JP2014088010A - Decorative hard coat film and decorative hard coat adhesive film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative hard coat film whose surface hardness does not deteriorate easily and which provides good punching workability and reworkability, despite its dominantly thin configuration.SOLUTION: Provided is a decorative hard coat film comprising a hard coat film having a hard coat layer on at least one surface of a substrate; a decorative layer disposed on a portion of a surface of the hard coat film; and a resin layer comprising an active energy ray-curable resin composition disposed on a decorative layer-side surface of the hard coat film, wherein a storage modulus (E') of a resin layer comprising the active energy ray-curable resin composition measured at a frequency of 3.5 Hz at 60°C is 2.0×10to 9.0×10. With the decorative hard coat film, despite its dominantly thin configuration, good punching workability and, further, suitable reworkability can be realized after being fixed to another member.

Description

  The present invention relates to a decorative hard coat film in which an active energy ray-curable resin composition is provided on the surface of a hard coat film having a decorative layer on a part of the surface.

  In an image display device such as a liquid crystal display device used for a small electronic terminal such as a mobile personal computer, an electronic notebook, or a mobile phone, a transparent image display panel is usually provided above the image display module. The image display panel is fixed to the image display module or the housing with a transparent adhesive tape or the like, but the image display panel is often provided with a decoration layer for the purpose of decoration or light shielding. Due to the difference in level, bubbles may be generated at the interface between the image display panel and the adhesive tape.

  In order to solve such a problem, an image obtained by filling the surface of the decorative layer side of the image display panel provided with the decorative layer with an ultraviolet curable resin and smoothing the step generated by the decorative layer with the ultraviolet curable resin A display panel has been proposed (see Patent Documents 1 and 2).

Patent No. 4640626 Patent No. 4968755

  Small electronic terminals such as mobile personal computers, electronic notebooks, and mobile phones are becoming thinner and smaller. In recent years, image display devices such as liquid crystal display devices used in the small electronic terminals have become increasingly lighter, thinner, and smaller. Is required. Conventionally, as an image display panel, a panel having a hard coat film provided on the surface of a panel made of a transparent resin has been used. However, with the demand for thinning of the image display device, the image display device has a small layer structure. Conversion is required.

  In response to the request for the reduction in thickness, the image display panel can be composed of only a hard coat film, so that the layer configuration can be reduced. However, if the transparent resin panel is simply replaced with a hard coat, the surface hardness of the image display panel tends to decrease, and the image display panel cracks when the image display panel is punched or reworked after being fixed with adhesive tape. There were cases where tears occurred.

  The problem to be solved by the present invention is to provide a decorated hard coat film that has a configuration superior in thinness but is less likely to cause a decrease in surface hardness and has good punchability and reworkability. .

In the present invention, a hard coat film having a hard coat layer on at least one surface of the substrate, a decorative layer provided on a part of the hard coat film surface, and an activity provided on the surface having the hard coat film decorative layer A storage elastic modulus (E ′) of 60 ° C. measured at a frequency of 3.5 Hz of the resin layer made of the active energy ray curable resin composition. 2.0 × 10 ^{8 to} 9.0 × 10 ⁸ with a decorative hard coat film, while having a configuration superior in thinness, suitable surface hardness and punching workability, and further after being fixed to another member Suitable reworkability can be realized.

  Further, the decorative hard coat pressure-sensitive adhesive film having a pressure-sensitive adhesive layer on the surface of the resin layer made of the active energy ray-curable resin composition of the decorative hard-coat film, in particular, the pressure-sensitive adhesive layer is a monomer mainly composed of an alkoxyalkyl acrylate. The decorative hard coat adhesive film, which is an adhesive layer made of an acrylic adhesive composition containing an acrylic copolymer as a component, provides excellent surface hardness and punching workability while being superior in thinness. And suitable reworkability can be expressed.

  Since the decorative hard coat film of the present invention has a configuration in which a decorative layer is directly provided on the hard coat film, it is advantageous for thinning the image display device. Moreover, by making the resin layer made of the active energy ray-curable resin composition provided on the decorative layer side into a specific resin layer, it is difficult for the surface hardness to decrease, and the hard coat layer or resin layer during the punching process Since it is difficult for cracks to occur, it has suitable punching workability. Furthermore, even when fixed to other members via an adhesive layer or adhesive tape, the hard coat layer and the resin layer are not easily cracked during rework, and the decorative hard coat is difficult to tear off. realizable. For this reason, the decorative hard coat film of the present invention is used for image display devices for electronic devices, particularly for image display devices for small electronic terminals such as mobile personal computers, electronic notebooks, and mobile phones, which are highly demanded for thinning and miniaturization. It can be suitably applied as an image display panel.

It is a figure which shows an example of the structural example of the decorating hard coat film of this invention. It is a figure which shows an example of the structural example of the decorating hard coat film of this invention.

  The decorated hard coat film of the present invention has a hard coat film having a hard coat layer on at least one surface of the substrate, a decorative layer provided on a part of the hard coat film surface, and a decorative layer of the hard coat film. It is a decorative hard coat film having a resin layer made of an active energy ray-curable resin composition provided on the surface.

[Base material]
The base material used for this invention can use the base material suitable for thickness reduction, It is preferable that the thickness is 50-160 micrometers, More preferably, it is 50-130 micrometers, More preferably, it is 60-110 micrometers. In the present invention, by setting the thickness of the base material within the range, curling is easily suppressed even when a hard coat layer is provided on one or both sides of a thin hard coat film. In addition, in cutting and punching when a hard coat layer with high hardness is provided, it is easy to suppress the elongation of the substrate due to the pressing of the cutting blade, and the hard coat layer in contact with the cutting blade is the hard coat layer on the other side The elongation of the base material does not become too large, and cracking of the hard coat layer can be suitably suppressed.

  As the substrate, it is preferable to use a film substrate having an elastic modulus of 3 to 7 GPa, and it is particularly preferable to use a film substrate having 3 to 5 GPa. When the elastic modulus is within this range, deformation of the film base material is less likely to occur when the hard coat film is formed, and it is suitable for suppressing cracking of the hard coat layer, and it is easy to suppress a decrease in hardness of the hard coat film surface. Moreover, since the flexibility of a film base material can be ensured, it becomes easy to follow a gently curved surface when a hard coat film is attached.

  As the film substrate used in the present invention, various resin film substrates generally used as a substrate of a hard coat film can be used. For example, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, cellophane, Diacetyl cellulose, triacetyl cellulose, acetyl cellulose butyrate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polymethylpentene, polysulfone, polyether ether ketone, polyether sulfone, Examples of the resin film include polyetherimide, polyimide, fluorine resin, nylon, and acrylic resin.

  The film substrate used in the present invention may be a substrate composed only of the resin film, but a film substrate provided with a thin primer layer on the resin film in order to improve adhesion to the hard coat layer. It may be. In addition, for the purpose of improving the adhesion with the hard coat layer, surface roughening treatment by sandblasting method or solvent treatment method, or corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, Surface treatment such as surface oxidation treatment can be performed.

[Hard coat layer]

  The hard coat layer used in the present invention can be a hard coat layer formed using various hard coat agents. As the hard coating agent, an active energy ray-curable resin composition can be suitably used. Especially, as a hard-coat agent which forms the hard-coat layer used for this invention, the hard-coat agent containing urethane (meth) acrylate can be used preferably. As urethane (meth) acrylate, various urethane (meth) acrylates used for hard coating agents can be used, among them, acrylate (a1) having a hydroxyl group and two or more (meth) acryloyl groups, and a polyisocyanate. What contains polyfunctional urethane (meth) acrylate (A) obtained by making it react with (a2) as an essential component is preferable.

  Examples of the acrylate (a1) having one hydroxyl group and two or more (meth) acryloyl groups in one molecule used in the present invention include trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, penta Examples include polyacrylates of polyhydric hydroxyl group-containing compounds such as erythritol tetra (meth) acrylate and dipentaerythritol penta (meth) acrylate, adducts of these polyacrylates with ε-caprolactone, and these polyacrylates Examples include adducts with alkylene oxides and epoxy acrylates. These acrylates (a1) can be used alone or in combination of two or more.

  Of these acrylates (a1), an acrylate having one hydroxyl group and 3 to 5 (meth) acryloyl groups in one molecule is preferable. Examples of such acrylates include pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and the like, and these are particularly preferable because a cured film having high hardness can be obtained.

  Examples of the polyisocyanate (a2) used in the present invention include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,5- Aromatic isocyanate compounds such as naphthalene diisocyanate and 4,4'-diphenylmethane diisocyanate; Alicyclic rings such as dicyclohexylmethane diisocyanate, isophorone diisocyanate, norbornane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated methylenebisphenylene diisocyanate, and 1,4-cyclohexane diisocyanate A compound having two isocyanate groups bonded to a hydrocarbon (hereinafter abbreviated as alicyclic diisocyanate); trimethylene diisocyanate, hexamethyl Compounds having two isocyanate groups attached to aliphatic hydrocarbons such as emissions diisocyanate (hereinafter, abbreviated as aliphatic diisocyanates.) And the like. These polyisocyanates can be used alone or in combination of two or more.

  Further, these polyisocyanates (a2) give high toughness to the coating film, and cracks and the like are less likely to occur. Therefore, aliphatic diisocyanates or alicyclic diisocyanates are preferred, and among them, isophorone diisocyanate, norbornane diisocyanate, hydrogenated xylylene. Range isocyanate, hydrogenated methylene bisphenylene diisocyanate and hexamethylene diisocyanate, 1,6-hexamethylene diisocyanate, dicyclohexylmethane-4,4′-diisocyanate are preferred.

  In particular, when forming a hard coat layer to be used as the outermost layer of the image display unit, as described above, in order to realize a balance between high hardness and shrinkage rate, as the hard coat agent used for the hard coat layer, active energy rays are used. The active energy ray-curable resin composition is characterized in that the cured coating film contains two or more different cyclic skeletons, at least one of which is a heterocyclic compound. It is preferable. As the active energy ray-curable resin used for the hard coating agent, a monofunctional one may be used, but in order to obtain high pencil hardness, a polyfunctional (meth) acrylate is preferable. For example, polyisocyanate ( Among a2), it is an addition reaction product of polyisocyanate (a2-1) having a cyclic skeleton and acrylate (a1-1) having one hydroxyl group and two or more (meth) acryloyl groups in one molecule. Examples thereof include cyclic skeleton-containing urethane acrylate. Particularly preferred is a urethane acrylate containing a cyclic skeleton obtained by addition reaction of a polyfunctional acrylate and a polyisocyanate having a cyclic skeleton, although it contains two or more cyclic skeletons, one of which is a heterocyclic skeleton. Thus, it is possible to obtain a coating film having a good balance between pencil hardness and curl after active energy ray curing.

  As a method for introducing a heterocyclic skeleton, for example, a polyfunctional (meth) acrylate having a cyclic skeleton and a polyfunctional (meth) acrylate containing a heterocyclic skeleton may be blended, respectively. Polyfunctional (meth) acroyl containing a heterocyclic skeleton different from (a2-1) in isocyanate (a2-1) and acrylate (a1) having one hydroxyl group and two or more (meth) acryloyl groups in one molecule An active energy ray-curable resin composition containing two or more different types of cyclic skeletons in one molecule using an acrylate (a1-2) having a group, and at least one of which is a heterocyclic skeleton, is obtained. It doesn't matter. Other methods for introducing two or more kinds of cyclic skeletons into one molecule include, for example, those obtained by adding the above (a1-2) to a trimer of polyisocyanate (a2-2) having an alicyclic cyclic skeleton Etc.

  Examples of the heterocyclic skeleton-containing polyfunctional acrylate (a1-2) include bis (acryloxyethyl) hydroxyethyl isocyanurate (Aronix M-215). As the single heterocyclic skeleton-containing polyfunctional (meth) acrylate, for example, bis (acryloxyethyl) hydroxyethyl isocyanurate (Aronix M-215), tris (2-hydroxyethyl) isocyanate triacrylate (Aronix M-315) , Caprolactone-modified tris (acryloxyethyl) isocyanurate (Aronix M-325), neopentyl glycol-modified trimethylolpropane diacrylate (Kayarad R-604), and the like.

  The urethane acrylate (A) used in the present invention is obtained by subjecting two components of the polyisocyanate (a2) and the acrylate (a1) to an addition reaction. The ratio of the acrylate (a1) to 1 equivalent of isocyanate in the polyisocyanate (a2) is usually preferably 0.1 to 50, more preferably 0.1 to 10, and preferably 0.9 to 1.3 as a hydroxyl equivalent. Is more preferable, and 1.01-1.24 is particularly preferable. Moreover, 30-150 degreeC is preferable and, as for the reaction temperature of the said polyisocyanate (a2) and the said acrylate (a1), 50-100 degreeC is more preferable. In addition, the end point of reaction can be confirmed by calculating | requiring an isocyanate group content rate by the loss | disappearance of the infrared absorption spectrum of 2250cm <-1> which shows an isocyanate group, or the method as described in JISK7301-1995, for example. Moreover, it is preferable that the average of the (meth) acryloyl group of urethane (meth) acrylate (A) is five or more.

  The molecular weight of the urethane acrylate (A) is preferably in the range of 500 to 1,500. When the molecular weight is within this range, a cured film having a sufficiently high hardness can be obtained and curing shrinkage can be reduced. Therefore, the curl of the film having the cured film can be easily reduced, which is preferable.

  The blending amount of the urethane acrylate (A) in 100 parts by weight of the resin component in the resin composition is preferably 5 to 90 parts by weight, more preferably 10 to 70 parts by weight, and even more preferably 10 to 60 parts by weight. . If the blending amount of the urethane acrylate (A) is within this range, a cured film having a sufficiently high hardness can be obtained, and there is no coating film defect, excellent surface antifouling properties, and curing shrinkage is reduced. This is preferable because the curl of the film having a cured coating can be easily reduced.

  In addition to the urethane acrylate (A), a urethane acrylate (B) other than the urethane acrylate (A) may be added to the active energy ray-curable resin composition used in the present invention. The urethane acrylate (B) is an acrylate (a1) having one hydroxyl group and two or more (meth) acryloyl groups in one molecule after an addition reaction between a polyol and the polyisocyanate (a2). Can be added. 10-150 weight part is preferable with respect to 100 weight part of said urethane acrylate (A), and, as for the compounding quantity at the time of mix | blending this urethane acrylate (B) in a resin composition, 50-130 weight part is more preferable.

  Moreover, it is also preferable to mix | blend the polymer (C) with a high (meth) acryloyl group equivalent in order to obtain high pencil hardness in the active energy ray hardening-type resin composition used for a hard-coat agent. As the polymer (C), for example, with respect to the (meth) acrylate polymer (c1) having a hydroxyl group, a carboxyl group, an epoxy group, etc. as a reactive functional group in the side chain, Examples thereof include a polymer having a (meth) acryloyl group obtained by reacting an α, β-unsaturated compound (c2) having a functional group such as an isocyanate group, a carboxyl group, an acid halide group, a hydroxyl group and an epoxy group capable of reacting. .

  As the photoinitiator used for the active energy ray-curable resin composition used as the hard coat agent, various materials can be used. Among them, benzophenone, benzyl, Examples include compounds that generate radicals by hydrogen abstraction such as Michler's ketone, thioxanthone, and anthraquinone. These compounds are generally used in combination with a tertiary amine such as methylamine, diethanolamine, N-methyldiethanolamine, or tributylamine that serves as a hydrogen abstracting agent.

  Another type of photopolymerization initiator includes, for example, a type of compound that generates radicals by intramolecular splitting. Specific examples include benzoin, dialkoxyacetophenone, acyloxime ester, benzyl ketal, hydroxyalkylphenone, halogenoketone and the like.

  Moreover, in the active energy ray-curable resin composition used as a hard coat agent for forming the hard coat layer, the amount of the active initiator used when the photoinitiator is added to the active energy ray-curable resin composition is the active energy. It is preferable to mix | blend 1-10 weight part with respect to 100 weight part of total weights of a linear curable resin composition, and it is still more preferable to mix | blend 4-9 weight part.

  Further, if necessary, a polymerization inhibitor such as hydroquinone, benzoquinone, tolhydronoquinone, paratertiary butylcatechol, etc. can be added in combination with a photopolymerization initiator.

  In the hard coat agent for forming the hard coat layer corresponding to the outermost layer of the image display unit used in the present invention, for the purpose of improving the surface properties such as surface slipperiness, stain resistance, and fingerprint resistance of the protective layer, the above An additive comprising a composition containing a compound having a fluorocarbon chain, a dimethylsiloxane chain, and a hydrocarbon chain having 12 or more carbon atoms may be added to the active energy ray-curable resin composition used for the hard coating agent. preferable. The additive amount of the additive containing a compound having a fluorocarbon chain, a dimethylsiloxane chain and a hydrocarbon chain having 12 or more carbon atoms is preferably 0.05 to 5% by weight with respect to the active energy ray-curable resin composition. 0.1 to 2% by weight is more preferable.

  Among these, a compound containing a fluorocarbon chain can be suitably used because it is excellent in surface properties such as stain resistance, fingerprint resistance, and magic wiping property. In particular, a heterocyclic ring is bonded to one or both ends of a poly (perfluoroalkylene ether) chain via a divalent linking group, and the heterocyclic ring has two or more (meta-metabolites via a divalent linking group. ) A compound having an acryloyl group bonded thereto is preferable.

[Hard coat film]
As the hard coat film used in the present invention, a hard coat film having a hard coat layer on at least one surface of a substrate can be used. Among these, a thin double-sided hard coat film having a hard coat layer on both sides of the substrate can be preferably used because it is thin and can easily realize suitable surface hardness and scratch resistance.

  As the surface hardness of the hard coat film, the pencil hardness is preferably H or more, and more preferably 2H or more. By setting the surface hardness, it becomes easy to obtain the scratch resistance of the decorative hard coat film. When the hard coat film is a double-sided hard coat film having hard coat layers on both sides, the pencil hardness of the hard coat layer on the side where the decorative layer is provided (hereinafter sometimes referred to as the first hard coat layer). Is preferably H or more, more preferably 2H or more. The pencil hardness of the hard coat layer used as the surface layer side (hereinafter sometimes referred to as the second hard coat layer) is preferably 2H or more, and more preferably 3H or more. By setting it as the said pencil hardness, it becomes easy to obtain the suitable damage prevention property and the workability at the time of punching.

  The thickness of the hard coat layer may be appropriately selected according to the application to be applied, but is preferably in the range of 1 to 15 μm when applied to a small electronic terminal or the like that is highly demanded to be thin. When the hard coat film is a double-sided hard coat film having hard coat layers on both sides, the thickness of the first hard coat layer is 1 to 6 μm, and the thickness of the second hard coat layer is 7 to 15 μm. It is preferable that By setting the thickness, it is easy to realize suitable surface characteristics such as surface hardness and scratch resistance, and thinning.

  When a hard coat film having a hard coat layer on both sides of the substrate described above is used as the hard coat film used in the present invention, the thickness of the first hard coat layer is set to the thickness of the second hard coat layer. 3/5 or less, preferably 1/10 to 3/5, more preferably 1/5 to 3/5, while maintaining curl and maintaining a suitable hardness, The stress to the first hard coat layer when the processing blade enters from the second hard coat layer side can be suppressed, and cracks in the first hard coat layer can be made difficult to occur.

  The hard coat film having the hard coat layer on both surfaces of the film base described above is configured such that the thickness of the constituent members is adjusted to a specific range and combined, thereby preventing curling and maintaining high surface hardness. It becomes a hard coat film excellent in crack resistance, that is, punching workability. For this reason, the hard coat film of this invention can be applied suitably for the screen panel use etc. of the portable electronic terminal in which fine processing is calculated | required.

  When a double-sided hard coat film having hard coat layers on both sides of the substrate is used, when a hard coat layer having a pencil hardness of H or higher, particularly 2H to 3H or higher is used, cutting or punching is performed. When performing, cracks of the hard coat layer, particularly cracks of the hard coat layer on the other side, are likely to occur with the hard coat layer in contact with the processing blade. However, with the above configuration, even if a hard coat layer with a pencil hardness of H or higher is used, the hard coat layer that comes into contact with the processing blade is greatly deformed by the pressing of the processing blade of the hard coat layer on the other side. The crack of a hard-coat layer can be suppressed suitably without becoming too much.

  Moreover, the hard coat film of the present invention is a hard coat film in which curling is unlikely to occur by laminating a hard coat layer in which physical property values are adjusted and combined in a specific range on each surface. For this reason, the hard coat film of the present invention has, for example, good laminating workability of a printing layer and a functional resin layer, and can be used for decoration and function addition in screen panel applications of portable electronic terminals.

  The hard coat film used in the present invention can be produced by applying and curing a hard coat agent used for the hard coat layer on at least one surface of the substrate.

  Examples of methods for applying a hard coating agent to a film substrate include gravure coating, roll coating, comma coating, air knife coating, kiss coating, spray coating, transfer coating, dip coating, spinner coating, wheeler coating, brush coating, and silk. Examples thereof include a solid coat using a screen, a wire bar coat, and a flow coat. Also, printing methods such as offset printing and letterpress printing may be used. Among these, gravure coating, roll coating, comma coating, air knife coating, kiss coating, wire bar coating, and flow coating are preferable because a coating film having a more constant thickness can be obtained.

  The hard coat agent curing device may be appropriately used according to the hard coat agent to be used, but when using the active energy ray-curable resin composition used for the hard coat agent as a hard coat agent, What is necessary is just to harden | cure by active energy rays, such as an electron beam and a radiation. Specific energy sources or curing devices include, for example, germicidal lamps, ultraviolet fluorescent lamps, carbon arc, xenon lamps, high pressure mercury lamps for copying, medium or high pressure mercury lamps, ultrahigh pressure mercury lamps, electrodeless lamps, metal halide lamps, natural light, etc. Or an electron beam using a scanning type or curtain type electron beam accelerator.

  Among these, ultraviolet rays are particularly preferable, and irradiation in an inert gas atmosphere such as nitrogen gas is preferable in terms of increasing the polymerization efficiency. Further, if necessary, heat may be used as an energy source and heat treatment may be performed after curing with active energy rays.

  When ultraviolet rays are used as a device for irradiating active energy rays, the light source is a low pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, metal halide lamp, electrodeless lamp (fusion lamp), chemical lamp, black light. Lamps, mercury-xenon lamps, short arc lamps, helium / cadmium lasers, argon lasers, sunlight, LEDs and the like can be mentioned. In addition, when the active energy ray-curable resin composition used in the present invention is applied to a film substrate to form a cured film, a flashing xenon-flash lamp is used. This is preferable because the influence of heat can be reduced.

  In the case of continuous production by roll-to-roll, the hard coat film is wound up in a roll shape, so that the hard coat layer to be applied / cured and the other surface having the hard coat layer are in contact with each other. As described above, when an additive such as a fluorocarbon chain or a dimethylsiloxane chain is used in the hard coat layer, the additive component may migrate to the surface on which the hard coat film is to be decorated, and may contaminate the surface. . In the hard coat film used in the present invention, in order to avoid the contamination on the surface to be decorated, the surface on which the hard coat layer is applied or the hard coat at the same time in the step of applying and curing the hard coat agent on the film substrate A protective film may be laminated on the other surface to which the layer is applied.

[Decoration layer]
The decorative layer of the decorative hard coat film of the present invention imparts various design properties to the hard coat film. As the decoration layer, for example, characters and figures visually recognized around the image display unit when used as an image display panel, or a black border-like decoration layer provided in a frame shape on the image display unit, etc. Is mentioned. Especially, when using the decoration layer provided in frame shape in an image display part, it is easy to express the effect of this invention especially suitably.

  As a method of providing the decorative layer on the hard coat film, a method by printing is simple, which is preferable. Examples of the printing method include a silk printing method, a screen printing method, a gravure printing method, and a thermal transfer printing method. Among these, a silk printing method, a screen printing method, and a thermal transfer printing method capable of printing a decorative layer having a high concealment property are preferable.

  As the ink used in the silk printing method and the screen printing method, various inks used for printing on a film can be used, and a solvent system or a UV curing system is used. In particular, solvent-based inks are preferably used because they only need to dry the solvent in a drying furnace, and therefore can be printed at low cost because no device such as a UV irradiation device is required.

  As the ink used for the thermal transfer system, a resin type or a wax type is used. Of these, the resin type is preferably used because of its excellent weather resistance.

  As thickness of a decoration layer, 30 micrometers or less are preferable, 1-15 micrometers is more preferable, and 2-10 micrometers is especially preferable. By setting it as the decorating layer of the said thickness, it is hard to produce a suitable color omission and a printing defect, and it becomes easy to obtain suitable designability.

[Resin layer comprising an active energy ray-curable resin composition layer]
The resin layer composed of the active energy ray-curable resin composition layer used for the decorative hard coat film of the present invention has a storage elastic modulus (E ′) at 60 ° C. measured at a frequency of 3.5 Hz of 2.0. A resin layer of × 10 ^{8 to} 9.0 × 10 ⁸ Pa, preferably 2.5 × 10 ^{8 to} 7.0 × 10 ⁸ Pa, more preferably 3.0 × 10 ^{8 to} 5.0 × 10 ⁸ Pa. use. By using the resin layer, it is difficult to cause a decrease in surface hardness even when a decorative hard coat film is formed. Can be realized. Furthermore, even when fixed to another member via an adhesive layer or an adhesive tape, the hard coat layer and the resin layer are not easily cracked during rework, and suitable reworkability can be realized.

Moreover, the resin layer which consists of an active energy ray hardening-type resin composition layer is suitable by making Martens hardness 70-100N / mm < ² > measured by pushing in a Vickers indenter of 136 degrees of edge angles with a load of 1 mN. It is preferable because it is easy to obtain excellent scratch resistance and surface hardness.

  The thickness of the resin layer composed of the active energy ray-curable resin composition layer is such that the maximum thickness is equal to or greater than the thickness of the decorative layer, so that the step of the decorative layer can be suitably filled, and the active energy It becomes easy to ensure the smoothness of the resin layer surface which consists of a wire curable resin composition layer.

  The active energy ray-curable resin composition used for the resin layer includes, for example, urethane acrylate (D), trifunctional or higher acrylate (E), monofunctional or bifunctional acrylate (F), and photopolymerization initiator (G). The thing which has is mentioned.

Here, the blending ratio of each of the components (D) to (G) is such that the urethane acrylate (D) is 30 to 60 parts by weight and trifunctional or more per 100 parts by weight of the total of the components (D) to (F). The proportion of acrylate (E) is 5 to 30 parts by weight, monofunctional or bifunctional acrylate (F) is 20 to 60 parts by weight, and the total of 100 parts by weight of components (D) to (F) The photopolymerization initiator (G) has a ratio of 0.1 to 10 parts by weight, and the cured product of the composition has appropriate flexibility and hardness, and is measured at a frequency of 3.5 Hz. The 60 ° C. storage elastic modulus (E ′) is preferable from the viewpoint of easy adjustment to a range of 2.0 × 10 ^{8 to} 9.0 × 10 ⁸ .

  Moreover, the viscosity of the said active energy ray hardening-type resin composition is 300-1000 mPa.s by the point which is excellent in coating property. The range of s is preferable, and the double bond concentration of the active energy ray-curable resin composition is preferably in the range of 4 to 6 mmol / g in terms of excellent balance between flexibility and curability.

  More specifically, the urethane acrylate (D) is an isocyanate group-containing urethane prepolymer obtained by reacting an aliphatic polyester diol (d1) and a diisocyanate (d2), and an acrylate (d3) having a hydroxyl group. Can be obtained by reacting. The urethane acrylate (D) obtained by the reaction is imparted with appropriate flexibility, can easily be adjusted to the desired storage elastic modulus (E ′), and has good workability and reworkability. This is preferable.

  In particular, in the present invention, by using the aliphatic polyester diol (d1) as a raw material monomer for the urethane acrylate (D), an appropriate flexibility can be imparted to the urethane acrylate (D). The aliphatic polyester diol (d1) used here is, for example, an aliphatic polycarboxylic acid such as malonic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, Reaction with aliphatic polyols such as butylene glycol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, glycerin, trimethylolpropane, pentaerythritol Examples of the diol compound obtained include diol compounds obtained by ring-opening polymerization of a lactone compound such as γ-butyrolactone, δ-valerolactone, and ε-caprolactone and the aliphatic polyol. Among these, the urethane acrylate (D) to be obtained is preferably a reaction product of ε-caprolactone and an aliphatic polyol from the viewpoint that good flexibility can be expressed.

  The number average molecular weight (Mn) of the aliphatic polyester diol (d1) is such that the obtained urethane acrylate (D) is a compound having excellent compatibility with other components, and the obtained urethane acrylate (D) is good. In addition to having excellent flexibility, the range of 300 to 1000 is preferable from the viewpoint of having both excellent curability and hardness in the cured product, and in particular, such an effect is remarkable in the range of 400 to 600. It is particularly preferable from the point of becoming. Here, the number average molecular weight (Mn) is a value calculated from the hydroxyl value of the aliphatic polyester diol (d1).

  Examples of the diisocyanate (d2) include fats such as aromatic diisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate, hexamethylene diisocyanate, and 2,2,4-trimethylhexane diisocyanate. Alicyclic diisocyanates such as aromatic isocyanate, 1,4-cyclohexane diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, methylcyclohexane diisocyanate, 1,2-bis (isocyanatomethyl) cyclohexane, norbornene diisocyanate. Among them, alicyclic diisocyanate is preferable and isophorone diisocyanate is particularly preferable in that the obtained urethane acrylate becomes a compound having excellent compatibility with other components.

  Examples of the acrylate (d3) having a hydroxyl group include hydroxy acrylate having one acryloyl group such as hydroxyethyl acrylate, hydroxypropyl acrylate, and hydroxybutyl acrylate, glycerin diacrylate, isocyanuric acid ethylene oxide-modified diacrylate, and pentaerythritol triacrylate. And hydroxyacrylates having two or more acryloyl groups such as ditrimethylolpropane triacrylate and dipentaerythritol pentaacrylate. Among these, a hydroxy acrylate having two or more acryloyl groups is preferable, and pentaerythritol triacrylate is particularly preferable in that the obtained urethane acrylate is a compound having an excellent balance between flexibility and curability.

  The urethane acrylate (D) obtained by reacting the above components preferably has a double bond concentration in the range of 4 to 6 mmol / g from the viewpoint of excellent balance between flexibility and curability.

  Next, the tri- or higher functional acrylate (E) can exhibit excellent curability and hardness in the cured product while maintaining good flexibility in the cured product of the active energy ray-curable resin composition. It is a possible ingredient. Here, the tri- or higher functional acrylate (E) is, for example, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, glycerin triacrylate, isocyanuric acid ethylene oxide-modified triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, diester Examples include pentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and compounds obtained by modifying the above acrylate with an alkyl group, ethylene oxide, propylene oxide, ε-caprolactone, or the like. Among these, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and ε-caprolactone-modified dipentaerythritol hexaacrylate are preferable in terms of excellent balance between flexibility and curability.

  Next, the monofunctional or bifunctional acrylate (F) is a component for reducing the viscosity of the active energy ray-curable resin composition and improving the coating properties of the composition, such as methyl acrylate, Ethyl acrylate, butyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, acryloyl morpholine, tetrahydrofurfuryl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, isobornyl acrylate, benzyl acrylate, phenoxy Acrylate, methoxypolyethylene glycol acrylate, methoxypolypropylene glycol acrylate, dimethylaminoethyl acrylate, (poly) ethylene glycol dia Relate, (poly) propylene glycol diacrylate, (poly) butylene glycol diacrylate, neopentyl glycol diacrylate, hexanediol diacrylate, bisphenol A ethylene oxide modified diacrylate, bisphenol F di ethylene oxide-modified acrylate. Among these, tetrahydrofurfuryl alcohol acrylic acid large amount ester and tetraethylene glycol diacrylate are preferable in terms of excellent adhesion to the first hard coat layer and relatively weak skin irritation.

  Various things can be used for the said photoinitiator (G). For example, photoinitiators that generate radicals by hydrogen abstraction such as benzophenone, thioxanthone, Michler ketone, oxyphenylacetate, benzoin, dialkoxyacetophenone, acyloxime ester, benzyl ketal, hydroxyalkylphenone, aminoalkylphenone, acylphosphine oxide, etc. Photoinitiators that generate radicals by intramolecular cleavage of Among these, 2-hydroxy-2-methyl-1-phenylpropan-1-one is particularly preferable because it is liquid and can be easily mixed with other components.

[Decorated hard coat film]
The decorative hard coat film of the present invention is provided with a resin layer made of an active energy ray-curable resin composition on the surface of the hard coat film provided with a decorative layer on the surface of the hard coat film. It is a decorated hard coat film. By setting it as the said structure, favorable rework property at the time of fixing with favorable surface hardness, punching workability, and another member is realizable.

  The decorative hard coat film of the present invention has a structure having a resin layer made of an active energy ray-curable resin composition on the surface of the hard coat film having a decorative layer, but the resin layer is a hard coat. A structure in which the surface of the hard coat film is flattened so as to cover the decorative layer provided on a part of the film surface (FIG. 1), or the surface of the hard coat film The resin layer is provided on the surface of the hard coat film other than the portion where the decorative layer is provided, and the thickness of the resin layer is equal to the thickness of the decorative layer, so that the resin layer side of the decorative hard coat film Any configuration of the configuration in which the surface is flattened (FIG. 2) may be used. The former configuration is preferable because the surface smoothness can be easily secured easily, and the latter configuration is preferable because the decorative hard coat film can be easily made thinner.

  Examples of the method of applying the active energy ray-curable resin composition layer of the decorative hard coat film of the present invention to the surface having the decorative layer of the hard coat film include a gravure coat, a roll coat, a comma coat, an air knife coat, Examples include kiss coat, spray coat, transfer coat, dip coat, spinner coat, wheeler coat, brush coat, solid coat with silk screen, wire bar coat, and flow coat. In addition, printing methods such as offset printing, letterpress printing, silk printing, and screen printing can be used.

  The curing device for the active energy ray curable resin composition may be appropriately used according to the active energy ray curable resin composition. When the active energy ray curable resin composition is used, the hard coating agent is used. The same equipment as the curing equipment can be used.

  Among these, as an apparatus for curing the active energy ray-curable resin composition used in the present invention, ultraviolet rays are particularly preferable.

  In order to increase the polymerization efficiency, it is preferable to irradiate in an inert gas atmosphere such as nitrogen gas. Furthermore, the method of hardening with an active energy ray in the state pressed smoothly with the film and the glass panel can be used. Further, if necessary, heat may be used as an energy source and heat treatment may be performed after curing with active energy rays.

  When ultraviolet rays are used as a device for irradiating active energy rays, the light source is a low pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, metal halide lamp, electrodeless lamp (fusion lamp), chemical lamp, black light. Lamps, mercury-xenon lamps, short arc lamps, helium / cadmium lasers, argon lasers, sunlight, LEDs and the like can be mentioned. In addition, when the active energy ray-curable resin composition used in the present invention is applied to a film substrate to form a cured film, a flashing xenon-flash lamp is used. This is preferable because the influence of heat can be reduced.

  Further, in the case of continuous production by roll-to-roll, the decorative hard coat film is wound up in a roll shape, so that the active energy ray curable resin composition layer to be applied and cured and the active energy ray curable resin composition The other side of the surface with the layer contacts. As described above, when an additive such as a fluorocarbon chain or a dimethylsiloxane chain is used in the hard coat layer, the additive component migrates to the active energy ray-curable resin composition surface of the decorative hard coat film and contaminates the surface. May end up. In the decorative hard coat film used in the present invention, in order to avoid the contamination of the active energy ray-curable resin composition surface, a hard coat layer is applied simultaneously to the film base material and cured. A protective film may be laminated on the surface to be coated or the other surface to which the hard coat layer is applied.

[Decorative hard coat adhesive film]
The decorative hard coat pressure-sensitive adhesive film of the present invention is obtained by bonding the pressure-sensitive adhesive layer to the surface of the decorative hard coat film on the active energy ray-curable resin layer side, or the active energy ray-curable resin of the decorative hard coat film. It can manufacture by apply | coating an adhesive layer directly to the composition layer side surface.

[Adhesive layer]
For the pressure-sensitive adhesive used in the pressure-sensitive adhesive layer used in the present invention, known acrylic, rubber-based, and silicone-based pressure-sensitive resins can be used. Among them, a (meth) acrylic acid alkyl ester monomer and a (meth) acrylic acid monomer having a C 1-4 alkyl group as a main monomer are (meth) acrylic. An acid ester copolymer is preferable from the viewpoint of adhesion to the active energy ray-curable resin composition layer.

  Specific examples of the (meth) acrylic acid alkoxyalkyl ester monomer constituting the (meth) acrylic acid ester copolymer include 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, and 2-methoxytriacrylate. Examples include ethylene glycol, 3-methoxypropyl acrylate, 3-ethoxypropyl acrylate, 4-methoxybutyl acrylate, 4-ethoxybutyl acrylate, and the like. Among these, 2-methoxyethyl acrylate and 2-ethoxyethyl acrylate are particularly preferable. By using the monomer, cohesive force necessary for fixing the decorative hard coat film to the pressure-sensitive adhesive layer can be imparted.

  As the (meth) acrylic acid alkyl ester monomer (H) having an alkyl group having 1 to 4 carbon atoms constituting the (meth) acrylic acid ester copolymer, specifically, ethyl acrylate, acrylic acid n- Propyl, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, methacrylic acid and sec-butyl, t-butyl methacrylate and the like.

  Among these, an acrylic acid alkyl ester monomer having an alkyl side chain having 1 to 4 carbon atoms is preferable, and n-butyl acrylate is particularly preferable. By using an acrylic acid alkyl ester having an alkyl side chain with a carbon number within the above range, high adhesion to the active energy ray-curable resin composition layer can be obtained.

  The carboxyl group-containing monomer constituting the (meth) acrylic acid ester copolymer is not particularly limited, but acrylic acid, methacrylic acid, itaconic acid, maleic acid, crotonic acid, acrylic acid dimer, ethylene oxide modified succinate Examples include acid acrylates. Of these, acrylic acid is preferred because of its high versatility.

  The amount of the carboxyl group-containing monomer used is preferably 1% by weight or less, more preferably 0.5% by weight or less, and more preferably 0.1% by weight or less in the monomer component constituting the acrylic copolymer. . By setting the content of the carboxyl group-containing monomer within the range, corrosion of the metal can be prevented.

  It is also preferable to use a vinyl monomer having a functional group that reacts with the cross-linking agent in order to increase the cohesive force of the pressure-sensitive adhesive layer by suitably performing a cross-linking reaction with the cross-linking agent. Although it does not specifically limit as a vinyl monomer which has a functional group which reacts with a crosslinking agent, Hydroxyl group-containing vinyl monomers, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate, etc. Is mentioned.

  The amount of the vinyl monomer having a functional group used is preferably 0.1% by weight to 10% by weight in the monomer component constituting the acrylic copolymer, and is 0.5% by weight to 5% by weight. It is particularly preferred.

  The weight average molecular weight Mw of the (meth) acrylic acid ester copolymer is preferably 300,000 to 1,600,000, more preferably 400,000 to 1,300,000, and further preferably 500,000 to 1,000,000. When the weight average molecular weight Mw of the (meth) acrylic acid ester copolymer is within the above range, the adhesiveness to the active energy ray-curable resin composition surface can be suitably imparted.

  Further, the molecular weight distribution (weight average molecular weight Mw / number average molecular weight Mn) of the (meth) acrylic acid ester copolymer is preferably 10 to 50, more preferably 10 to 30, and still more preferably 10 to 20. By setting the molecular weight distribution (weight average molecular weight Mw / number average molecular weight Mn) of the (meth) acrylic acid ester copolymer within the above range, it is difficult to leave bubbles when sticking to the image display unit.

In the present invention, the weight average molecular weight Mw of the carboxyl group-containing (meth) acrylic acid ester copolymer (H) can be measured by gel permeation chromatography (GPC). More specifically, as a GPC measurement device, “SC8020” manufactured by Tosoh Corporation can be used to measure and obtain the following GPC measurement conditions based on polystyrene conversion values.
(GPC measurement conditions)
Sample concentration: 0.5% by weight (tetrahydrofuran solution)
Sample injection volume: 100 μL
・ Eluent: Tetrahydrofuran (THF)
・ Flow rate: 1.0 mL / min
Column temperature (measurement temperature): 40 ° C
Column: “TSKgel GMHHR-H” manufactured by Tosoh Corporation
・ Detector: Differential refraction

  The pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer used in the present invention preferably contains a crosslinking agent as a component other than the above-mentioned copolymer in order to increase the cohesive force of the pressure-sensitive adhesive layer.

  Examples of the crosslinking agent used include isocyanate crosslinking agents, epoxy crosslinking agents, chelating crosslinking agents, azirine crosslinking agents, and polyfunctional acrylates. Among these, an isocyanate-based crosslinking agent rich in reactivity with the components of the (meth) acrylic copolymer is preferable.

  0.05-2 mass parts is preferable, as for the compounding quantity of the crosslinking agent added to the adhesive layer of the said double-sided adhesive sheet and an adhesive film, 0.07-1.5 mass parts is more preferable, 0.1-1 mass Part is more preferred. By setting the content of the crosslinking agent in this range, it is easy to adjust the gel fraction of the pressure-sensitive adhesive layer to a suitable range.

In the pressure-sensitive adhesive layer used in the present invention, the gel fraction represented by the following formula when immersed in toluene for 24 hours is preferably 30 to 80%, more preferably 30 to 70%. 40-60% is most preferred. By setting the gel fraction of the pressure-sensitive adhesive layer within the above range, it is easy to suppress peeling over time in fixing to the image display unit, and it is difficult to leave bubbles when being applied to the image display unit.
Gel fraction (%) = [(mass after immersion of toluene in double-sided PSA sheet) / (mass before immersion of toluene in double-sided PSA sheet)] × 100

  The thickness of the pressure-sensitive adhesive layer used in the present invention is preferably 5 to 30 μm, and more preferably 8 to 20 μm. By setting it as this thickness range, while being able to obtain high pencil hardness on the surface of a decoration hard coat adhesive film, it becomes easy to obtain favorable punching workability.

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these.

(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 (hereinafter referred to as “NBDI”), 0.5 parts by mass of p-methoxyphenol, dibutyl After charging 0.5 parts by mass of tin diacetate and raising the temperature to 70 ° C. while blowing air, pentaerythritol triacrylate (hereinafter referred to as “PE3A”) / pentaerythritol tetraacrylate (hereinafter referred to as “PE4A”). ) 795 parts by mass of a mixture (mixture having a mass ratio of 75/25) was added dropwise over 1 hour. After completion of the dropwise addition, the mixture is reacted at 70 ° C. for 3 hours, and further reacted until the infrared absorption spectrum of 2250 cm ⁻¹ showing the isocyanate group disappears, and the alicyclic compound-containing polyfunctional urethane acrylate (A1) / PE4A mixture (mass ratio) A 80/20 mixture, a butyl acetate solution having a nonvolatile content of 80% by mass) was obtained. The molecular weight (calculated value) of urethane acrylate (A1) is 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 (hereinafter referred to as “IPDI”), 0.5 parts by mass of p-methoxyphenol, dibutyl After charging 0.5 parts by mass of tin diacetate and raising the temperature to 70 ° C., 795 parts by mass of a PE3A / PE4A mixture (a mixture with a mass ratio of 75/25) was added dropwise over 1 hour. After completion of the dropwise addition, the mixture is reacted at 70 ° C. for 3 hours, and further reacted until the infrared absorption spectrum of 2250 cm ⁻¹ showing the isocyanate group disappears, and the alicyclic compound-containing polyfunctional urethane acrylate (A2) / PE4A mixture (mass ratio) A 80/20 mixture, a butyl acetate solution having a nonvolatile content of 80% by mass) was obtained. The molecular weight (calculated value) of urethane acrylate (A2) is 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 (hereinafter referred to as “IPDI”), 0.5 parts by mass of p-methoxyphenol, dibutyl After charging 0.5 parts by mass of tin diacetate and raising the temperature to 70 ° C., 369 parts by mass of 369 parts by mass of bis (acryloxyethyl) hydroxyethyl isocyanurate and a mixture of PE3A / PE4A (a mixture with a mass ratio of 75/25) The solution was 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 continued until the infrared absorption spectrum of 2250 cm ⁻¹ showing the isocyanate group disappears, and a polyfunctional compound containing an alicyclic compound and a heterocyclic compound in one molecule. A urethane acrylate (A3) / PE4A mixture (a mixture having a mass ratio of 91/9, a butyl acetate solution having a nonvolatile content of 80% by mass) was obtained. The molecular weight (calculated value) of urethane acrylate (A3) is 889.

(Synthesis Example 4)
<Synthesis of urethane acrylate (A4)>
In a flask equipped with a stirrer, a gas introduction tube, a condenser, and a thermometer, Aronix M-305 [Pentaerythritol triacrylate / pentaerythritol tetraacrylate = 60/40 (weight ratio) mixture manufactured by Toa Gosei Co., Ltd., hydroxyl value] 116 mg KOH / g] 549.1 parts, dibutyltin diacetate 0.1 part, Sumilizer BHT [Antioxidant manufactured by Sumitomo Chemical Co., Ltd.] 0.6 part, Metoquinone [polymerization inhibitor manufactured by Seiko Chemical Industry Co., Ltd.] 0.1 part and 160.0 parts of butyl acetate were added, and it heated up gradually, mixing uniformly. Upon reaching 60 ° C., 90.9 parts of Desmodur H (Hexamethylene diisocyanate, NCO% = 50%, manufactured by Sumitomo Bayer Urethane Co., Ltd.) was added, followed by reaction at 80 ° C. for 5 hours to obtain urethane acrylate (A4) 800 Got a part.

(Synthesis Example 5)
<Synthesis of polymer (B1)>
In a flask equipped with a stirrer, a gas introduction tube, a cooling tube, and a thermometer, 250 parts by mass of glycidyl methacrylate (hereinafter referred to as “GMA”), 1.3 parts by mass of lauryl mercaptan, and methyl isobutyl ketone (hereinafter, “MIBK”). 1000 parts by mass and 7.5 parts by mass of 2,2′-azobisisobutyronitrile (hereinafter referred to as “AIBN”) were added and stirred at 90 ° C. over 1 hour while stirring under a nitrogen stream. The temperature was raised and reacted at 90 ° C. for 1 hour. Next, while stirring at 90 ° C., a mixed solution consisting of 750 parts by mass of GMA, 3.7 parts by mass of lauryl mercaptan, and 22.5 parts by mass of AIBN was dropped over 2 hours, and then reacted at 100 ° C. for 3 hours. Thereafter, 10 parts by weight of AIBN was charged, and further reacted at 100 ° C. for 1 hour, then heated to around 120 ° C. and reacted for 2 hours. Cool to 60 ° C., replace the nitrogen introduction tube with an air introduction tube, add 507 parts by mass of acrylic acid (hereinafter referred to as “AA”), 2 parts by mass of p-methoxyphenol, and 5.4 parts by mass of triphenylphosphine. After mixing, the reaction solution was bubbled with air, heated to 110 ° C., and reacted for 8 hours. Thereafter, 1.4 parts by mass of p-methoxyphenol was added, and after cooling to room temperature, MIBK was added so that the nonvolatile content was 50% by mass, and the polymer (B1) (MIBK solution having a nonvolatile content of 50% by mass) was added. Obtained. In addition, the weight average molecular weight of the obtained polymer (B1) was 31,000 (in terms of polystyrene by GPC), and the (meth) acryloyl group equivalent was 300 g / eq.

  Using the various urethane acrylates (A1) to (A4) and / or the polymer (B1) synthesized above, an active energy ray-curable resin composition to be a hard coat coating material was prepared.

(Adjustment example 1)
Ethyl acetate 23.01 parts by mass, alicyclic compound-containing polyfunctional urethane acrylate (A1) / PE4A mixture (a mixture with a mass ratio of 80/20, butyl acetate solution with a nonvolatile content of 80% by mass) 19.64 parts by mass, alicyclic Formula compound-containing polyfunctional urethane acrylate (A2) / PE4A mixture (mixture with a mass ratio of 80/20, butyl acetate solution with a nonvolatile content of 80% by mass) 19.64 parts by mass, alicyclic compound and heterocyclic in one molecule Polyfunctional urethane acrylate (A3) / PE4A mixture containing a compound (mixture with a mass ratio of 91/9, butyl acetate solution with a nonvolatile content of 80% by mass) 15.71 parts by mass, dipentaerythritol hexaacrylate (hereinafter “DPHA”) 18.86 parts by mass, photoinitiator 1-hydroxycyclohexyl phenyl ketone (hereinafter referred to as “HCPK”) .) 2.51 parts by mass, 0.63 parts by mass of photoinitiator diphenyl 2,4,6-trimethylbenzoylphosphine oxide (hereinafter referred to as “TPO”) were mixed uniformly, and the nonvolatile content was 40% by mass. The hard coat agent (1) was prepared by diluting with propylene glycol monomethyl ether (hereinafter referred to as “PGME”).
(Preparation Example 2)
Ethyl acetate 23.01 parts by mass, alicyclic compound-containing polyfunctional urethane acrylate (A1) / PE4A mixture (a mixture with a mass ratio of 80/20, butyl acetate solution with a nonvolatile content of 80% by mass) 19.64 parts by mass, alicyclic Formula compound-containing polyfunctional urethane acrylate (A2) / PE4A mixture (mixture with a mass ratio of 80/20, butyl acetate solution with a nonvolatile content of 80% by mass) 19.64 parts by mass, alicyclic compound and heterocyclic in one molecule Polyfunctional urethane acrylate (A3) / PE4A mixture containing a compound (mixture with a mass ratio of 91/9, butyl acetate solution with a nonvolatile content of 80% by mass) 15.71 parts by mass, dipentaerythritol hexaacrylate (hereinafter “DPHA”) 18.86 parts by mass, photoinitiator 1-hydroxycyclohexyl phenyl ketone (hereinafter referred to as “HCPK”) 2.51 parts by weight, photoinitiator diphenyl 2,4,6-trimethylbenzoylphosphine = oxide (hereinafter referred to as “TPO”) 0.63 parts by weight, reactive fluorine antifouling agent (OPTOOL DAC-HP; After uniformly mixing 2.0 parts by mass of Daikin Industries, Ltd. (nonvolatile content 20% by mass), the mixture is diluted with propylene glycol monomethyl ether (hereinafter referred to as “PGME”) so that the nonvolatile content becomes 40% by mass. Thus, a hard coating agent (2) was prepared.

(Preparation Example 3)
13.74 parts by mass of ethyl acetate, 47.08 parts by mass of alicyclic compound-containing polyfunctional urethane acrylate (A2) / PE4A mixture (mixture with a mass ratio of 80/20, butyl acetate solution with a nonvolatile content of 80% by mass), polymer (B1) (MIBK solution having a nonvolatile content of 50% by mass) 20.92 parts by mass, DPHA 12.74 parts by mass, photoinitiator HCPK 1.30 parts by mass, photoinitiator TPO 0.92 parts by mass, reactive fluorine antifouling agent ( Optool DAC-HP; Daikin Industries, Ltd., 20 parts by mass of non-volatile content 2.0 parts by mass uniformly mixed, and then propylene glycol monomethyl ether (hereinafter referred to as “PGME”) so that the non-volatile content is 40% by mass )) To prepare a hard coat agent (3).

(Adjustment Example 4)
After adding butyl acetate to urethane acrylate (A4) and diluting to a non-volatile content concentration of 35%, Irgacure # 184 [Photopolymerization initiator, 1-hydroxy-cyclohexyl, manufactured by Ciba Specialty Chemicals Co., Ltd.] -Phenyl-ketone] 3.2 parts was blended to prepare a hard coat agent (4).

(Synthesis Example 7)
<Synthesis of urethane acrylate (A5)>
In a flask equipped with a stirrer, a gas introduction tube, a condenser, and a thermometer, Plaxel 205U [Daicel aliphatic polycaprolactone diol, hydroxyl value 212 mgKOH / g, number average molecular weight (Mn) 529] 133 parts by mass, dibutyl 0.1 parts by mass of tin diacetate, Sumilizer BHT [Antioxidant manufactured by Sumitomo Chemical Co., Ltd.] 2.3 parts by mass, 0.2 parts by mass of Metoquinone [Polymerization inhibitor manufactured by Seiko Chemical Industry Co., Ltd.] Mix evenly. After adding 111 parts of Desmodur I [isophorone diisocyanate manufactured by Sumitomo Bayer Urethane Co., Ltd., NCO% = 47%], the temperature was gradually raised to 85 ° C., and the mixture was reacted for 1 hour. 247 parts of Aronix M-305 [pentaerythritol triacrylate / pentaerythritol tetraacrylate = 60/40 (weight ratio) mixture, hydroxyl value 116 mgKOH / g] manufactured by Toa Gosei Co., Ltd.] were added and reacted at 85 ° C. for 3 hours. 493.6 parts by mass of urethane acrylate (A5) having a heavy bond concentration of 5.39 mmol / g was obtained.

(Synthesis Example 6)
<Synthesis of urethane acrylate (A6)>
In a flask equipped with a stirrer, a gas introduction tube, a condenser and a thermometer, Plaxel L205AL [Daicel aliphatic polyester diol, hydroxyl value 224 mgKOH / g, number average molecular weight (Mn) 501] 125 parts by mass, dibutyltin Add 0.1 parts by mass of diacetate, Sumilizer BHT [Antioxidant manufactured by Sumitomo Chemical Co., Ltd.] 2.3 parts by mass, 0.2 part by mass of Metoquinone [Polymerization inhibitor manufactured by Seiko Chemical Industry Co., Ltd.] Mixed. After adding 111 parts of Desmodur I [isophorone diisocyanate manufactured by Sumitomo Bayer Urethane Co., Ltd., NCO% = 47%], the temperature was gradually raised to 85 ° C., and the mixture was reacted for 1 hour. 247 parts of Aronix M-305 [pentaerythritol triacrylate / pentaerythritol tetraacrylate = 60/40 (weight ratio) mixture, hydroxyl value 116 mgKOH / g] manufactured by Toa Gosei Co., Ltd.] were added and reacted at 85 ° C. for 3 hours. 485.6 parts by mass of urethane acrylate (A6) having a heavy bond concentration of 5.31 mmol / g was obtained.

  Active energy ray-curable resin compositions (1) to (8) were prepared using the various urethane acrylates (A5) and (A6) synthesized above.

(Adjustment Example 5)
Urethane acrylate (A5) or urethane acrylate (A6), multifunctional monomer 1 (“Aronix M-305” pentaerythritol triacrylate / pentaerythritol tetraacrylate manufactured by Toa Gosei Co., Ltd.), multifunctional monomer 2 (Nippon Kayaku) "Kayarad DPCA-60" ε-caprolactone-modified dipentaerythritol hexaacrylate), monofunctional monomer 1 ("Biscoat 150D" tetrahydrofurfuryl alcohol acrylic acid polyester produced by Osaka Organic Chemical Industry Co., Ltd.), single By mixing functional monomer 2 (“Aronix M-240” tetraethylene glycol diacrylate, manufactured by Toa Gosei Co., Ltd.) and photoinitiator (Darocur 1173, manufactured by BASF Corp.) in the parts by mass shown in Table 1 below. Double bond densitometer as described in Radiation-curable resin composition with a value of (1) to (8) was prepared.

<Acrylic copolymer (1)>
Preparation of acrylic copolymer In a reaction vessel equipped with a stirrer, cold flow cooler, thermometer, dropping funnel and nitrogen gas inlet, n-butyl acrylate 80% by weight, acrylic acid 4% by weight, methyl methacrylate 15% by weight An acrylic copolymer having a weight average molecular weight of 700,000 is obtained by dissolving 0.2 part of 2,2′-azobisisobutylnitrile as a polymerization initiator in 100% by weight of ethyl acetate, purging with nitrogen, and polymerizing at 80 ° C. for 8 hours. (1) was obtained.

<Acrylic copolymer (2)>
Preparation of acrylic copolymer In a reaction vessel equipped with a stirrer, cold flow cooler, thermometer, dropping funnel and nitrogen gas inlet, 2-methoxyethyl acrylate 75% by weight, n-butyl acrylate 24% by weight, acrylic acid 1% by weight of hydroxyethyl and 0.2 part of 2,2′-azobisisobutylnitrile as a polymerization initiator are dissolved in 100% by weight of ethyl acetate, and after nitrogen substitution, polymerized at 80 ° C. for 8 hours to give a weight average molecular weight of 70. Ten thousand acrylic copolymers (2) were obtained.

  The pressure-sensitive adhesives (1) and (2) were prepared using the various acrylic copolymers (1) and (2) synthesized above.

<Adhesive (1)>
The acrylic copolymer (1) was diluted to 100% by weight with ethyl acetate to obtain an adhesive (1) having a resin solid content of 30%.

<Adhesive (2)>
The acrylic copolymer (2) was diluted to 100% by weight with ethyl acetate to obtain an adhesive (2) having a resin solid content of 30%.

<Adhesive sheet (1)>
0.1% by weight of an isocyanate crosslinking agent (Nihon Polyurethane Coronate L-45, solid content 45%) was added to 100% by weight of the pressure-sensitive adhesive (1) and stirred for 15 minutes, and then one side was peeled off with a silicone compound. It was coated on a 50 μm thick polyester film (hereinafter referred to as “# 50 release film”) so that the thickness after drying was 50 μm, and dried at 75 ° C. for 5 minutes. A 38 μm-thick polyester film (hereinafter referred to as # 38 release film) having one surface peel-treated with the obtained pressure-sensitive adhesive sheet and a silicone compound was bonded. Thereafter, it was aged at 23 ° C. for 7 days to obtain an adhesive sheet (1) having a thickness of 10 μm and a gel fraction of 70%.

<Adhesive sheet (2)>
Thickness after drying on the # 50 release film after adding 0.1% by weight of an isocyanate-based crosslinking agent (Nihon Polyurethane Coronate HX, solid content 75%) to 100% by weight of the pressure-sensitive adhesive (2). Was applied to a thickness of 50 μm and dried at 75 ° C. for 5 minutes. The obtained adhesive sheet and a # 38 release film were bonded together. Thereafter, it was aged at 23 ° C. for 7 days to obtain a pressure-sensitive adhesive sheet (2) having a thickness of 10 μm and a gel fraction of 50%.

Example 1
A film made of polyethylene terephthalate having a thickness of 75 μm (Cosmo Shine A4300 manufactured by Toyobo Co., Ltd.) was used as the film base, and the hard coat agent (1) prepared above was applied to one side of the film base and 90 ° C. at 90 ° C. After drying for 2 seconds, using an ultraviolet irradiation device (“F450” manufactured by Fusion UV Systems Japan Co., Ltd., lamp: 120 W / cm, H bulb) in an air atmosphere, ultraviolet rays are irradiated with an irradiation light amount of 0.2 J / cm ^2. The hard coat layer (1) having a thickness of 3 μm is formed, and the hard coat agent (2) prepared as described above is applied to many surfaces of the film substrate on which the hard coat layer (1) is formed. After drying for 90 seconds, an ultraviolet irradiation device (“F450” manufactured by Fusion UV Systems Japan Co., Ltd., lamp: 120 W / c in an air atmosphere) , With H bulb) to obtain a hard coat layer (2) is formed hard coat film having a thickness of 12μm was irradiated with ultraviolet rays irradiation dose 0.2 J / cm ² (1). Further, Seiko Advance Co., Ltd. ink SG740 and 700EX were applied to the surface of the hard coat layer (1) of the hard coat film (1) in a frame shape (outer dimensions 45 mm × 45 mm, line width 10 mm (area without decorative layer: 25 mm × 25 mm) )) Is silk-printed so that the thickness after drying becomes 5 μm, dried at 85 ° C. for 30 minutes to provide a decorative layer, and then the active energy ray-curable resin composition (1 ) Is applied so that the thickness of the part without the decorative layer is 25 μm, and an ultraviolet irradiation device (“F450” manufactured by Fusion UV Systems Japan Co., Ltd., lamp: 120 W / cm, H bulb) in an air atmosphere. Was used to irradiate ultraviolet rays at an irradiation light amount of 0.2 J / cm ² to obtain a decorated hard coat film (1) having a total thickness of 115 μm. Furthermore, the above-mentioned adhesive sheet (1) is bonded to the active energy ray-curable resin composition layer (1) surface of the decorative hard coat film (1) to provide an adhesive layer, and the decorative hard coat adhesive film has a total thickness of 125 μm. (1) was obtained.

(Example 2)
A decorative hard coat pressure-sensitive adhesive film (2) having a total thickness of 125 μm was obtained in the same manner as in Example (1) except that the pressure-sensitive adhesive sheet (2) was used for the pressure-sensitive adhesive layer.

(Example 3)
Except for the decorated hard coat film (2) using the active energy ray-curable resin composition (2) for the active energy ray-curable resin composition layer, the total thickness was 125 μm in the same manner as in Example (2). The decorative hard coat adhesive film (3) was obtained.

(Example 4)
A total thickness of 125 μm was obtained in the same manner as in Example (2) except that the active energy ray-curable resin composition layer was a decorated hard coat film (3) using the active energy ray-curable resin composition (3). The decorative hard coat adhesive film (4) was obtained.

(Example 5)
Except for the decorated hard coat film (4) using the active energy ray curable resin composition (4) for the active energy ray curable resin composition layer, the total thickness was 125 μm in the same manner as in Example (2). The decorative hard coat adhesive film (5) was obtained.

(Example 6)
A decorative hard coat pressure-sensitive adhesive film having a total thickness of 120 μm in the same manner as in Example (2) except that the decorated hard coat film (5) having an active energy ray-curable resin composition layer thickness of 20 μm was used. (6) was obtained.

(Example 7)
A decorative hard coat adhesive film having a total thickness of 110 μm was used in the same manner as in Example (2) except that a decorated hard coat film (6) in which the thickness of the active energy ray-curable resin composition layer was 10 μm was used. (7) was obtained.

(Example 8)
A decorative hard coat pressure-sensitive adhesive film (8) having a total thickness of 120 μm, in the same manner as in Example (1) except that a decorative hard coat film (7) having a thickness of 7 μm was used as the hard coat layer (2). Got.

Example 9
A decorative hard coat pressure-sensitive adhesive film (9) having a total thickness of 127 μm, in the same manner as in Example (1), except that a decorative hard coat film (8) having a thickness of 5 μm was used for the hard coat layer (1). Got.

(Example 10)
A decorative hard coat adhesive film having a total thickness of 125 μm, in the same manner as in Example (2), except that the decorated hard coat film (9) in which the hard coat layer (1) was formed with the hard coat agent (4) was used. (10) was obtained.

(Example 11)
A decorative hard coat adhesive film having a total thickness of 125 μm, in the same manner as in Example (2), except that the decorated hard coat film (10) in which the hard coat layer (2) was formed with the hard coat agent (3) was used. (11) was obtained.

(Example 12)
A decorated hard coat pressure-sensitive adhesive film (12) having a total thickness of 122 μm was obtained in the same manner as in Example (2) except that the decorated hard coat film (11) without the hard coat layer (1) was used.

(Example 13)
A total thickness of 150 μm was obtained in the same manner as in Example (2) except that a decorative hard coat film (12) using a 125 μm-thick polyethylene terephthalate film (Cosmo Shine A4300 manufactured by Toyobo Co., Ltd.) was used as the film substrate. A decorated hard coat adhesive film (13) was obtained.

(Comparative Example 1)
The total thickness is the same as in Example (2) except that the active energy ray-curable resin composition layer is a decorated hard coat adhesive film (13) using the active energy ray-curable resin composition (5). A decorative hard coat pressure-sensitive adhesive film (14) of 125 μm was obtained.

(Comparative Example 2)
The total thickness is the same as in Example (2) except that the active energy ray-curable resin composition layer is a decorated hard coat adhesive film (14) using the active energy ray-curable resin composition (6). A decorative hard coat pressure-sensitive adhesive film (15) of 125 μm was obtained.

(Comparative Example 3)
The total thickness was the same as in Example (2) except that the active energy ray-curable resin composition layer was a decorated hard coat adhesive film (15) using the active energy ray-curable resin composition (7). A decorative hard coat pressure-sensitive adhesive film (16) of 125 μm was obtained.

(Comparative Example 4)
The total thickness was the same as in Example (2) except that the active energy ray-curable resin composition layer was a decorated hard coat adhesive film (16) using the active energy ray-curable resin composition (8). A decorative hard coat adhesive film (17) of 125 μm was obtained.

(Comparative Example 5)
A decorative hard coat pressure-sensitive adhesive film (18) having a total thickness of 125 μm was obtained in the same manner as in Comparative Example (3) except that the pressure-sensitive adhesive sheet (1) was used for the pressure-sensitive adhesive layer.

(Comparative Example 6)
A decorative hard coat pressure-sensitive adhesive film (19) having a total thickness of 125 μm was obtained in the same manner as in Comparative Example (4) except that the pressure-sensitive adhesive sheet (1) was used for the pressure-sensitive adhesive layer.

  The following evaluation was performed about the adhesive sheet obtained by the said Example and comparative example, an active energy ray hardening-type resin composition coating film, and a decoration hard coat adhesive film. The obtained results are shown in Tables 2-5.

<Adhesive strength measurement method>
The release films on one side of the pressure-sensitive adhesive sheets (1) and (2) obtained above are peeled off and bonded to a PET substrate having a thickness of 25 μm to produce a pressure-sensitive adhesive tape having a width of 25 mm and a length of 10 cm. The glass plate and the decorated hard coat film obtained above in an environment of a temperature of 23 ° C. and a relative humidity of 50% RH are applied to the active energy ray-curable resin composition surface with a 2 kg roller in one reciprocation. After pressure bonding, and allowed to stand in an environment of a temperature of 23 ° C. and a relative humidity of 50% RH for 1 hour, 180 ° peeling adhesion at a peeling speed of 300 mm / min was measured. The measurement results are shown in Table 2.

<Measurement method of Martens hardness>
The active energy ray-curable resin compositions (1) to (8) obtained above are applied on a glass plate and irradiated with an ultraviolet ray irradiation device (“F450” manufactured by Fusion UV Systems Japan Co., Ltd., lamp: 120 W). / Cm, H bulb) was used to irradiate ultraviolet rays with an irradiation light amount of 0.2 J / cm ² to form a 25 μm-thick coating film, and then the Martens hardness of the coating film surface was determined using a Fisherscope HM2000Xyp (Fischer Instrument). Measured by pushing a Vickers indenter having a ridge angle of 136 ° with a load of 1 mN. The measurement results are shown in Table 3.

<Measuring method of dynamic viscoelastic spectrum>
The active energy ray-curable resin compositions (1) to (8) obtained above are applied on a glass plate and irradiated with an ultraviolet ray irradiation device (“F450” manufactured by Fusion UV Systems Japan Co., Ltd., lamp: 120 W). / Cm, H bulb) was used to irradiate ultraviolet rays at an irradiation light amount of 0.2 J / cm ² and punch a 25 μm-thick coating film into a shape of JIS K 7127 test piece type 5 with a dumbbell cutter. . Using the obtained test piece, it was measured by a dynamic viscoelasticity measuring device RSA-II (frequency 3.5 Hz, heating rate 3 ° C./min) manufactured by Rheometrics, and a storage elastic modulus at 60 ° C. was obtained. It was. The measurement results are shown in Table 3.

<Pencil hardness measurement method>
The active energy ray-curable resin compositions (1) to (8) obtained above are applied on a glass plate and irradiated with an ultraviolet ray irradiation device (“F450” manufactured by Fusion UV Systems Japan Co., Ltd., lamp: 120 W). / Cm, H bulb) was used to irradiate ultraviolet rays with an irradiation light amount of 0.2 J / cm ² to obtain a coating film having a thickness of 25 μm. The pencil hardness of the hard coat layer (2) surface of the decorative hard coat pressure-sensitive adhesive film obtained in the above-mentioned Examples and Comparative Examples, and the pencil hardness of the active energy ray-curable resin compositions (1) to (8) was measured according to JIS. Based on the provisions of K 5600-5-4 (1999 edition), measurement was performed using a pencil scratch tester (manual type) for coating film manufactured by Imoto Seisakusho Co., Ltd. The results of the active energy ray-curable resin compositions (1) to (8) measured by the method are listed in Table 3. Table 4 shows the pencil hardness of the surface of the hard coat layer (2) of the decorative hard coat adhesive film.

<Reworkability evaluation method>
The decorative hard coat pressure-sensitive adhesive film obtained above is bonded to a glass plate using a roller, and subjected to heat and pressure defoaming treatment under conditions of 50 ° C., 5 atm, 20 minutes under 23 ° C., 50% environmental conditions. After standing for a period of time, the decorative hard coat pressure-sensitive adhesive film and the state of the glass when the decorative hard coat pressure-sensitive adhesive film was peeled off in the 90 ° direction at a peeling speed of 300 mm / min were evaluated. The judgment criteria are as follows.
A: The decorative hard coat adhesive film is not torn, and no adhesive remains on the glass.
○: Adhesive remains on the glass without tearing the decorative hard coat adhesive film.
X: The decorative hard coat adhesive film is torn off, and the adhesive and the decorative hard coat adhesive film remain on the glass.

<Punching workability evaluation method>
Using a big blade (blade angle 42 degrees), a 3 mm diameter circular punch was punched out from the hard coat layer (2) surface of the decorative hard coat adhesive film. Then, the decorative hard coat adhesive film was affixed on the glass plate, and the crack of the hard coat layer and the active energy ray curable resin composition layer was observed with a microscope (50 times) from the surface of the hard coat layer. The judgment criteria are as follows.
A: Hard coat layer or active energy ray curable resin composition layer has no cracks O: Hard coat layer or active energy ray curable resin composition layer has no significant cracks X: Hard coat layer or active energy ray curable resin composition layer There are significant cracks in the resin composition layer

  As apparent from the above table, it was found that the decorative hard coat pressure-sensitive adhesive film of the present invention was excellent in reworkability and punching workability while having high pencil hardness. On the other hand, the decorative hard coat pressure-sensitive adhesive films of Comparative Examples 1 and 2 had insufficient pencil hardness, and Comparative Examples 3 to 6 were likely to cause scratches and cracks during reworking and punching.

1 Hard Coat Film 2 Hard Coat Layer (1)
3 Hard coat layer (2)
4 Substrate 5 Decorating layer 6 Resin layer

Claims (11)

A hard coat film having a hard coat layer on at least one surface of the substrate, a decorative layer provided on a part of the hard coat film surface, and an active energy ray-curable resin provided on the surface of the hard coat film having the decorative layer A resin layer made of the composition,
The storage elastic modulus (E ′) at 60 ° C. measured at a frequency of 3.5 Hz of the resin layer made of the active energy ray-curable resin composition is 2.0 × 10 ^{8 to} 9.0 × 10 ⁸ Pa. A decorative hard coat film characterized by being.   The decorative hard coat film according to claim 1, wherein the total thickness is 100 to 170 µm, and the maximum thickness of the resin layer made of the active energy ray-curable resin composition is 5 to 30 µm. 3. The Martens hardness measured by pushing a Vickers indenter having a ridge angle of 136 ° of the resin layer made of the active energy ray-curable resin composition with a load of 1 mN is 70 to 100 N / mm ^2. Decorative hard coat film.   The decorative hard coat film according to any one of claims 1 to 3, wherein the hard coat film is a hard coat film having a hard coat layer on both surfaces of a substrate.   The decorative hard coat film according to any one of claims 1 to 4, wherein a pencil hardness of the hard coat layer on the other side of the surface on which the decorative layer of the hard coat film is provided is 3H or more.   The decorated hard coat film according to any one of claims 1 to 5, wherein the active energy ray-curable resin composition is a composition mainly composed of urethane (meth) acrylate.   The resin layer comprising the active energy ray-curable resin composition is a resin layer that covers a decorative layer provided on a part of the surface of the hard coat film, and the surface of the resin layer is a flattened resin layer. The decorated hard coat film according to any one of 1 to 6.   The resin layer comprising the active energy ray-curable resin composition is provided on the hard coat film surface other than the portion provided with the decorative layer on the hard coat film surface, and comprises the active energy ray-curable resin composition. The decorative hard coat film according to any one of claims 1 to 6, wherein the thickness of the resin layer and the thickness of the decorative layer are the same.   The decorative hard coat film according to any one of claims 1 to 8, which is used for an image display panel of an image display device of a small electronic terminal.   A decorative hard coat, wherein a pressure-sensitive adhesive layer is provided on the surface of the resin layer comprising the active energy ray-curable resin composition of the decorative hard coat film according to claim 1. Adhesive film.   The decorative hard coat pressure-sensitive adhesive film according to claim 10, wherein the pressure-sensitive adhesive layer is a pressure-sensitive adhesive layer comprising an acrylic pressure-sensitive adhesive composition containing an acrylic copolymer containing an alkoxyalkyl acrylate as a main monomer component.

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