone-based pressure-sensitive adhesive layer can be used. The silicone pressure-sensitive adhesive layer can be formed by using a silicone pressure-sensitive adhesive.

  As said silicone adhesive, what contains what is generally called a gum component and a resin component can be used. Moreover, as said silicone type adhesive, what contains a crosslinking agent, a metal catalyst, etc. besides the above-mentioned component can be used.

  As said gum component, what mainly becomes a binder component of an adhesive can be used, for example, polyorganosilicone etc. can be used. As the polyorganosilicone, a peroxide curable type and an addition curable type are known, and any of them can be used, but it is possible to achieve both excellent rework and air release properties and excellent impact resistance. In doing so, it is preferable to use a material containing an addition-curable polyorganosilicone.

As the addition-curable polyorganosilicone, for example, a polyorganosiloxane having a structure (—Si—CH═CH ₂ group) in which a polymerizable unsaturated double bond is bonded to a silicon atom can be used.

  Moreover, as said addition-curable polyorganosilicone, what has either of the structures (1)-(4) mentioned later can be used, and what has the following structures (1) and (2) is used. It is preferable to do.

  Specific examples of the addition-curable polyorganosilicone include addition-curable dimethylpolysiloxane, addition-curable dimethylphenylpolysiloxane, addition-curable polyethylphenylsiloxane, and addition-curable polymethylphenylsiloxane. it can.

  As the addition-curable polyorganosilicone, it is preferable to use a polyorganosilicone having a phenyl group because reworkability and air release properties can be further improved. Further, as the addition-curable polyorganosilicone, it is preferable to use an addition-curable dimethylpolysiloxane because it is easy to achieve both excellent air detachability and good followability to the adherend. .

  As the addition-curable polyorganosilicone, those having a weight average molecular weight of 50,000 to 1,000,000 are preferably used, and those having a weight average molecular weight of 100,000 to 500,000 are more preferable. It is more preferable to use a material having a weight average molecular weight of 200,000 to 350,000 in order to obtain a pressure-sensitive adhesive layer having particularly excellent air bleeding properties.

  Moreover, as said silicone type adhesive, what contains the said resin component can be used as needed other than an above described component.

  The resin component can be appropriately selected from conventionally known ones, but a polyorganosilicone having a relatively low molecular weight is preferably used, and an addition-curable polyorganosilicone is more preferably used.

  As polyorganosilicones that can be used as the resin component, for example, those having at least one selected from the group consisting of the following general formulas (5) to (8) can be used. It is preferable to use those having 6). The ratio (molar ratio) between the formula (5) and the formula (6) is preferably formula (5): formula (6) = 0.4: 1 to 1.4: 1, 0.6: It is more preferable to use one that is 1 to 1.2: 1.

(R represents a monovalent hydrocarbon group or a hydroxyl group.)

  As the polyorganosilicone as the resin component, among those exemplified as the gum component, those having a weight average molecular weight of preferably 100 to 10,000, more preferably 300 to 8000, and still more preferably 3000 to 6000 are used. Can do.

  The mass ratio of the polyorganosilicone that is the gum component and the polyorganosilicone that is the resin component is preferably 100: 0 to 65:35, more preferably 95: 5 to 70:30, It is particularly preferable that the ratio is 93: 7 to 80:20 because it is easy to achieve a high degree of excellent air bleeding, reworkability, and impact resistance.

  In addition, the resin component and the gum component may be premixed. Examples of the resin, gum component and solvent premixed are “X-40-3306”, “X-40-3229”, “X-40-3323” (manufactured by Shin-Etsu Chemical Co., Ltd.). Can be used.

  In addition, as the crosslinking agent that may be contained in the silicone-based pressure-sensitive adhesive, those having a structure capable of reacting with the functional group of the gum component or the resin component can be used, for example, a hydrogen atom in a silicon atom A cross-linking agent containing a siloxane having a structure (-Si-H group) in which is bonded can be used.

  Moreover, as a metal catalyst that may be contained in the silicone-based pressure-sensitive adhesive, it is preferable to use, for example, an organometallic catalyst belonging to Group 10 of the periodic table of elements, and specifically, a platinum-based catalyst may be used. Since it is excellent in the reaction promotion effect, it is more preferable.

  As the crosslinking agent and the catalyst, those previously mixed may be used, or those in which they form a complex may be used.

  In addition to the above-described components, the silicone-based pressure-sensitive adhesive may contain a solvent such as methyl ethyl ketone or toluene in order to improve application workability.

  As a silicone type adhesive layer formed using the said silicone type adhesive, it is preferable to use that whose gel fraction is 85 mass%-99 mass%, and it is 86 mass%-97 mass%. It is more preferable to use a material having a mass of 87% to 92% by mass, for example, excellent reworkability and air bleedability for an information display portion of a display, and excellent impact resistance. It is further preferable for obtaining a compatible pressure-sensitive adhesive layer.

The gel fraction is applied to one side of a polyester film “A4300 # 100” manufactured by Toyobo Co., Ltd., which is a base material, using a lip coater so that the thickness after drying is 30 μm. Then, after drying at 140 ° C. for 2 minutes, a single-sided adhesive tape is produced by curing at 40 ° C. for 48 hours, and refers to the mass calculated before and after immersing it in toluene and the value calculated by the following equation.
Gel fraction (% by mass) = {(mass of silicone-based adhesive layer after immersing single-sided adhesive tape in toluene) / (mass of silicone-based adhesive layer before immersing single-sided adhesive tape in toluene)} × 100

  Moreover, as a silicone type adhesive layer formed using the said silicone type adhesive, it is preferable that the total light transmittance (JIS K7361) in the visible light is 90% or more, and it is 92% or more. More preferably, it is more preferably 93% or more. Moreover, as said silicone type adhesive layer, it is preferable to use the thing whose haze (JIS K7136) in the visible light is 2% or less, It is more preferable to use what is 1% or less. In order to obtain a hard coat film with high transparency, it is more preferable to use a film of 8% or less.

[Embodiment]
Since the hard coat film of the present invention has excellent scratch resistance and can maintain surface functions such as antifouling properties and antifogging properties for a long period of time, it can be used in various applications. Especially, the hard coat film of this invention can be installed and used on surfaces, such as a liquid crystal display (LCD) and an organic electroluminescent display. In particular, since the hard coat film of the present invention can achieve durability such as suitable scratch resistance and excellent antifouling property and slipperiness even if it is thin, an electronic notebook, a mobile phone, a smartphone, a portable audio player, It can be suitably used for the purpose of protecting a display of a portable electronic terminal which is highly demanded to be reduced in size and thickness, such as a mobile personal computer and a tablet terminal.

  The hard coat film of the present invention can be used, for example, by being attached to the front or back surface of a transparent panel provided to protect an information display module such as an LCD module or an organic EL module.

  In addition, the hard coat film of the present invention can be used by being laminated on the surface of an information display portion on which a touch panel function called a so-called on-cell type or in-cell type is mounted.

  Examples of the information display device of the present invention include those having a configuration in which the hard coat film of the present invention is laminated on the surface of a non-glass member such as a polarizing plate via an adhesive layer or the like.

  Examples of the non-glass member include a polarizing plate. As the polarizing plate, a general polarizing plate in which a polarizer protective layer is laminated on both sides of the polarizer can be used.

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

(Synthesis Example 1: Synthesis of urethane acrylate (A1))
In a flask equipped with a stirrer, a gas introduction tube, a cooling tube, and a thermometer, 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 After charging and heating to 70 ° C. while blowing air, a mixture (mass ratio) of pentaerythritol triacrylate (hereinafter abbreviated as “PE3A”) and pentaerythritol tetraacrylate (hereinafter abbreviated as “PE4A”). 75/25 mixture) 795 parts by mass were added dropwise over 1 hour.

After completion of the dropwise addition, 3 hours at 70 ° C., the reaction was continued, by reacting further to the infrared absorption spectrum of 2250 cm ^-1 indicating the isocyanate group disappeared, butyl acetate containing a PE4A urethane acrylate (A1) A solution (non-volatile content 80 mass%, hereinafter abbreviated as “urethane acrylate (A1) solution”) was obtained. The molecular weight (calculated value) of the urethane acrylate (A1) was 802.

(Synthesis Example 2: Synthesis of urethane acrylate (A2))
In a flask equipped with a stirrer, a gas introduction tube, a cooling tube, and a thermometer, 254 parts by mass of butyl acetate, 222 parts by mass of isophorone diisocyanate, 0.5 parts by mass of p-methoxyphenol, 0.5 parts by mass of dibutyltin diacetate After charging and heating to 70 ° C., 795 parts by mass of a mixture of PE3A and PE4A (a mixture with a mass ratio of 75/25) was added dropwise over 1 hour.

After completion of the dropwise addition, 3 hours at 70 ° C., the reaction was continued, by reacting further to the infrared absorption spectrum of 2250 cm ^-1 indicating the isocyanate group disappeared, butyl acetate containing a PE4A urethane acrylate (A2) A solution (non-volatile content 80 mass%, hereinafter abbreviated as “urethane acrylate (A2) solution”) was obtained. The molecular weight (calculated value) of the urethane acrylate (A2) was 818.

(Synthesis Example 3: Synthesis of urethane acrylate (A3))
In a flask equipped with a stirrer, a gas introduction tube, a cooling tube, and a thermometer, 254 parts by mass of butyl acetate, 222 parts by mass of isophorone diisocyanate, 0.5 parts by mass of p-methoxyphenol, 0.5 parts by mass of dibutyltin diacetate After charging and heating to 70 ° C., 369 parts by mass of bis (acryloxyethyl) hydroxyethyl isocyanurate and 398 parts by mass of a mixture of PE3A and PE4A (mass ratio 75/25) were added dropwise over 1 hour. did.

After completion of the dropwise addition, 3 hours at 70 ° C., the reaction was continued, by reacting further to the infrared absorption spectrum of 2250 cm ^-1 indicating the isocyanate group disappeared, butyl acetate containing a PE4A urethane acrylate (A3) A solution (non-volatile content 80 mass%, hereinafter abbreviated as “urethane acrylate (A3) solution”) was obtained. The molecular weight (calculated value) of the urethane acrylate (A3) was 889.

(Preparation Example 1: Preparation of hard coat agent)
Urethane acrylate (A1) solution obtained in Synthesis Example 1, urethane acrylate (A2) solution obtained in Synthesis Example 2, urethane acrylate (A3) solution obtained in Synthesis Example 3, dipentaerythritol hexaacrylate and dipenta Mixture of erythritol pentaacrylate (dipentaerythritol hexaacrylate / dipentaerythritol pentaacrylate = 60/40 (mass ratio)), photopolymerization initiator (“Irgacure 184” manufactured by BASF Japan Ltd., 1-hydroxycyclohexyl phenyl ketone), Silane coupling agent ("X-12-1050", a structure in which R ₁ , R ₂ and R ₃ in general formula (2) are methyl groups, and R ₅ in general formula (3) is a hydrogen atom A compound having a structure, wherein the compound (x1-2) The molar ratio of the structure represented by the general formula (2) to the structure represented by the general formula (3) [structure represented by the general formula (2) / structure represented by the general formula (3)] = 1: 5), a silane coupling agent (“X-12-1048”, a structure in which R ₁ , R ₂ and R _{3 in} the general formula (2) are methyl groups, and R ₅ in the general formula (3) A compound having a structure which is a hydrogen atom, which corresponds to the compound (x1-2), and a molar ratio of the structure represented by the general formula (2) to the structure represented by the general formula (3) [general formula Structure represented by (2) / structure represented by general formula (3)] = 1: 1), silane coupling agent (3-acryloxypropyltrimethoxysilane, corresponding to the compound (x1-1)), silane Coupling agent (3-acryloxyoctyltrimethoxysilane, front Corresponding to compounds (x1-1)), ethyl acetate, 2-propanol, by mixing in accordance with weight parts as described in Table 1-3, the hard coat agent (1) to (25) were prepared.

(Preparation Example 2: Preparation of coating agent (1) for surface layer formation)
A coating agent (1) having a nonvolatile content of 0.1% by mass (hydrolyzable silyl group) by diluting 1 part by mass of “X-71-190” manufactured by Shin-Etsu Chemical Co., Ltd. with 199 parts by mass of “Novec7200” manufactured by 3M And a compound having a silanol group).

Example 1
The hard coat agent (1) is applied onto a polyester film (Toyobo Co., Ltd., Cosmo Shine A4300, thickness 100 μm) using a wire bar, dried at 85 ° C. for 2 minutes, and then irradiated with ultraviolet rays in an air atmosphere. Using a device (“MIDN-042-C1” manufactured by Eye Graphics Co., Ltd., lamp: 120 W / cm, high-pressure mercury lamp), ultraviolet rays are irradiated at an irradiation light amount of 0.25 J / cm ² , thereby providing a 10 μm thick hardware. A film having a coat layer (x-1) was obtained.

The surface layer is formed by applying the coating agent (1) for forming the surface layer to the surface of the hard coat layer (x-1) of the obtained film using a wire bar # 4 and drying at 85 ° C. for 2 minutes. (Y-1) was formed to obtain a laminated film. The obtained laminated film is cured in an air atmosphere at 60 ° C. for one week, so that —Si—O—Si— bond is formed at the interface between the hard coat layer (x-1) and the surface layer (y-1). Formed. Finally, the hard coat film was produced by irradiating an ultraviolet-ray with the irradiation light quantity of 0.25 J / cm < ² > from the surface layer side of a laminated | multilayer film in nitrogen atmosphere.

(Example 2)
The interface between the hard coat layer (x-2) and the surface layer (y-1) was the same as in Example 1 except that the hard coat agent (2) was used instead of the hard coat agent (1). A hard coat film in which a bond was formed was prepared.

(Example 3)
The interface between the hard coat layer (x-3) and the surface layer (y-1) was the same as in Example 1 except that the hard coat agent (3) was used instead of the hard coat agent (1). A hard coat film in which a bond was formed was prepared.

Example 4
The interface between the hard coat layer (x-4) and the surface layer (y-1) was the same as in Example 1 except that the hard coat agent (4) was used instead of the hard coat agent (1). A hard coat film in which a bond was formed was prepared.

(Example 5)
The interface between the hard coat layer (x-5) and the surface layer (y-1) was the same as in Example 1 except that the hard coat agent (5) was used instead of the hard coat agent (1). A hard coat film in which a bond was formed was prepared.

(Example 6)
The interface between the hard coat layer (x-6) and the surface layer (y-1) was the same as in Example 1 except that the hard coat agent (6) was used instead of the hard coat agent (1). A hard coat film in which a bond was formed was prepared.

(Example 7)
The interface between the hard coat layer (x-7) and the surface layer (y-1) was the same as in Example 1 except that the hard coat agent (7) was used instead of the hard coat agent (1). A hard coat film in which a bond was formed was prepared.

(Example 8)
The interface between the hard coat layer (x-8) and the surface layer (y-1) in the same manner as in Example 1 except that the hard coat agent (8) was used instead of the hard coat agent (1). A hard coat film in which a bond was formed was prepared.

Example 9
The interface between the hard coat layer (x-9) and the surface layer (y-1) was the same as in Example 1 except that the hard coat agent (9) was used instead of the hard coat agent (1). A hard coat film in which a bond was formed was prepared.

(Example 10)
The interface between the hard coat layer (x-10) and the surface layer (y-1) was the same as in Example 1 except that the hard coat agent (10) was used instead of the hard coat agent (1). A hard coat film in which a bond was formed was prepared.

(Example 11)
The interface between the hard coat layer (x-11) and the surface layer (y-1) was the same as in Example 1 except that the hard coat agent (11) was used instead of the hard coat agent (1). A hard coat film in which a bond was formed was prepared.

(Example 12)
The interface between the hard coat layer (x-12) and the surface layer (y-1) was the same as in Example 1 except that the hard coat agent (12) was used instead of the hard coat agent (1). A hard coat film in which a bond was formed was prepared.

(Example 13)
The interface between the hard coat layer (x-13) and the surface layer (y-1) was the same as in Example 1 except that the hard coat agent (13) was used instead of the hard coat agent (1). A hard coat film in which a bond was formed was prepared.

(Example 14)
The interface between the hard coat layer (x-14) and the surface layer (y-1) was the same as in Example 1 except that the hard coat agent (14) was used instead of the hard coat agent (1). A hard coat film in which a bond was formed was prepared.

(Example 15)
The interface between the hard coat layer (x-15) and the surface layer (y-1) was the same as in Example 1, except that the hard coat agent (15) was used instead of the hard coat agent (1). A hard coat film in which a bond was formed was prepared.

(Example 16)
The interface between the hard coat layer (x-16) and the surface layer (y-1) was the same as in Example 1 except that the hard coat agent (16) was used instead of the hard coat agent (1). A hard coat film in which a bond was formed was prepared.

(Example 17)
The interface between the hard coat layer (x-17) and the surface layer (y-1) was the same as in Example 1 except that the hard coat agent (17) was used instead of the hard coat agent (1). A hard coat film in which a bond was formed was prepared.

(Example 18)
After forming a pre-curing laminated film in the same manner as in Example 2, the pre-curing laminated film is rolled into a roll through a polystyrene film (Asahi Kasei Chemicals, OPS film GM type, thickness 20 μm). Winded up. At that time, the polystyrene film was in contact with the surface of the layer formed using the coating agent (1) for forming the surface layer.

  The material wound up in the form of a roll is allowed to stand in an air atmosphere at 60 ° C. for one week, thereby allowing —Si—O at the interface between the hard coat layer (x-5) and the surface layer (y-1). A hard coat film in which a —Si— bond was formed was produced.

(Comparative Example 1)
The interface between the hard coat layer (x-18) and the surface layer (y-1) was the same as in Example 1 except that the hard coat agent (18) was used instead of the hard coat agent (1). A hard coat film in which a bond was formed was prepared.

(Comparative Example 2)
The interface between the hard coat layer (x-19) and the surface layer (y-1) was the same as in Example 1 except that the hard coat agent (19) was used instead of the hard coat agent (1). A hard coat film in which a bond was formed was prepared.

(Comparative Example 3)
The interface between the hard coat layer (x-20) and the surface layer (y-1) in the same manner as in Example 1 except that the hard coat agent (20) was used instead of the hard coat agent (1). A hard coat film in which a bond was formed was prepared.

(Comparative Example 4)
The interface between the hard coat layer (x-21) and the surface layer (y-1) was the same as in Example 1 except that the hard coat agent (21) was used instead of the hard coat agent (1). A hard coat film in which a bond was formed was prepared.

(Comparative Example 5)
The interface between the hard coat layer (x-22) and the surface layer (y-1) was the same as in Example 1 except that the hard coat agent (22) was used instead of the hard coat agent (1). A hard coat film in which a bond was formed was prepared.

(Comparative Example 6)
The interface between the hard coat layer (x-23) and the surface layer (y-1) was the same as in Example 1 except that the hard coat agent (23) was used instead of the hard coat agent (1). A hard coat film in which a bond was formed was prepared.

(Comparative Example 7)
The interface between the hard coat layer (x-24) and the surface layer (y-1) was the same as in Example 1 except that the hard coat agent (24) was used instead of the hard coat agent (1). A hard coat film in which a bond was formed was prepared.

(Comparative Example 8)
The interface between the hard coat layer (x-25) and the surface layer (y-1) was the same as in Example 1 except that the hard coat agent (25) was used instead of the hard coat agent (1). A hard coat film in which a bond was formed was prepared.

(Comparative Example 9)
The interface between the hard coat layer (x-26) and the surface layer (y-1) was the same as in Example 1 except that the hard coat agent (26) was used instead of the hard coat agent (1). A hard coat film in which a bond was formed was prepared.

(Comparative Example 10)
The interface between the hard coat layer (x-27) and the surface layer (y-1) was the same as in Example 1 except that the hard coat agent (27) was used instead of the hard coat agent (1). A hard coat film in which a bond was formed was prepared.

(Comparative Example 11)
The interface between the hard coat layer (x-28) and the surface layer (y-1) was the same as in Example 1 except that the hard coat agent (28) was used instead of the hard coat agent (1). A hard coat film in which no bond was formed was prepared.

[Measurement of plastic hardness]
A highly transparent adhesive tape “ZB7010W-15” manufactured by DIC Corporation was bonded to the back surface (the surface not having the hard coat layer and the surface layer) of the hard coat film, and the resultant was bonded to a glass plate.

  The plastic hardness of the surface layer constituting the hard coat film was determined by using a Fischer scope HM2000Xyp (Fischer Instruments) with a Vickers indenter with an edge angle of 136 ° under a 1 mN load in an environment of 23 ° C. and 50% RH. Measured by pushing.

[Measurement of water contact angle]
Using the automatic contact angle meter “DROMPAMSTER500” manufactured by Kyowa Interface Science Co., Ltd., 3 μL of purified water was deposited on the surface of the surface layer of the hard coat film obtained above, and the contact angle after 1 second was measured. did. In addition, the water contact angle of the hard coat film which does not have a surface layer measured the water contact angle of arbitrary surfaces by the method similar to the above.

  The contact angle calculation method in this measurement was based on the sessile drop method among the test methods described in JIS R3257.

[Evaluation of antifouling properties]
The index finger was pressed against the surface of the surface layer of the hard coat film for 10 seconds under a load of 500 g, and the surface was visually observed under a three-wavelength fluorescent lamp. The antifouling property was evaluated according to the following criteria after evaluation with 10 monitors.

  ○: 10 to 5 people evaluated that the surface of the hard coat film had almost no fingerprint attached.

  (Triangle | delta): Four to two people evaluated that the adhesion of the fingerprint was hardly on the surface of the said hard coat film.

  X: Less than two persons evaluated that there was almost no fingerprint adhesion on the surface of the hard coat film.

[Sliding evaluation method (dynamic friction coefficient)]
A friction element was prepared by fixing cotton canvas # 11 to the tip of a 10 mm diameter stainless steel round bar (weight approximately 82 g) with double-sided adhesive tape, and the surface layer of the hard coat film was made at a speed of 1000 mm / min. The coefficient of dynamic friction was calculated by measuring the frictional resistance when rubbing with

[Measurement of pencil hardness]
A hard coat film cut into 10 cm square is fixed to a glass plate with a cellophane tape so that the surface layer is on top, and then the pencil hardness of the surface layer is measured according to JIS K 5600-5-4 (1999). Measured using a pencil scratch tester for coating film (load: 750 g, manual type) manufactured by Imoto Seisakusho Co., Ltd.

[Evaluation of scratch resistance]
A highly transparent adhesive tape “ZB7010W-15” manufactured by DIC Corporation was bonded to the back surface (the surface not having the hard coat layer and the surface layer) of the hard coat film, and was bonded to a transparent glass plate. Next, steel wool (Bonster # 0000) was grounded to the surface layer of the hard coat film with a load of 500 g / cm ² and then rubbed 3000 times so that the friction distance was 100 mm and the friction speed was 60 reciprocations / minute. The scratch resistance was determined based on the following criteria from the result of visual observation of the friction part using the transmitted light of a fluorescent lamp.

  A: There were no scratches.

  ○: Scratches with a length of less than 5 mm were attached.

  X: Scratches with a length of 5 mm or more were attached.

[Anti-fouling durability 1 <Evaluation based on water contact angle after wear test>]
The water contact angle of the friction part of the hard coat film used in the above [Evaluation of scratch resistance] was measured by the same method as described in the column of [Measurement of water contact angle], and the water contact angle after friction was measured. Was measured.

[Anti-fouling durability 2 <fingerprint>]
The antifouling property of the friction part of the hard coat film used in the above [Evaluation of Scratch Resistance] was determined by the same method as described in the column of [Evaluation of Antifouling].

[Anti-fouling durability evaluation 3 <Magic>]
The surface of the surface layer of the hard coat film obtained above was rubbed 10 times with a magic (Macra Care, black) manufactured by Zebra Co. under a load of 500 g, and the repellency of the ink was visually observed. Further, the wiping condition of the ink after wiping the test portion with Kimwipe five times was visually observed. The determination was made according to the criteria described in Table 5.

  As is apparent from the above table, the hard coat films of the present invention of Examples 1 to 18 were hard coat films having excellent antifouling properties and scratch resistance and excellent durability. On the other hand, the hard coat films of Comparative Examples 1 to 11 did not have sufficient scratch resistance and antifouling durability.

Claims (11)

A hard coat film in which a hard coat layer (X) and a surface layer (Y) are sequentially laminated on at least one surface of a substrate,
The hard coat layer (X) has a hydrolyzable silyl group or silanol group and a radical polymerizable functional group (x1), a radical polymerizable compound (x2) other than the compound (x1), and a polymerization initiator Is a layer formed using a hard coat agent containing
The compound (x1) is contained in an amount of 2.9% by mass or more based on the total of the radical polymerizable compound (x2) and the polymerization initiator, and the plasticity of the surface on the surface layer (Y) side of the hard coat film A hard coat film having a hardness of 1000 N / mm ² or more. A hydrolyzable silyl group or silanol group of the compound (x1) and a functional group of the compound (y1) used for forming the surface layer (Y) react to form a bond (xy). Item 2. The hard coat film according to Item 1. The hard coat film according to claim 1 or 2, wherein the radical polymerizable functional group of the compound (x1) and the radical polymerizable functional group of the radical polymerizable compound (x2) are polymerized. The compound (x1) is a compound (x1-1) represented by the following general formula (1) or a compound (x1-2) having a structure represented by the following general formula (2) and general formula (3). The hard coat film according to claim 1, which is contained.

(R ₁ , R ₂ and R _{3 in the} general formula (1) each independently represent a hydrogen atom or an alkyl group, R ₄ represents an alkylene group having 4 to 10 carbon atoms, and R ₅ represents a hydrogen atom or Represents a methyl group.)

(R ₁ , R ₂ and R _{3 in} general formula (2) each independently represent a hydrogen atom or an alkyl group, and R _{5 in} general formula (3) represents a hydrogen atom or a methyl group.) The compound (x1-2) has a molar ratio of the structure represented by the following general formula (2) to the structure represented by the following general formula (3) [structure represented by the general formula (2) / the following general formula (3). The hard coat film according to claim 4, which is a compound (x1-2-1) having a structure represented by 5/1 to 1/5. The hard coat film according to claim 1, wherein the radical polymerizable compound (x2) is urethane (meth) acrylate. The hard coat film according to any one of claims 1 to 6, wherein a water contact angle of a surface constituted by the surface layer (Y) is 110 ° or more. Furthermore, the hard coat film of any one of Claims 1-7 which has a decorating layer or an adhesive layer. An information display device in which the hard coat film according to claim 1 is laminated. The information display apparatus which has the structure by which the hard coat film of any one of Claims 1-9 was stuck to the non-glass member which comprises the surface of the information display part of an on-cell type touch panel apparatus or an in-cell type touch panel apparatus. The information display device according to claim 10, wherein the non-glass member is a polarizing plate.