JP2011031527A - Hard-coat film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hard-coat film that has high hardness and high scratch resistance, and also, restorableness against flaws. <P>SOLUTION: The hard-coat film 1 is configured so that a hard-coat layer 20 and a restoring layer 30 are sequentially formed at the one-face side of a light-transmitting base material 10 from the side of the light-transmitting base material 10. The hard-coat layer 20 comprises a cured material of a curable resin composition for a hard-coat layer containing a binder component. The restoring layer 30 comprises a cured material of a curable resin composition for a restoring layer containing a urethane acrylate and/or a urethane methacrylate obtained by reacting an organic isocyanate having two or more isocyanate groups in one molecule with a hidroxy modified acrylate and/or a hydroxy modified methacrylate and a polycaprolactone-containing multifunctional alcohol. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a hard coat film which is used for the purpose of protecting the surface of a display or the like and which is provided with a hard coat layer and a restoring layer on a light-transmitting substrate.

  An image display surface in an image display device such as a liquid crystal display, a CRT display, a projection display, a plasma display, or an electroluminescence display is required to be provided with scratch resistance so as not to be damaged during handling. On the other hand, by utilizing a hard coat film provided with a hard coat (HC) layer on a substrate, and a hard coat film (optical laminate) provided with optical functions such as antireflection and antiglare properties, In general, the scratch resistance of an image display surface of an image display apparatus is improved.

  In Patent Document 1, a polyalkylene oxide chain-containing polymer having a molecular weight of 1000 or more having 3 or more reactive functional groups at its terminal on a light-transmitting resin substrate, and a molecular weight having 2 or more reactive functional groups. Hard coated hard coating layer coating composition comprising less than 10,000 compounds, and at least a part of the surface of which is coated with an organic component and containing inorganic fine particles having reactive functional groups introduced by the organic component on the surface A coat layer is provided to improve the hardness.

  In the product inspection of the optical laminate having a hard coat film or hard coat layer, in the pencil hardness test for evaluating the hardness, if the surface of the hard coat layer is scratched, the quality is deteriorated. Most unfavorable.

  The hard coat film of Patent Document 1 is hard to be scratched, but once it has been scratched, the scratch does not disappear and the visibility of a display using such a hard coat film is reduced.

JP 2008-165040 A

  The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a hard coat film having high hardness and scratch resistance but also having a resilience against scratches.

As a result of intensive studies on the above problems, the present inventors have provided a hard coat layer having high hardness as a base layer on a light-transmitting substrate, and specific urethane acrylate and / or urethane on the base layer. By providing a layer having a restoring property comprising a cured product of a composition containing methacrylate, it was found that a hard coat film having a high hardness and scratch resistance but having a restoring property to scratches was obtained. It came to complete.
That is, the features of the present invention that solve the above problems are as follows.

The hard coat film according to the present invention is a hard coat film provided with a hard coat layer and a restorative layer in order from the light transmissive substrate side on one side of the light transmissive substrate,
The hard coat layer comprises a cured product of a curable resin composition for a hard coat layer containing a binder component,
The restorable layer is a urethane acrylate obtained by reacting organic isocyanate having two or more isocyanate groups in one molecule, hydroxy-modified acrylate and / or hydroxy-modified methacrylate and polycaprolactone-containing polyfunctional alcohol, and / or Or it consists of hardened | cured material of the curable resin composition for recoverable layers containing a urethane methacrylate.

  The hard coat layer is made of a cured product of a curable resin composition for a hard coat layer containing a binder component, has excellent hardness, prevents the impact on the hard coat film from being transmitted to the light transmissive substrate, Has the effect of increasing hardness.

  The restorative layer is made of a cured product of the curable resin composition for the restorable layer containing the specific urethane acrylate and / or urethane methacrylate, and is more flexible than the hard coat layer and has resilience to scratches, It has the effect of preventing the visibility of the hard coat film from being reduced by scratches. And the effect of the said hard-coat layer and a restoring layer is fully exhibited by providing a hard-coat layer and a restoring layer in this order on the one surface side of a transparent base material.

  The hardness of the hard coat layer as defined in JIS K5600-5-4 (1999) is preferably 2H or more in order to exhibit sufficient hardness as an underlayer.

  The hard coat film which concerns on this invention WHEREIN: It is preferable from the point of the hardness improvement of a hard coat film that the film thickness of the said recoverable layer is 5-30 micrometers.

  In the hard coat film according to the present invention, the hydroxy-modified acrylate and / or hydroxy-modified methacrylate is preferably polycaprolactone-modified alkyl acrylate and / or polycaprolactone-modified alkyl methacrylate.

  In the hard coat film according to the present invention, the hydroxy-modified acrylate and / or hydroxy-modified methacrylate is preferably a mixture of two or more hydroxy-modified acrylates and / or hydroxy-modified methacrylates having different caprolactone unit repeating numbers.

  In the hard coat film according to the present invention, it is preferable that the maximum difference in the number of repetitions between hydroxy-modified acrylates and / or hydroxy-modified methacrylates having different numbers of repetitions of caprolactone units is 9 or less.

  In the hard coat film according to the present invention, the curable resin composition for a recoverable layer further contains one or more compounds selected from the group consisting of a long-chain alkyl group-containing compound, a silicone-based compound, and a fluorine-based compound. It is preferable from the viewpoint of improving the scratch resistance of the hard coat film.

  In the hard coat film according to the present invention, the one or more compounds selected from the group consisting of the long-chain alkyl group-containing compound, the silicone-based compound, and the fluorine-based compound have a photocurable group. It is preferable from the viewpoint of improving adhesion and solvent resistance.

  In the hard coat film according to the present invention, the long chain alkyl group of the long chain alkyl group-containing compound preferably has 13 to 25 carbon atoms from the viewpoint of improving the scratch resistance of the hard coat film.

  In a preferred embodiment of the hard coat film according to the present invention, an antistatic layer, an antiglare layer, an antifouling layer, a low refractive index layer, and the hard layer are provided on the surface of the restorative layer opposite to the hard coat layer. It is also possible to provide one or more layers selected from the group consisting of second hard coat layers that are the same as or different from the coat layers.

In the present invention, the “hard coat layer” refers to a layer having a hardness of “H” or higher in a pencil hardness test (4.9 N load) defined in JIS K5600-5-4 (1999).
In the present invention, “scratch” refers to a scratch in the pencil hardness test (4.9 N load) specified in JIS K5600-5-4 (1999).
In the present invention, the photocurable group means a functional group capable of curing a coating film by proceeding a polymerization reaction or a crosslinking reaction by light irradiation, and examples thereof include photoradical polymerization, photocationic polymerization, and photoanion. Examples thereof include those in which the reaction proceeds by a reaction form such as polymerization reaction such as polymerization, addition polymerization or condensation polymerization that proceeds through photodimerization.

  The hard coat film according to the present invention is composed of a cured product of a composition containing a hard coat layer and a specific urethane acrylate and / or urethane methacrylate from the light transmissive substrate side on one side of the light transmissive substrate. By having the layers in this order, it is excellent in hardness and scratch resistance, has a resilience against scratches, and provides good visibility.

FIG. 1 is a diagram schematically showing an example of a layer configuration of a hard coat film according to the present invention. FIG. 2 is a diagram schematically showing another example of the layer configuration of the hard coat film according to the present invention. FIG. 3 is a diagram schematically showing another example of the layer configuration of the hard coat film according to the present invention.

  Hereinafter, the hard coat film according to the present invention will be described first, and then the method for producing the hard coat film will be described.

In the present invention, (meth) acrylate represents acrylate and / or methacrylate.
In the present invention, the “hard coat layer” generally indicates a hardness of “H” or higher in a pencil hardness test (4.9 N load) defined by JIS K5600-5-4 (1999).
In the present invention, “scratch” refers to a scratch in the pencil hardness test (4.9 N load) specified in JIS K5600-5-4 (1999).
The light of the present invention includes not only electromagnetic waves having wavelengths in the visible and invisible regions, but also particle beams such as electron beams, and radiation or ionizing radiation that collectively refers to electromagnetic waves and particle beams.
In the present invention, the photocurable group means a functional group capable of curing a coating film by proceeding a polymerization reaction or a crosslinking reaction by light irradiation, and examples thereof include photoradical polymerization, photocationic polymerization, and photoanion. Examples thereof include those in which the reaction proceeds by a reaction form such as polymerization reaction such as polymerization, addition polymerization or condensation polymerization that proceeds through photodimerization.
In this invention, a film thickness means the film thickness at the time of drying (dry film thickness).
In the present invention, the molecular weight means a weight average molecular weight which is a polystyrene equivalent value measured by gel permeation chromatography (GPC) when having a molecular weight distribution, and when having no molecular weight distribution, Mean molecular weight.
In the present invention, the average particle diameter of the fine particles means a 50% particle diameter (d50 median diameter) when the particles in the solution are measured by a dynamic light scattering method and the particle size distribution is represented by a cumulative distribution. . The average particle size can be measured using a Microtrac particle size analyzer manufactured by Nikkiso Co., Ltd.
The fine particles may be agglomerated particles, and in the case of agglomerated particles, the secondary particle diameter may be within the above range.
In the definition of film and sheet in JIS-K6900, a sheet is a thin and generally flat product whose thickness is small relative to the length and width. A film has a thickness compared to the length and width. A thin, flat product that is extremely small and has an arbitrarily limited maximum thickness, usually supplied in the form of a roll. Accordingly, it can be said that a sheet having a particularly thin thickness is a film, but the boundary between the sheet and the film is not clear and is difficult to distinguish clearly. Therefore, in the present invention, both a thick sheet and a thin sheet are used. Including meaning, it is defined as “film”.

(Hard coat film)
The hard coat film according to the present invention is a hard coat film provided with a hard coat layer and a restorative layer in order from the light transmissive substrate side on one side of the light transmissive substrate,
The hard coat layer comprises a cured product of a curable resin composition for a hard coat layer containing a binder component,
The restorable layer is a urethane acrylate obtained by reacting organic isocyanate having two or more isocyanate groups in one molecule, hydroxy-modified acrylate and / or hydroxy-modified methacrylate and polycaprolactone-containing polyfunctional alcohol, and / or Or it consists of hardened | cured material of the curable resin composition for recoverable layers containing a urethane methacrylate.

  The hard coat layer is made of a cured product of a curable resin composition for a hard coat layer containing a binder component, has excellent hardness, prevents the impact on the hard coat film from being transmitted to the light transmissive substrate, Has the effect of increasing hardness.

  The restorative layer is made of a cured product of the curable resin composition for the restorable layer containing the specific urethane acrylate and / or urethane methacrylate, and is more flexible than the hard coat layer and has resilience to scratches, It has the effect of preventing the visibility of the hard coat film from being reduced by scratches.

  By providing the hard coat layer and the restorative layer in this order on the one surface side of the light transmissive base material from the light transmissive base side, the effects of the hard coat layer and the restorative layer are sufficiently exhibited. In the case where only the restoring layer is provided on the light-transmitting substrate, the hardness is insufficient. On the other hand, in the case where only the hard coat layer is provided, the scratch is difficult to be scratched, but the resilience against the scratch. Visibility is reduced when there are no scratches.

  In a preferred embodiment of the hard coat film according to the present invention, an antistatic layer, an antiglare layer, an antifouling layer, a low refractive index layer, and the hard layer are provided on the surface of the restorative layer opposite to the hard coat layer. It is also possible to provide one or more layers selected from the group consisting of second hard coat layers that are the same as or different from the coat layers. In the hard coat film according to the present invention, if the hard coat layer is provided on one surface side of the light-transmitting substrate, and the restoring layer is provided adjacent to the hard coat layer, the gist of the present invention is achieved. The other layers can be provided on the surface of the restorable layer opposite to the hard coat layer without departing from the scope.

FIG. 1 is a schematic view showing an example of a layer configuration of a hard coat film according to the present invention.
The hard coat layer 20 and the restoring layer 30 are provided on one surface side of the light transmissive substrate 10 from the light transmissive substrate 10 side.

FIG. 2 is a schematic view showing another example of the layer configuration of the hard coat film according to the present invention.
On one surface side of the light transmissive substrate 10, the hard coat layer 20, the restoring layer 30, and the low refractive index layer 40 are provided in this order from the light transmissive substrate 10 side.

FIG. 3 is a schematic view showing another example of the layer configuration of the hard coat film according to the present invention.
On one surface side of the light transmissive substrate 10, the hard coat layer 20, the restoring layer 30, the antistatic layer 50, and the low refractive index layer 40 are provided in this order from the light transmissive substrate 10 side.

  Hereinafter, an antistatic layer, an antiglare layer, which is an essential element of the hard coat film according to the present invention, a light-transmitting substrate, a hard coat layer, a restorative layer, and other layers that can be appropriately provided as necessary. The antifouling layer, the low refractive index layer, and the second hard coat layer that is the same as or different from the hard coat layer will be described in detail.

(Light transmissive substrate)
The light-transmitting substrate used in the present invention is a plastic film or sheet having a high light-transmitting property (transparency), and is particularly limited as long as it satisfies the physical properties that can be used as the light-transmitting substrate of the optical laminate. It can be selected and used as appropriate.
Usually, the base material used for the optical layered body is transparent, translucent, colorless, or colored, but is required to have optical transparency. In addition, the measurement of light transmittance uses the value measured in room temperature and air | atmosphere using the ultraviolet visible spectrophotometer (For example, Shimadzu Corporation UV-3100PC).

  In the present invention, the thickness of the light-transmitting substrate can be appropriately selected and used. However, from the viewpoint that the surface of the hard coat film is hard to break and imparts hardness, a light-transmitting group of 10 to 200 μm is used. A material is preferably used, and more preferably 30 to 150 μm.

  Preferable materials for the light-transmitting substrate include cellulose acylate, cycloolefin polymer, polycarbonate, acrylate polymer, or polyester. Here, “mainly” means a component having the highest content ratio among the constituent components of the base material.

Specific examples of cellulose acylate include cellulose triacetate, cellulose diacetate, and cellulose acetate butyrate.
Examples of the cycloolefin polymer include a norbornene polymer, a monocyclic olefin polymer, a cyclic conjugated diene polymer, a vinyl alicyclic hydrocarbon polymer resin, and more specifically, ZEONEX and ZEONOR (norbornene resin) manufactured by Nippon Zeon Co., Ltd., Sumilite FS-1700 manufactured by Sumitomo Bakelite Co., Ltd., Arton (modified norbornene resin) manufactured by JSR Corporation, Appel (cyclic olefin) manufactured by Mitsui Chemicals Copolymer), Topas (cyclic olefin copolymer) manufactured by Ticona, Optretz OZ-1000 series (alicyclic acrylic resin) manufactured by Hitachi Chemical Co., Ltd., and the like.
Specific examples of the polycarbonate include aromatic polycarbonates based on bisphenols (such as bisphenol A) and aliphatic polycarbonates such as diethylene glycol bisallyl carbonate.
Specific examples of the acrylate polymer include poly (meth) methyl acrylate, poly (meth) ethyl acrylate, methyl (meth) acrylate-butyl (meth) acrylate copolymer, and the like.
Specific examples of the polyester include polyethylene terephthalate and polyethylene naphthalate.

As the light-transmitting substrate used in the present invention, the most transparent material is cellulose acylate, and triacetyl cellulose is preferably used among them.
A triacetyl cellulose film (TAC film) is a light-transmitting substrate capable of setting an average light transmittance to 50% or more in a visible light region of 380 to 780 nm. The average light transmittance of the substrate is preferably 70% or more, and more preferably 85% or more.
Since the TAC film has optical isotropy, it can be preferably used in the case of a liquid crystal display application.

  In addition, as triacetyl cellulose in the present invention, in addition to pure triacetyl cellulose, cellulose acetate propionate, cellulose acetate butyrate, and the like are used in combination with components other than acetic acid as fatty acids forming esters with cellulose. Also good. Further, these triacetyl celluloses may be added with other additives such as other cellulose lower fatty acid esters such as diacetyl cellulose, or plasticizers, antistatic agents, ultraviolet absorbers and the like, if necessary.

  In the present invention, the TAC film may be subjected to surface treatment (eg, saponification treatment, glow discharge treatment, corona discharge treatment, ultraviolet (UV) treatment, flame treatment), and a primer layer (adhesive layer). It may be formed. The light-transmitting substrate of the present invention includes those including the surface treatment and the primer layer.

(Hard coat layer)
The hard coat layer is made of a cured product of a curable resin composition for a hard coat layer containing a binder component, has excellent hardness, prevents the impact on the hard coat film from being transmitted to the light transmissive substrate, Has the effect of increasing hardness.

  The hardness of the pencil hardness test (4.9 N load) specified in JIS K5600-5-4 (1999) of the hard coat layer may be H or more, and 2H or more is sufficient hardness as an underlayer. Preferred for expression.

  The film thickness of the hard coat layer may be appropriately set according to the performance required for the hard coat film, and is not particularly limited, but is preferably 2 to 50 μm, more preferably 3 to 25 μm. It is particularly preferable that the thickness is ˜20 μm. If it is 2 μm or more, it is easy to obtain a hardness of 2H or more, and if it exceeds 50 μm, cracks are likely to occur, and warping (so-called curl) of the entire hard coat film due to curing shrinkage of the binder component tends to occur.

(Curable resin composition for hard coat layer)
The curable resin composition for a hard coat layer of the present invention will be described.
The curable resin composition for a hard coat layer of the present invention contains a binder component, in addition, fine particles for the purpose of imparting hardness, antiglare agent, antifouling agent and antistatic agent for the purpose of imparting functionality, and coating suitability. It may contain a leveling agent for the purpose of controlling the above, and an easy lubricant for the purpose of preventing blocking.

(Binder component)
The binder component used in the curable resin composition for the hard coat layer is a component having a reactive functional group and being cured to become a matrix of the hard coat layer. The binder component is cross-linked with the reactive functional groups and reactive inorganic fine particles described later by the reactive functional group, forms a network structure, and imparts hardness to the hard coat layer.
In the present invention, the binder component is a concept including a monomer, an oligomer, a polymer, and a resin.

  As the reactive functional group, a polymerizable unsaturated group is suitably used, preferably a photocurable unsaturated group, and particularly preferably an ionizing radiation curable unsaturated group. Specific examples thereof include ethylenically unsaturated bonds such as (meth) acryloyl group, vinyl group and allyl group, and epoxy group.

  The binder component is preferably a curable organic resin, preferably a translucent material that transmits light when used as a coating film, and an ionizing radiation curable resin that is a resin curable by ionizing radiation represented by ultraviolet rays or electron beams, Other known curable resins and the like may be appropriately employed according to required performance. Examples of the ionizing radiation curable resin include (meth) acrylate-based, oxetane-based, and silicone-based resins.

As the binder component, one or more binder components can be used.
The content of the binder component relative to the total solid content of the curable resin composition for the hard coat layer may be appropriately adjusted according to the required performance of the hard coat film, but is preferably included in an amount of 5 to 90% by mass. It is more preferable that 20-80 mass% is contained.

  The binder component preferably has two or more reactive functional groups, more preferably three or more from the viewpoint of increasing the crosslink density in the hard coat layer and increasing the hardness.

Examples of such a binder component include pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane hexa ( And meth) acrylates and modified products thereof.
Examples of modified products include EO (ethylene oxide) modified products, PO (propylene oxide) modified products, CL (caprolactone) modified products, and isocyanuric acid modified products.

  As the binder component, pentaerythritol triacrylate and / or dipentaerythritol hexaacrylate is preferably used, and pentaerythritol triacrylate is particularly preferably used.

  In addition, as the trifunctional or higher functional acrylate resin, commercially available products can be used. Specifically, KAYARAD, KAYAMER series (for example, DPHA, PET30, GPO303, TMPTA, THE330) manufactured by Nippon Kayaku Co., Ltd. , TPA330, D310, D330, PM2, PM21, DPCA20, DPCA30, DPCA60, DPCA120); Aronix series manufactured by Toagosei Co., Ltd. (for example, M305, M309, M310, M315, M320, M327, M350, M360, M402) , M408, M450, M7100, M7300K, M8030, M8060, M8100, M8530, M8560, M9050); NK ester series (for example, TMPT, A-TMPT, A, manufactured by Shin-Nakamura Chemical Co., Ltd.) TMM-3, A-TMM3L, A-TMMT, A-TMPT-6EO, A-TMPT-3CL, A-GLY-3E, A-GLY-6E, A-GLY-9E, A-GLY-11E, A- GLY-18E, A-GLY-20E, A-9300, AD-TMP-4CL, AD-TMP); NK Economer series (for example, ADP51, ADP33, ADP42, ADP26, ADP15) manufactured by Shin-Nakamura Chemical Co., Ltd. ); New Frontier series manufactured by Daiichi Kogyo Seiyaku Co., Ltd. (eg, TMPT, TMP3, TMP15, TMP2P, TMP3P, PET3, TEICA); Ebecryl series manufactured by Daicel UCB Co., Ltd. (eg, TMPTA, TMPTAN) , 160, TMPEOTA, OTA480, 53, PETIA, 2047 40, 140, 1140, PETAK, DPHA); SARTOMER CD501, CD9021, CD9052, SR351, SR351HP, SR351LV, SR368, SR368D, SR415, SR444, SR454, SR454HP, SR492, SR499, SR502, SR9008, SR9012 SR9020HP, SR9035, CD9051, SR350, SR9009, SE9011, SR295, SR355, SR399, SR399LV, SR494, SR9041 and the like.

  Examples of the bifunctional or higher urethane acrylate include trade names AH-600, AT-600, UA-306H, UA-306T, and UA-306I manufactured by Kyoeisha Chemical Co., Ltd. Urethane (meth) acrylates preferably used include urethane (meth) acrylates obtained by reacting a monomer or multimer of isophorone diisocyanate, a pentaerythritol polyfunctional acrylate and a dipentaerythritol polyfunctional acrylate.

  A commercially available product can be used as the urethane (meth) acrylate resin, and specific examples include the purple light series manufactured by Nippon Synthetic Chemical Industry Co., Ltd., such as UV1700B, UV6300B, UV765B, UV7640B, and UV7600B; Art Resin series manufactured by Kogyo Co., Ltd., such as Art Resin HDP, Art Resin UN 9000H, Art Resin UN 3320HA, Art Resin UN 3320HB, Art Resin UN 3320HC, Art Resin UN 3320HS, Art Resin UN901M, Art Resin UN902MS, Art Resin UN903, etc. And UA100H, U4H, U6H, U15HA, UA32P, U6LPA, U324A, U9HAMI, etc. manufactured by Shin-Nakamura Chemical Co., Ltd .; Ebecryl series manufactured by, for example, 1290, 5129, 254, 264, 265, 1259, 1264, 4866, 9260, 8210, 204, 205, 6602, 220, 4450 and the like; Arakawa Chemical Industries, Ltd. For example, 371, 371MLV, 371S, 577, 577BV, 577AK, etc .; Mitsubishi Rayon Co., Ltd. RQ series, etc .; DIC Corporation, Unidic series, etc. are mentioned. And DPHA40H (manufactured by Nippon Kayaku Co., Ltd.), CN9006, CN968 (manufactured by SARTOMER), and the like. Among these, UV1700B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), DPHA40H (manufactured by Nippon Kayaku Co., Ltd.), Art Resin HDP (manufactured by Negami Kogyo Co., Ltd.), beam set 371, beam set 577 (Arakawa) Chemical Industry Co., Ltd.), U15HA (manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like.

  As bifunctional or more functional epoxy acrylates, trade name SP series (SP-4060, 1450, etc.), VR series (VR-60, 1950; VR-90, 1100, etc.) manufactured by Showa Polymer Co., Ltd .; Nippon Synthetic Chemical Examples include trade names UV-9100B and UV-9170B manufactured by Kogyo Co., Ltd .; trade names EA-6320 / PGMAc and EA-6340 / PGMAc manufactured by Shin-Nakamura Chemical Co., Ltd.

  Moreover, as a bifunctional or more functional oligomer, Toagosei Co., Ltd. brand name macromonomer series AA-6, AS-6, AB-6, AA-714SK etc. are mentioned.

(Other components of curable resin composition for hard coat layer)
In addition to the binder component, fine particles, a polymerization initiator, an antistatic agent, an antiglare agent, and the like can be appropriately added to the curable resin composition for the hard coat layer in addition to the binder component for the purpose of imparting hardness and other functionality. . Furthermore, various additives, such as a reactive or non-reactive leveling agent and various sensitizers, may be mixed. When an antistatic agent and / or an antiglare agent are included, antistatic properties and / or antiglare properties can be further imparted to the hard coat layer.

(Fine particles)
The curable resin composition for a hard coat layer preferably contains fine particles from the viewpoint of improving the hardness of the hard coat layer. As the fine particles, known particles that can be used for the hard coat layer may be appropriately employed depending on the required performance.

  The average particle diameter of the fine particles is preferably 1 to 100 nm from the viewpoint of the transparency of the hard coat layer. By being the said range, it is easy to provide hardness, maintaining the transparency of a hard-coat layer. The fine particles may be agglomerated particles. In the case of agglomerated particles, the secondary particle diameter may be within the above range.

  The fine particles preferably have a narrow particle size distribution and are monodispersed from the viewpoint of improving hardness while maintaining the restoration rate when only the binder component is used without impairing transparency.

  There is no restriction | limiting in particular in content in the curable resin composition for hard-coat layers of microparticles, What is necessary is just to set suitably in consideration of hardness etc. The content of the fine particles is preferably 10 to 80% by mass with respect to the total solid content of the curable resin composition for the hard coat layer from the viewpoint of improving the hardness of the hard coat layer, and is 30 to 70% by mass. Is more preferable.

  The fine particles are not limited to having a single material or a single average particle diameter, but may be a combination of two or more kinds having different materials and average particle diameters. When two or more types are used in combination, the average particle size of each particle is preferably within 1 to 100 nm.

  The reactive inorganic fine particles of the present invention are improved in hardness by using solid particles having no voids or porous structure inside the particles rather than particles having voids or porous structure inside the particles such as hollow particles. From the point of view, it is preferable.

  The fine particles may be inorganic fine particles or organic fine particles, but are preferably inorganic fine particles from the viewpoint of imparting hardness.

Examples of the inorganic fine particles include metal oxides such as silica (SiO ₂ ), aluminum oxide, zirconia, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide, and cerium oxide. Examples thereof include fine particles, fine metal fluoride particles such as magnesium fluoride and sodium fluoride. Metal fine particles, metal sulfide fine particles, metal nitride fine particles and the like may be used.

  From the viewpoint of high hardness, silica and aluminum oxide are preferable. In addition, in order to form a high refractive index layer relative to other layers provided on the hard coat layer, fine particles having a high refractive index when a film such as zirconia, titania, antimony oxide, etc. is formed are appropriately selected. Can be used. Similarly, in order to obtain a relatively low refractive index layer, fine particles having a low refractive index during film formation such as fluoride fine particles such as magnesium fluoride and sodium fluoride can be appropriately selected and used. Furthermore, when it is desired to impart antistatic properties and conductivity, indium tin oxide (ITO), tin oxide, or the like can be appropriately selected and used. These can be used alone or in combination of two or more.

  Examples of commercially available silica fine particles include Nissan Chemical Industries, Ltd., IPA-ST, IPASTMS, and IPAST (L).

  Examples of the organic fine particles include plastic beads. Specific examples of the plastic beads include polystyrene beads, melamine resin beads, acrylic beads, acrylic-styrene beads, benzoguanamine beads, benzoguanamine / formaldehyde condensation beads, polycarbonate beads, and polyethylene beads. The plastic beads preferably have a hydrophobic group on the surface, and examples thereof include styrene beads.

  The inorganic fine particle is a reactive inorganic fine particle having a reactive functional group capable of forming a covalent bond by crosslinking reaction between the particles or the binder component on the fine particle surface at least on a part of the particle surface. preferable. The hardness of the hard coat layer can be further improved by a cross-linking reaction between the reactive inorganic fine particles or between the reactive inorganic fine particles and the binder component.

  As the reactive functional group, a polymerizable unsaturated group is suitably used, preferably a photocurable unsaturated group, and particularly preferably an ionizing radiation curable unsaturated group. Specific examples thereof include ethylenically unsaturated bonds such as (meth) acryloyl group, vinyl group and allyl group, and epoxy group.

The reactive inorganic fine particles include those having two or more inorganic fine particles as a core per particle. Moreover, the reactive inorganic fine particle can raise the crosslinking point in the matrix of a hard-coat layer with respect to content by making a particle size small.
The reactive inorganic fine particles may further impart a function to the hard coat layer, and are appropriately selected and used according to the purpose.

  As the reactive inorganic fine particles, conventionally known ones may be used. For example, as commercially available products, reactive silica fine particles (trade name HC-601, manufactured by ADEKA Corporation), (trade names KZ7537, manufactured by JSR Corporation) are used. Can be used.

  As the reactive inorganic fine particles, powdery fine particles that do not contain a dispersion medium may be used. However, it is preferable to use a fine particle in a solvent-dispersed sol because the dispersion step can be omitted and the productivity is high.

(Polymerization initiator)
In order to initiate or promote the radical polymerizable functional group or the cationic polymerizable functional group, a radical polymerization initiator, a cationic polymerization initiator, a radical and a cationic polymerization initiator may be appropriately selected and used as necessary. . These polymerization initiators are decomposed by light irradiation and / or heating to generate radicals or cations to advance radical polymerization and cationic polymerization.

Any radical polymerization initiator may be used as long as it can release a substance that initiates radical polymerization by light irradiation and / or heating. For example, examples of the photo radical polymerization initiator include imidazole derivatives, bisimidazole derivatives, N-aryl glycine derivatives, organic azide compounds, titanocenes, aluminate complexes, organic peroxides, N-alkoxypyridinium salts, thioxanthone derivatives, and the like. More specifically, 1,3-di (tert-butyldioxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetrakis (tert-butyldioxycarbonyl) benzophenone, 3-phenyl-5- Isoxazolone, 2-mercaptobenzimidazole, bis (2,4,5-triphenyl) imidazole, 2,2-dimethoxy-1,2-diphenylethane-1-one (trade names: Irgacure 651, Ciba Japan Co., Ltd.) 1-hydroxy-cyclohexyl-phenyl- T (trade name Irgacure 184, manufactured by Ciba Japan), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one (trade names Irgacure 369, Ciba Japan ( Co., Ltd.), bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium) (trade name Irgacure 784, manufactured by Ciba Japan Co., Ltd.), etc., but is not limited thereto.

  In addition to the above, commercially available products can be used. Specifically, Irgacure 907, Irgacure 379, Irgacure 819, Irgacure 127, Irgacure 500, Irgacure 754, Irgacure 250, Irgacure 1800, Irgacure 1870 manufactured by Ciba Japan Co., Ltd. , Irgacure OXE01, DAROCUR TPO, DAROCUR1173, Japan Siber Hegner Co., Ltd. of SpeedcureMBB, SpeedcurePBZ, SpeedcureITX, SpeedcureCTX, SpeedcureEDB, Esacure ONE, Esacure KIP150, Esacure KTO46, manufactured by Nippon Kayaku Co., of (stock) KAYACURE DETX-S, KAYACURE CTX , KAYACURE BMS, K YACURE DMBI, and the like.

Moreover, the cationic polymerization initiator should just be able to discharge | release the substance which starts cationic polymerization by light irradiation and / or a heating. Examples of the cationic polymerization initiator include sulfonic acid ester, imide sulfonate, dialkyl-4-hydroxysulfonium salt, arylsulfonic acid-p-nitrobenzyl ester, silanol-aluminum complex, (η ⁶ -benzene) (η ⁵ -cyclopentadidiene). Enyl) iron (II) and the like are exemplified, and more specifically, benzoin tosylate, 2,5-dinitrobenzyl tosylate, N-tosiphthalimide and the like are exemplified, but not limited thereto.

  Examples of radical polymerization initiators that can be used as cationic polymerization initiators include aromatic iodonium salts, aromatic sulfonium salts, aromatic diazonium salts, aromatic phosphonium salts, triazine compounds, iron arene complexes, and the like. More specifically, iodonium chloride such as diphenyliodonium, ditolyliodonium, bis (p-tert-butylphenyl) iodonium, bis (p-chlorophenyl) iodonium, bromide, borofluoride, hexafluorophosphate salt, hexafluoro Iodonium salts such as antimonate salts, chlorides of sulfonium such as triphenylsulfonium, 4-tert-butyltriphenylsulfonium, tris (4-methylphenyl) sulfonium, bromides, borofluorides, hexaf Sulfonium salts such as orophosphate salts and hexafluoroantimonate salts, 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2-phenyl-4,6-bis (trichloromethyl) -1, 2,4,6-substituted-1,3,5 triazine compounds such as 3,5-triazine, 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, etc. It is not limited to these.

(Solvent of curable resin composition for hard coat layer)
Specific examples of the solvent include methanol, ethanol, normal propanol, isopropanol (IPA), normal butanol, sec-butanol, isobutanol, tert-butanol, methyl glycol, propylene glycol monomethyl ether (PGME), methyl glycol acetate, methyl cellosolve. Alcohols such as ethyl cellosolve and butyl cellosolve; ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclohexanone and diacetone alcohol; methyl formate, methyl acetate, ethyl acetate, ethyl lactate, butyl acetate, etc. Esters; nitrogen-containing compounds such as nitromethane, N-methylpyrrolidone, N, N-dimethylformamide; diisopropyl ether, tetrahydrofuran , Dioxane, dioxolane and the like; methylene chloride, chloroform, trichloroethane, halogenated hydrocarbons such as tetrachloroethane; dimethylsulfoxide, other objects, such as propylene carbonate; or mixtures thereof.
Since the hardness of the hard coat film can be improved, it is selected from the group consisting of methyl isobutyl ketone (MIBK), propylene glycol monomethyl ether (PGME), normal propanol, isopropanol, normal butanol, sec-butanol, isobutanol, and tert-butanol. One or more impermeable solvents are preferred. By using a non-permeable solvent, the binder component does not penetrate into the light-transmitting substrate, so that the hardness of the hard coat layer can be increased.
In addition, in this invention, osmosis | permeation means dissolving or swelling a light transmissive base material.

(Antistatic agent)
Specific examples of the antistatic agent include quaternary ammonium salts, pyridinium salts, various cationic compounds having cationic groups such as primary to tertiary amino groups, sulfonate groups, sulfate ester bases, and phosphate ester bases. , Anionic compounds having an anionic group such as phosphonate group, amphoteric compounds such as amino acid series and aminosulfate ester series, nonionic compounds such as amino alcohol series, glycerin series and polyethylene glycol series, and alkoxides of tin and titanium And metal chelate compounds such as acetylacetonate salts thereof, and compounds obtained by increasing the molecular weight of the compounds listed above. In addition, it has a tertiary amino group, a quaternary ammonium group, or a metal chelate portion, and has a monomer or oligomer that can be polymerized by ionizing radiation, or a polymerizable functional group that can be polymerized by ionizing radiation, and Polymerizable compounds such as organometallic compounds such as coupling agents can also be used as antistatic agents.

  Examples of the antistatic agent include conductive polymers. The conductive polymer is not particularly limited, for example, aromatic conjugated poly (paraphenylene), heterocyclic conjugated polypyrrole, polythiophene, aliphatic conjugated polyacetylene, heteroatom-containing polyaniline, mixed type Conjugated poly (phenylene vinylene), a double chain conjugated system that has a plurality of conjugated chains in the molecule, and a conductive polymer that is a polymer obtained by grafting or block-copolymerizing the conjugated polymer chain to a saturated polymer. And the like.

Moreover, electroconductive fine particles are mentioned as another example of the said antistatic agent. Specific examples of the conductive fine particles include those made of a metal oxide. Examples of such metal oxides include ZnO (refractive index 1.90, the numerical value in parentheses below represents the refractive index), CeO ₂ (1.95), Sb ₂ O ₂ (1.71), SnO. ₂ (1.997), indium tin oxide (1.95) often referred to as ITO, In ₂ O ₃ (2.00), Al ₂ O ₃ (1.63), antimony-doped tin oxide (abbreviation) ATO, 2.0), aluminum-doped zinc oxide (abbreviation: AZO, 2.0), and the like. The conductive fine particles preferably have an average particle size of 0.1 nm to 0.1 μm. By being within such a range, when the conductive fine particles are dispersed in a binder, a composition capable of forming a highly transparent film having almost no haze and good total light transmittance can be obtained.

(Anti-glare agent)
Examples of the antiglare agent include fine particles, and the shape of the fine particles may be a true sphere or an ellipse, and preferably a true sphere. The fine particles may be inorganic or organic, but those formed of an organic material are preferred. The fine particles exhibit anti-glare properties and are preferably transparent. Specific examples of the fine particles include plastic beads, and more preferably those having transparency. Specific examples of plastic beads include styrene beads (refractive index 1.59), melamine beads (refractive index 1.57), acrylic beads (refractive index 1.49), acrylic-styrene beads (refractive index 1.54), Examples thereof include polycarbonate beads and polyethylene beads. The addition amount of the fine particles is 2 to 30 parts by mass, preferably about 10 to 25 parts by mass with respect to 100 parts by mass of the curable resin composition for hard coat layer.

(Restorable layer)
The restorative layer contains a urethane (meth) acrylate obtained by reacting an organic isocyanate having two or more isocyanate groups in one molecule, a hydroxy-modified (meth) acrylate, and a polycaprolactone-containing polyfunctional alcohol. It consists of the hardened | cured material of the curable resin composition for adhesive layers, has a softness | flexibility superior to a hard-coat layer, has the restoring property with respect to a damage | wound, and has the effect which prevents the visibility fall of the hard-coat film by a damage | wound.

  The film thickness of the recoverable layer may be appropriately set according to the performance required for the hard coat film, and is not particularly limited, but is preferably 5 to 30 μm. If it is 5 μm or more, it becomes easy to obtain restorability, and if it exceeds 30 μm, cracks (so-called cracks) tend to occur, or the entire hard coat film warps due to curing shrinkage of a binder component such as urethane (meth) acrylate (so-called Curling is likely to occur.

(Curable resin composition for restoring layer)
Hereinafter, the curable resin composition for a recoverable layer which is cured to become a recoverable layer will be described.
Urethane obtained by reacting organic isocyanate having two or more isocyanate groups in one molecule, hydroxy-modified (meth) acrylate and polycaprolactone-containing polyfunctional alcohol for curable resin composition for restorative layer (Meth) acrylate is included.

(Urethane (meth) acrylate of curable resin composition for restorative layer)
The urethane (meth) acrylate contained in the curable resin composition for the restorable layer comprises an organic isocyanate having two or more isocyanate groups in one molecule, a hydroxy-modified (meth) acrylate, and a polycaprolactone-containing polyfunctional alcohol. It was obtained by reacting. By recovering the curable resin composition for a recoverable layer containing the urethane (meth) acrylate, a recoverable layer having excellent scratch resistance and recoverability can be obtained.

  Content of the said urethane (meth) acrylate in the curable resin composition for a restoring layer is not specifically limited, What is necessary is just to adjust suitably according to the performance by which a hard-coat film is requested | required. The urethane (meth) acrylate is contained in an amount of 5 to 95% by mass with respect to the total solid content of the curable resin composition for the recoverable layer, from the viewpoint of the excellent recoverability, hardness and scratch resistance of the hard coat film. It is preferable that 30 to 70% by mass is contained.

  Commercially available urethane (meth) acrylates include caprolactone-modified urethane acrylate (manufactured by Daicel-Cytec Co., Ltd., KRM7735), urethane acrylate (manufactured by SARTOMER, CN9996, CN9873) (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., UV3200B). ) Is available.

  Hereinafter, the organic isocyanate, hydroxy-modified (meth) acrylate, and polycaprolactone-containing polyfunctional alcohol, which are raw materials for the urethane (meth) acrylate, will be described in order.

(Organic isocyanate)
The organic isocyanate is an organic compound having two or more isocyanate groups in one molecule, but the number of isocyanate groups contained in one molecule of the organic isocyanate is preferably three or more.

  Organic isocyanates having two isocyanate groups in one molecule include tolylene diisocyanate, naphthalene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate. And diisocyanate monomers such as methyl-2,6-diisocyanate hexanoate and norbornane diisocyanate.

  The organic isocyanate having three or more isocyanate groups in one molecule includes a compound represented by the following chemical formula (1) obtained by modifying a diisocyanate monomer with an isocyanurate, and a chemical formula (2) represented by the following formula in which a diisocyanate monomer is adduct modified. A compound represented by the following formula, a compound represented by the following chemical formula (3) obtained by biuret modification of a diisocyanate monomer, an isocyanate such as 2-isocyanatoethyl-2,6-diisocyanate caproate, triaminononane triisocyanate Examples include prepolymers.

化学式（１）において、Ｒは、下記（１−１）〜（１−７）よりなる群から選ばれるいずれかである。

In the chemical formula (1), R is any one selected from the group consisting of the following (1-1) to (1-7).

化学式（２）において、Ｒは、上記化学式（１）のＲと同じである。

In the chemical formula (2), R is the same as R in the chemical formula (1).

(Hydroxy-modified (meth) acrylate)
The hydroxy-modified (meth) acrylate has a structure in which the hydrogen atom of the carboxyl group of (meth) acrylic acid is replaced with an atomic group having a hydroxyl group. Specifically, polycaprolactone-modified alkyl (meth) acrylate represented by the following chemical formula (4), hydroxyalkyl (meth) acrylate represented by the following chemical formula (5), 2-hydroxy-3-phenoxy Propyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl-phthalic acid, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (Meth) acrylate, glycerol mono (meth) acrylate, pentaerythritol tri (meth) acrylate and the like. Of these, polycaprolactone-modified alkyl (meth) acrylate is preferred. The polycaprolactone-modified alkyl (meth) acrylate may have any number of repeating caprolactone units of 1 to 25. However, if the number of repeating caprolactone units is too large, the strength of the restorable layer decreases, so the number of repetitions is 5 or less is preferable.

化学式（４）において、Ｒは水素原子又はメチル基、ｎは１〜１０の整数、ｍは１〜２５の整数である。

In the chemical formula (4), R is a hydrogen atom or a methyl group, n is an integer of 1 to 10, and m is an integer of 1 to 25.

化学式（５）において、Ｒは水素原子又はメチル基、ｌは１〜１０の整数である。

In the chemical formula (5), R is a hydrogen atom or a methyl group, and l is an integer of 1 to 10.

  The hydroxy-modified (meth) acrylate may be a mixture of two or more hydroxy-modified (meth) acrylates having different numbers of repeating caprolactone units. That is, a mixture of two or more kinds of polycaprolactone-modified alkyl (meth) acrylates having different numbers of repeating caprolactone units, or a mixture of hydroxy-modified (meth) acrylate polycaprolactone unmodified and polycaprolactone-modified alkyl (meth) acrylate. May be. In this case, it is possible to provide a urethane (meth) acrylate capable of forming a recoverable layer capable of exhibiting particularly excellent scratch resistance.

  When the hydroxy-modified (meth) acrylate is a mixture as described above, the maximum difference in the number of repeating caprolactone units between the hydroxy-modified (meth) acrylates is preferably 9 or less, and the average of the number of repetitions is 5 or less. Preferably there is. When the maximum difference in the number of repeating caprolactone units is 9 or less, the scratch resistance of the recoverable layer can be further improved. Further, if the average number of repeating caprolactone units is 5 or less, it is possible to prevent the strength of the restorable layer from being lowered due to the excessive number of repeating caprolactone units.

(Polycaprolactone-containing polyfunctional alcohol)
Specific examples of polycaprolactone-containing polyfunctional alcohols include polycaprolactone diols, polycaprolactone triols, polycaprolactone tetraols, and polycaprolactone polyols having 5 or more functional groups.
The polycaprolactone-containing polyfunctional alcohol may have any number of repeating caprolactone units. However, if the number of repeating caprolactone units is too large, the strength of the recoverable layer decreases, and the number of repeating may be 5 or less. preferable. The polycaprolactone-containing polyfunctional alcohol may be a mixture of two or more polycaprolactone-containing polyfunctional alcohols having different numbers of repeating caprolactone units.

In addition, the polycaprolactone-containing polyfunctional alcohol is more preferable as the number of functional groups (—O— [CO (CH ₂ ) ₅ O] _n —H) is larger. As the number of functional groups (—O— [CO (CH ₂ ) ₅ O] _n —H) increases, the number of photocurable groups in the urethane (meth) acrylate increases, so that the crosslinking density increases, and as a result, restoration This is because the scratch resistance of the adhesive layer is improved.

  Note that urethane (meth) acrylates that contain polycaprolactone-containing polyfunctional alcohol in the reaction raw material may curl or process when cured even if the number of photocurable groups increases and the crosslinking density increases. There is little risk of decline.

(Other components of curable resin composition for restoring layer)
The curable resin composition for a restoring layer of the present invention may contain one or more compounds selected from the group consisting of a long-chain alkyl group-containing compound, a silicone compound, and a fluorine compound. By containing the compound, the scratch resistance and adhesion of the recoverable layer can be improved.

  The long-chain alkyl group-containing compound, silicone compound and fluorine compound preferably have a photocurable group. When the compound has a photocurable group, the curable resin composition for the recoverable layer can be reduced in viscosity and converted into a high solid, and the adhesiveness and solvent resistance of the recoverable layer can be improved. it can.

  Hereinafter, the long-chain alkyl group-containing compound, the silicone compound, and the fluorine compound will be described in order.

(Long chain alkyl group-containing compound)
The long-chain alkyl group-containing compound improves the surface slipperiness of the restorable layer and improves the scratch resistance of the restorable layer.

  The long chain alkyl group of the long chain alkyl group-containing compound preferably has 13 to 25 carbon atoms. When the carbon number of the long-chain alkyl group is 13 to 25, the scratch resistance of the recoverable layer can be further improved.

  Furthermore, the long-chain alkyl group-containing compound is preferably a polyether-modified product. When the long-chain alkyl group-containing compound is a polyether-modified product, antistatic properties can be imparted to the recoverable layer.

  Specific examples of the long-chain alkyl group-containing compound having a long-chain alkyl group having 13 to 25 carbon atoms include tridecanol, myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, polyoxyethylene cetyl alcohol, polyoxyethylene stearyl alcohol, Long chain alcohols such as glycerol monostearate; tridecyl (meth) acrylate, myristyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, stearoxy polyethylene glycol mono (meth) acrylate, etc. These active energy ray-curable compounds are listed.

(Silicone compound)
Specific examples of the silicone compound include polydimethylsiloxane, alkyl-modified polydimethylsiloxane, carboxyl-modified polydimethylsiloxane, amino-modified polydimethylsiloxane, epoxy-modified polydimethylsiloxane, fluorine-modified polydimethylsiloxane, and (meth) acrylate-modified polydimethyl. Examples thereof include siloxane.

(Fluorine compounds)
Specific examples of the fluorine-based compound include compounds having a fluoroalkyl group such as a fluoroalkyl carboxylate, a fluoroalkyl quaternary ammonium salt, and a fluoroalkylethylene oxide adduct; a perfluoroalkyl carboxylate and a perfluoroalkyl quaternary ammonium salt. A compound having a perfluoroalkyl group such as a perfluoroalkylethylene oxide adduct; a compound having a fluorocarbon group; a tetrafluoroethylene polymer; a copolymer of vinylidene fluoride and tetrafluoroethylene; a copolymer of vinylidene fluoride and hexafluoropropylene Fluorine-containing (meth) acrylic acid ester; Fluorine-containing (meth) acrylic acid ester polymer; Fluorine-containing (meth) acrylic acid alkyl ester polymer; Fluorine-containing (meth) acrylic acid Copolymers of esters and other monomers.

  Examples of other optional components include a polymerization initiator, other binder components, and a solvent.

(Polymerization initiator)
Examples of polymerization initiators include isopropyl benzoin ether, isobutyl benzoin ether, benzophenone, Michler ketone, o-benzoylmethyl benzoate, acetophenone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, ethyl anthraquinone, isoamyl p-dimethylaminobenzoate Ester, p-dimethylaminobenzoic acid ethyl ester, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1 -One, 2-benzyl-2-dimethylamino-1 (4-morpholinophenyl) -butanone-1, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, methylbenzyl Rumeto, and the like.
Moreover, you may use the polymerization initiator quoted by the said curable resin composition for hard-coat layers.

(Other binder components)
Examples of other binder components that may be contained in the restorable layer curable resin composition include monofunctional or polyfunctional monomers or oligomers having a (meth) acryloyl group. Specifically, monohydroxyethyl (meth) acrylate phthalate, 2-ethoxyhexyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-ethoxyethoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polycaprolactone-modified hydroxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, N-vinylpyrrolidone, acryloylmorpholine, isobornyl (meth) Monofunctional monomers such as acrylate, vinyl acetate, styrene; neopentyl glycol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,6-hexanedio Rudi (meth) acrylate, 1,4-butanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate , Dipropylene glycol di (meth) acrylate, bisphenol F diglycidyl ether acrylic acid adduct, bisphenol A diglycidyl ether acrylic acid adduct, bisphenol F ethylene oxide modified diacrylate, bisphenol A ethylene oxide modified diacrylate, etc. Monomers of trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and 3 mol of trimethylolpropane Tri (meth) acrylate of pyrene oxide adduct, 6 mol ethylene oxide adduct of trimethylolpropane tri (meth) acrylate, glycerin propoxytri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone of dipentaerythritol Multifunctional monomers such as adduct hexa (meth) acrylate; unsaturated polyester, polyester (meth) acrylate, polyether (meth) acrylate, acrylic (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate And other oligomers.

(Solvent of curable resin composition for recoverable layer)
The solvent is not particularly limited, and examples thereof include aromatic hydrocarbon solvents such as toluene and xylene, alcohol solvents such as methanol, ethanol, isopropyl alcohol, n-butanol and isobutanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, Examples include ketone solvents such as cyclohexanone, and ester solvents such as ethyl acetate, propyl acetate, butyl acetate, and isobutyl acetate.

(Other layers)
As described above, the hard coat film according to the present invention is basically composed of a light-transmitting substrate, a hard coat layer, and a restoring layer. However, in consideration of the function or use as a hard coat film, the antistatic layer, the antiglare layer, and the antifouling layer are provided on the opposite side of the restorative layer from the hard coat layer within the scope of the present invention. One or two or more layers selected from the group consisting of a low refractive index layer and a second hard coat layer that is the same as or different from the hard coat layer may be provided.

(Antistatic layer)
The antistatic layer is made of a cured product of a curable resin composition for an antistatic layer containing an antistatic agent and a curable resin. The thickness of the antistatic layer is preferably about 30 nm to 3 μm.

  As the antistatic agent, the same materials as those mentioned above for the antistatic agent for the hard coat layer can be used.

  As a curable resin contained in the curable resin composition for an antistatic layer, a known resin can be appropriately selected and used alone or in combination of two or more. For example, what was mentioned by the other binder component of the said curable resin composition for recoverable layers can be used.

(Anti-glare layer)
The antiglare layer is made of a cured product of a curable resin composition for an antiglare layer containing an antiglare agent and a curable resin. As the curable resin, a known resin can be appropriately selected, and one kind or two or more kinds can be used.

(Anti-glare agent)
As the antiglare agent, the same antiglare agents as those described above for the hard coat layer can be used.

(Anti-fouling layer)
According to a preferred embodiment of the present invention, an antifouling layer may be provided for the purpose of preventing dirt on the outermost surface of the hard coat film. The antifouling layer can further improve the antifouling property and scratch resistance of the hard coat film. The antifouling layer comprises a cured product of a curable resin composition for an antifouling layer comprising an antifouling agent and a curable resin composition.

  The antifouling agent and curable resin contained in the curable resin composition for the antifouling layer can be appropriately selected from known antifouling agents and curable resins, and one or more can be used.

(Low refractive index layer)
The low refractive index layer is a layer having a lower refractive index than the layer adjacent to the light transmissive substrate side of the layer, and is made of a cured product of the curable resin composition for the low refractive index layer. In the curable resin composition for a low refractive index layer, a known low refractive index curable resin or fine particles can be appropriately used so that the refractive index is lower than that of the adjacent layer.

(Second hard coat layer)
From the viewpoint of further improving the hardness of the hard coat film, a second hard coat layer may be provided.
The second hard coat layer may be the same as the hard coat layer, and the composition of the two hard coat layers may be the same or different.

(Method for producing hard coat film)
The method for producing a hard coat film according to the present invention includes the curable resin composition for hard coat layer and the curable resin composition for recoverable layer described above from the light transmissive substrate side on one side of the light transmissive substrate. Applying and forming a coating film,
It includes a step of irradiating the coating film with light and curing.

(Preparation of curable resin composition for hard coat layer and curable resin composition for recoverable layer)
The curable resin composition for a hard coat layer is usually prepared by mixing and dispersing each component listed in the curable resin composition for a hard coat layer in a solvent according to a general preparation method. A paint shaker or a bead mill can be used for mixing and dispersing.
Similarly, the curable resin composition for the restorable layer is also prepared by mixing and dispersing each component listed in the above curable resin composition for the restorable layer in accordance with a general preparation method.

  A curable resin composition for a hard coat layer is applied on a light transmissive substrate to form a coating film, dried as necessary, and the coating film is cured by light irradiation to form a hard coat layer.

The application method is not particularly limited as long as it is a method that can uniformly apply the curable resin composition for the hard coat layer to the surface of the light-transmitting substrate. The spin coating method, the dip method, the spray method, Various methods such as a slide coating method, a bar coating method, a roll coater method, a meniscus coater method, a flexographic printing method, a screen printing method, and a speed coater method can be used.
In addition, the coating amount of the curable resin composition for the hard coat layer on the light-transmitting substrate varies depending on the performance required of the obtained hard coat film, but the coating amount after drying is in the range of ^{1g / m 2 ~30g / m 2} , particularly preferably in the range of ^{5g / m 2 ~25g / m 2} .

  Examples of the drying method include reduced-pressure drying or heat drying, and a method combining these drying methods. For example, when a ketone solvent is used as the solvent, it is usually dried at a temperature in the range of room temperature to 80 ° C., preferably 40 ° C. to 60 ° C., for 20 seconds to 3 minutes, preferably 30 seconds to 1 minute. A process is performed.

  Next, according to the reactive functional group contained in the curable resin composition for hard coat layer, light is applied to the coating film applied with curable resin composition for hard coat layer and dried as necessary. The reactivity of the reactive inorganic fine particles contained in the reactive functional groups of the binder component and, if necessary, contained in the constituent components of the curable resin composition for hard coat layer by irradiating and curing the coating film The functional group is cross-linked to form a hard coat layer made of a cured product of the hard coat layer curable resin composition.

For light irradiation, ultraviolet rays, visible light, electron beams, ionizing radiation, etc. are mainly used. In the case of ultraviolet curing, ultraviolet rays or the like emitted from light such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, or a metal halide lamp are used. The irradiation amount of the energy ray source is about 50 to 5000 mJ / cm ² as an integrated exposure amount at an ultraviolet wavelength of 365 nm.
Heating may be performed in addition to light irradiation. When heating, the treatment is usually performed at a temperature of 40 ° C to 120 ° C. Moreover, you may react by leaving it to stand for 24 hours or more at room temperature (25 degreeC).

(Formation of restorable layer)
After forming the hard coat layer, apply the curable resin composition for the restorative layer on the hard coat layer in the same manner as the curable resin composition for the hard coat layer to form a coating film, and dry it as necessary. By applying light, the coating film is cured to form a restorable layer, and the hard coat film according to the present invention is obtained.

  The application method, drying method, and curing method of the curable resin composition for the recoverable layer may be performed in the same manner as the formation of the hard coat layer, and can be adjusted as appropriate.

Further, the coating amount of the curable resin composition for the restorable layer on the hard coat layer varies depending on the performance required of the obtained hard coat film, but the coating amount after drying is 5 g / in the range of ^{m 2} ~30g / m ^2, particularly preferably in the range of ^{10g / m 2 ~20g / m 2} .

In addition, before the hard coat layer curable resin composition is applied and the hard coat layer is completely formed, that is, the hard coat layer curable resin composition is half-cured (half-cured), and the half-cured state The hardenable layer is coated with the curable resin composition for a recoverable layer and dried, and the hardcoat layer and the recoverable layer are simultaneously irradiated with light and / or heated to be fully cured (completely cured). A hard coat film may be obtained.
In the case of half-curing, the integrated exposure amount at an ultraviolet wavelength of 365 nm is, for example, about 5 to 50 mJ / cm ² .

(Formation of other layers)
After the hard coat layer and the restorative layer are formed on the light-transmitting substrate, the other layer of the curable resin composition is applied onto the restorable layer, and is dried as necessary. What is necessary is just to harden by heating and to provide another layer.

Hereinafter, the present invention will be described more specifically with reference to examples. These descriptions do not limit the present invention.
As the silica fine particles (1), Nissan Chemical Industries, Ltd., IPAST (L), average particle size of 40 nm, colloidal silica, and a solid content 30% solution were used.
As the silica fine particles (2), Nissan Chemical Industries, Ltd., IPA-ST, average particle size of 12 nm, colloidal silica, and 30% solid content liquid were used.
DPHA manufactured by Nippon Kayaku Co., Ltd. was used as dipentaerythritol hexaacrylate.
As pentaerythritol triacrylate, Nippon Kayaku Co., Ltd. product, PET30 was used.
As a caprolactone-modified urethane acrylate obtained by reacting an organic isocyanate having two or more isocyanate groups in one molecule, a hydroxy-modified acrylate and / or a hydroxy-modified methacrylate, and a polycaprolactone-containing polyfunctional alcohol, Daicel Cytec KRM7735 manufactured by Co., Ltd. was used.
As a urethane acrylate other than the caprolactone-modified urethane acrylate, BS371 manufactured by Arakawa Chemical Industries, Ltd. was used.
M9050 manufactured by Toagosei Co., Ltd. was used as the polyester acrylate.
As a silane coupling agent, 3-methacryloxypropyltrimethoxysilane, KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd., was used.
As a polymerization initiator, Irgacure 184 manufactured by Ciba Japan Co., Ltd. was used.
As the light transmissive substrate, a TAC film (thickness 80 μm, triacetyl cellulose resin film, trade name: TF80UL, manufactured by Fuji Film Co., Ltd.) was used.
Abbreviations for each compound are as follows.
DPHA: dipentaerythritol hexaacrylate PETA: pentaerythritol triacrylate MIBK: methyl isobutyl ketone IPA: isopropanol

(Preparation of reactive silica fine particles (1))
The silica fine particles (1) were subjected to solvent substitution from IPA to MIBK using a rotary evaporator to obtain a MIBK dispersion having 30% by mass of silica particles. By adding 5 parts by mass of 3-methacryloxypropylmethyldimethoxysilane to 100 parts by mass of this MIBK dispersion and subjecting it to heat treatment at 50 ° C. for 1 hour, the solid content of the surface-treated reactive silica fine particles having an average particle diameter of 40 nm is obtained. A 30% by mass MIBK dispersion was obtained.

(Preparation of curable resin composition)
Components of the composition shown below were blended to prepare curable resin composition R1 for restorable layer and curable resin compositions H1 to H6 for hard coat layer, respectively.

(Curable resin composition R1 for restoring layer)
KRM7735 (caprolactone-modified urethane acrylate): 45 parts by mass Irgacure 184: 4 parts by mass MIBK: 51 parts by mass

(Curable resin composition for hard coat layer H1)
Silica fine particles (2): 18 parts by mass (in terms of solid content)
DPHA: 27 parts by mass Irgacure 184: 4 parts by mass MIBK: 51 parts by mass

(Curable resin composition for hard coat layer H2)
Reactive silica fine particles (1): 20 parts by mass (in terms of solid content)
DPHA: 25 parts by mass Irgacure 184: 4 parts by mass MIBK: 51 parts by mass

(Curable resin composition for hard coat layer H3)
DPHA: 45 parts by mass Irgacure 184: 4 parts by mass MIBK: 51 parts by mass

(Curable resin composition for hard coat layer H4)
PET 30: 45 parts by mass Irgacure 184: 4 parts by mass MIBK: 51 parts by mass

(Curable resin composition for hard coat layer H5)
M9050: 45 parts by mass Irgacure 184: 4 parts by mass MIBK: 51 parts by mass

(Curable resin composition for hard coat layer H6)
BS371: 45 parts by mass Irgacure 184: 4 parts by mass MIBK: 51 parts by mass

Example 1: Production of Hard Coat Film The curable resin composition H1 for hard coat layer was applied to one side of the TAC film as a curable resin composition for hard coat layer, and was heated in a hot oven at a temperature of 70 ° C. Dry for 2 seconds, evaporate the solvent in the coating film, and cure the coating film by irradiating ultraviolet rays so that the integrated light quantity becomes 200 mJ, thereby forming a hard coat layer (lower layer) with a film thickness of 9 μm (13 g / cm ² ). Formed. Furthermore, on the hard coat layer, the curable resin composition R1 for recoverable layer was applied as a recoverable layer curable resin composition, and dried in a heat oven at a temperature of 70 ° C. for 60 seconds. The solvent inside is evaporated, and the coating film is cured by irradiating ultraviolet rays with an integrated light amount of 200 mJ to form a 10 μm-thickness restoring layer (upper layer). Produced.

  Examples The curable resin composition for forming the hard coat layer and the restorative layer as the curable resin composition for the hard coat layer and the curable resin composition for the restorable layer, respectively, except that those shown in Table 1 were used. In the same manner as in Example 1, hard coat films of Examples 2 to 6 were produced. In Comparative Examples 1 and 2, only the restorative layer having a film thickness of 10 μm and 20 μm was formed on the TAC film using the curable resin composition R1 for the restorative layer without providing the hard coat layer. A hard coat film was obtained. In Comparative Example 3, a hard coat film was formed by forming only a 9 μm thick hard coat layer using a curable resin composition for a hard coat layer on a TAC film without providing a recoverable layer.

(Evaluation of hard coat film)
About the produced hard coat film of Examples 1-6 and Comparative Examples 1-3, pencil hardness and the resilience of a flaw were evaluated as follows. The results are shown in Table 1.

(Evaluation: Pencil hardness)
Pencil hardness test: The hardness of the pencil scratch test is a test specified by JIS-S-6006 after conditioning the prepared hard coat film (the optical laminate) at a temperature of 25 ° C. and a relative humidity of 60% for 2 hours. The pencil hardness test (4.9N load) specified in JIS K5600-5-4 (1999) was performed using a pencil for testing (hardness 2H to 4H), the pencil hardness was evaluated, and the highest hardness that was not damaged Was measured.
In Table 1, an evaluation of 3.5H means a case where there are two flaws in a 5H test in a 4H hardness test, and an evaluation of 3H means that a flaw is 3 in a 5H test in a 4H hardness test. Means more than books.

(Evaluation: Restoration)
When the pencil with the lowest hardness was scratched in the pencil hardness test, the pencil was left at room temperature for 30 minutes after being scratched, and evaluated according to the following evaluation criteria.
Evaluation ○: Restorable layer is restored and scratches are eliminated. Evaluation ×: Restorable layer is not restored and scratches are present.

From Table 1, in Examples 1 to 6, good results were obtained in pencil hardness and restorability.
On the other hand, in Comparative Examples 1 and 2 having only the restorative layer, the function of the underlayer was not obtained because there was no hard coat layer, the pencil hardness was as low as 2H, and there were no scratches.
Since Comparative Example 3 having only the hard coat layer also had no restoring layer, both the pencil hardness and the restoring property were inferior to those of the Examples.

DESCRIPTION OF SYMBOLS 1 Hard coat film 10 Light transmissive base material 20 Hard coat layer 30 Restorable layer 40 Low refractive index layer 50 Antistatic layer

Claims (10)

A hard coat film provided with a hard coat layer and a restorative layer in order from the light transmissive substrate side on one side of the light transmissive substrate,
The hard coat layer comprises a cured product of a curable resin composition for a hard coat layer containing a binder component,
The restorable layer is a urethane acrylate obtained by reacting organic isocyanate having two or more isocyanate groups in one molecule, hydroxy-modified acrylate and / or hydroxy-modified methacrylate and polycaprolactone-containing polyfunctional alcohol, and / or Or the hard coat film which consists of hardened | cured material of the curable resin composition for recoverable layers containing urethane methacrylate.   The hard coat film according to claim 1, wherein the hardness of the hard coat layer is 2H or more in a pencil hardness test (4.9 N load) defined in JIS K5600-5-4 (1999).   The hard coat film according to claim 1 or 2, wherein the restorable layer has a thickness of 5 to 30 µm.   The hard coat film according to any one of claims 1 to 3, wherein the hydroxy-modified acrylate and / or hydroxy-modified methacrylate is polycaprolactone-modified alkyl acrylate and / or polycaprolactone-modified alkyl methacrylate.   The hydroxy-modified acrylate and / or hydroxy-modified methacrylate is a mixture of two or more hydroxy-modified acrylates and / or hydroxy-modified methacrylates having different numbers of repeating caprolactone units. The hard coat film according to one item.   The hard coat film according to claim 5, wherein the maximum difference in the number of repetitions between hydroxy-modified acrylates and / or hydroxy-modified methacrylates having different numbers of repeating caprolactone units is 9 or less.   The curable resin composition for a restorable layer further contains at least one compound selected from the group consisting of a long-chain alkyl group-containing compound, a silicone compound, and a fluorine compound. The hard coat film according to any one of 6.   The hard coat film according to claim 7, wherein at least one compound selected from the group consisting of the long-chain alkyl group-containing compound, the silicone-based compound, and the fluorine-based compound has a photocurable group.   9. The hard coat film according to claim 7, wherein the long-chain alkyl group of the long-chain alkyl group-containing compound has 13 to 25 carbon atoms.   On the surface of the restorative layer opposite to the hard coat layer, an antistatic layer, an antiglare layer, an antifouling layer, a low refractive index layer and a second hard coat layer which is the same as or different from the hard coat layer are formed. The hard coat film according to any one of claims 1 to 9, wherein one or more layers selected from a group are provided.

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