JP2010069839A - Hard coat film and method of manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hard coat film excelling in hardness and scratch resistance, particularly excelling in pencil hardness, without needing a protective sheet. <P>SOLUTION: The hard coat film 1 is provided with a hard coat layer 20 on one face of a transparent base material film 10. The opposite face of the transparent base material film, of the hard coat layer, has a surface roughness of No.40-15000 in the grain size of an abrasive specified in JIS R6001. A method of manufacturing the hard coat film is also provided. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a hard coat film in which a hard coat layer is provided on a transparent substrate film, which is used for the purpose of protecting the surface of a display or the like, and a method for producing the hard coat film.

  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 using a hard coat film in which a hard coat (HC) layer is provided on a base film, and a hard coat film (optical laminate) having optical functions such as antireflection and antiglare properties. Generally, the scratch resistance of the image display surface of the image display device is improved.

  As a method for improving the hardness of the hard coat layer, there is a method of adding inorganic fine particles, and generally, a hard coat film in which a hard coat layer having inorganic fine particles added is provided on a base film has been produced.

  Generally, a pencil hardness test as defined in JIS K5600-5-4 (1999) is adopted for evaluating the hardness and scratch resistance of a hard coat film.

  In Patent Document 1, an intermediate layer obtained by curing a composition containing a photocurable resin and a thermosetting resin is provided on a transparent substrate, and a hard coat layer is further provided on the intermediate layer to achieve a pencil hardness of 3H. I am trying.

  Further, products such as hard coat films may be scratched on the surface due to impact or the like during transportation in the production process, and a protective sheet for preventing such scratches may be used. However, from the viewpoint of process simplification and manufacturing cost reduction, it is required to omit the protection process by such a protection sheet and reduce the cost of the protection sheet.

JP 2008-107762 A

  The present invention has been made in view of the above problems, and an object thereof is to provide a hard coat film excellent in hardness and scratch resistance, particularly a hard coat film excellent in pencil hardness, which does not require a protective sheet. To do.

As a result of intensive investigations on the above problems, the present inventors have found that the hard coat layer provided on the transparent substrate film has a surface roughness of the abrasive grain size of 40 to 15000 as defined in JIS R6001. The inventors have found that excellent pencil hardness can be exhibited, and have completed the present invention.
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 in which a hard coat layer is provided on one side of a transparent substrate film, and the surface of the hard coat layer opposite to the transparent substrate film is defined in JIS R6001. It has the surface roughness of the particle size 40-15000th of the abrasive | polishing material to perform.

  By having a surface roughness with a grain size of 40 to 15000, the pencil hardness of the hard coat layer surface is particularly excellent.

  In a preferred embodiment of the hard coat film of the present invention, the hardness of a pencil hardness test (500 g load) specified in JIS K5600-5-4 (1999) of the hard coat layer can be 3H or more. is there.

The manufacturing method of the 1st hard coat film which concerns on this invention is a manufacturing method of the said hard coat film, Comprising: The grinding | polishing which has the particle size of 40-15000 of the abrasives prescribed | regulated to one side of a transparent base film or JISR6001 Applying a curable resin composition for a hard coat layer containing a photocurable binder component to the abrasive side of the sheet to form a coating film;
While drying the coating film, or after drying, a polishing sheet having a grain size of No. 40 to 15000 of the abrasive specified in JIS R6001 on the side opposite to the transparent substrate film or polishing sheet of the coating film Bonding the surface on the abrasive side or one surface of the transparent substrate film to a three-layer structure of transparent substrate film / dried coating film / polishing sheet;
Irradiating the dried coating film with light from the transparent substrate film side after the three-layer structure formation, curing the dried coating film, and forming a hard coat layer;
Including a step of peeling the abrasive sheet from the hard coat layer and imparting a surface roughness of No. 40 to 15000 of the abrasive defined in JIS R6001 on the surface of the hard coat layer opposite to the transparent substrate film. It is characterized by that.

The manufacturing method of the 2nd hard coat film which concerns on this invention is a manufacturing method of the said hard coat film, Comprising: Of the abrasive sheet which has the particle size of No. 40-15000 of the abrasives prescribed | regulated to the one surface side of a base material or JISR6001 A process of applying a transfer mold curable resin composition on the abrasive side to form a coating film,
Then, after drying the coating film or after drying, the surface of the abrasive sheet side of the abrasive sheet or one surface of the substrate is bonded to the opposite side of the substrate or abrasive sheet of the coating film, A process of forming a three-layer structure of a substrate / dried coating film / abrasive sheet;
Next, the dried coating film after the formation of the three-layer structure is cured, the abrasive sheet is peeled off from the cured coating film, and the surface of the coating film opposite to the substrate is defined in JIS R6001. A surface roughness transfer layer having a surface roughness of the abrasive grain size 40 to 15000 defined in JIS R6001 is provided on the base material by providing the surface roughness of the abrasive grain size 40 to 15000. Obtaining a transfer mold,
Next, a step of applying a curable resin composition for a hard coat layer containing a photocurable binder component to one surface side of the transparent substrate film or the surface roughness transfer layer side of the transfer mold to form a coating film,
Next, while drying or drying the coating film of the curable resin composition for the hard coat layer, on the side of the coating film opposite to the transparent base film or the transfer mold, the transfer mold Bonding the surface on the surface roughness transfer layer side or one surface of the transparent substrate film to a transparent substrate film / dried coating film / transfer type three-layer structure;
Next, the step of irradiating the dried coating film from the transparent substrate film side after the formation of the three-layer structure including the transfer mold, curing the dried coating film, and forming a hard coat layer,
Subsequently, the transfer mold is peeled from the hard coat layer, and the surface roughness of the abrasive grain size of 40 to 15000 specified in JIS R6001 is applied to the surface of the hard coat layer opposite to the transparent substrate film. It is characterized by including.

The third method for producing a hard coat film according to the present invention is a method for producing the above hard coat film, which is an abrasive sheet having a grain size of No. 40 to 15000 of the abrasive as defined in one side of the substrate or JIS R6001. A process of applying a transfer mold curable resin composition on the abrasive side to form a coating film,
Then, after drying the coating film or after drying, the surface of the abrasive sheet side of the abrasive sheet or one surface of the substrate is bonded to the opposite side of the substrate or abrasive sheet of the coating film, A process of forming a three-layer structure of a substrate / dried coating film / abrasive sheet;
Next, the dried coating film after forming the three-layer structure of the substrate / dried coating film / polishing sheet is cured, the polishing sheet is peeled off from the cured coating film, and the coating film substrate The surface roughness of the abrasive grain size No. 40-15000 specified in JIS R6001 is given to the surface opposite to that of the abrasive grain size No. 40-15000 No. 40-15000 specified in JIS R6001 on the base material. Obtaining a first generation transfer mold having a surface roughness transfer layer having a thickness;
Next, the same or different transfer as the transfer type curable resin composition on the one surface side of the second substrate or the surface roughness transfer layer side of the first generation transfer mold Applying the mold curable resin composition to form a coating film, while drying or drying the coating film, on the opposite side of the coating film from the second substrate or the first generation transfer mold The surface of the first generation transfer mold on the surface roughness transfer layer side or one surface of the second substrate, and the second substrate / dried coating / first generation transfer mold three-layer structure And curing the dried coating film after the formation of the three-layer structure including the first generation transfer mold, peeling the first generation transfer mold from the cured coating film, By giving the surface roughness of the grain size 40-15000 of the abrasive defined in JIS R6001 to the surface opposite to the material, the second A step of obtaining a second generation transfer mold comprising a surface roughness transfer layer having a surface roughness of a grain size of 40 to 15000 of an abrasive defined in JIS R6001 on a substrate;
If necessary, the same process as the second generation transfer mold is repeated to obtain the latest generation transfer mold,
Applying a curable resin composition for a hard coat layer containing a photocurable binder component to one surface side of the transparent substrate film or the surface roughness transfer layer side of the latest generation transfer type including the second generation, and a coating film The process of
Next, while drying or drying the coating film of the curable resin composition for the hard coat layer, the latest generation is provided on the opposite side of the coating to the transparent substrate film or the latest generation transfer mold. Bonding the surface of the transfer mold on the surface roughness transfer layer side or one surface of the transparent substrate film to form a three-layer structure of transparent substrate film / dried coating film / latest generation transfer type;
Next, the step of irradiating the dried coating film with light from the transparent substrate film side after the formation of the three-layer structure including the latest generation transfer mold, curing the dried coating film, and forming a hard coat layer,
Next, the latest generation transfer mold is peeled off from the hard coat layer, and the surface roughness of the abrasive grain size of 40 to 15000 specified in JIS R6001 is given to the surface of the hard coat layer opposite to the transparent substrate film. Including the step of:

In the manufacturing method of the third hard coat film, as the latest generation transfer type including the second generation, obtaining an odd number generation transfer type,
Next, a hard coat film may be obtained using the odd-number generation transfer mold.

In the manufacturing method of the third hard coat film, as the latest generation transfer mold including the second generation, obtaining an even number generation transfer mold,
Next, a hard coat film may be obtained using the even-number generation transfer mold.

  By using an abrasive sheet having a grain size of No. 40-15000 as defined in JIS R6001, the surface roughness can be easily imparted to the hard coat layer, the hardness of the hard coat layer, scratch resistance, In particular, pencil hardness can be improved.

  In the present invention, the “hard coat layer” means a layer having a hardness of “H” or higher in a pencil hardness test (500 g load) defined in JIS K5600-5-4 (1999).

  The hard coat film according to the present invention has a surface roughness of the abrasive grain size of 40 to 15000 specified in the above JIS R6001, so that it is particularly excellent in pencil hardness, omits the surface protection step by the protective sheet, and is manufactured at a low cost. Can be reduced. Further, recording with a pencil on the hard coat film surface and erasing of the recording with an eraser are also possible.

  Hereinafter, the hard coat film according to the present invention will be described first, and then the transparent base film and the hard coat layer, which are essential components of the hard coat film, will be described in order.

In the present invention, the abrasive sheet is a group consisting of a polishing cloth of JIS R6251 having a surface roughness of a grain size of No. 40 to 15000 defined in JIS R6001, an abrasive paper of JIS R6252, and a water-resistant abrasive paper of JIS R6253. Means at least one selected from
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 said average particle diameter can be measured using the Nikkiso Co., Ltd. Microtrac particle size analyzer or Nanotrac particle size analyzer.
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 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 (500 g load) defined by JISK5600-5-4 (1999).
The light of the present invention includes not only electromagnetic waves having wavelengths in the visible and non-visible 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 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.

  Moreover, in this invention, a film thickness is a film thickness at the time of drying (dry film thickness), and means the thickness from the bottom face of a film | membrane to the highest point of a film | membrane. The film thickness may be measured using a known film thickness meter. For example, the film thickness can be measured with a digital thick tester manufactured by Mitutoyo Corporation. As a specific measuring method, for example, the film thickness of the transparent substrate film is measured, the film thickness of the transparent substrate film and the hard coat layer is measured after the hard coat layer is formed, and the latter transparent substrate is measured. A value obtained by subtracting the film thickness of only the transparent base film from the film thickness of the film and the hard coat layer is the film thickness of the hard coat layer.

I. Hard coat film The hard coat film according to the present invention is a hard coat film provided with a hard coat layer on one side of a transparent substrate film,
The surface of the hard coat layer opposite to the transparent substrate film has a surface roughness of a grain size of No. 40 to 15000 as defined in JIS R6001.

  FIG. 1 is a cross-sectional view schematically showing a hard coat film 1 according to the present invention. A hard coat layer 20 is provided on one surface side of the transparent substrate film 10, and the surface of the hard coat layer 20 has a surface roughness of the abrasive grain size of 40 to 15000 defined in JIS R6001.

In the hard coat film according to the present invention, the surface of the hard coat layer has a surface roughness of No. 40 to 15000 of the abrasive defined in JIS R6001 as described above. The surface roughness is excellent in hardness and scratch resistance, and particularly in pencil hardness.
Thus, since it is excellent in pencil hardness, the hard coat film concerning this invention is strong to the impact to the surface at the time of manufacture or transportation, and it is not necessary to provide a protective sheet on the hard coat film surface. Therefore, the process and cost for providing the protective sheet are not required, and the process can be simplified and the manufacturing cost can be reduced.

  Further, recording on the surface of the hard coat layer using a pencil and erasing of the recording with an eraser are possible, and the recording medium (recording means) using a pencil can also be used.

From the point of transparency (light transmittance) of the hard coat film, the abrasive grain size of 1200 to 15000 specified in JIS R6001 is preferable.
From the viewpoint of the steel wool resistance of the hard coat film, the abrasive grain size of 120 to 1200 specified in JIS R6001 is preferred.

  In a preferred embodiment of the hard coat film of the present invention, the hardness of a pencil hardness test (500 g load) specified in JIS K5600-5-4 (1999) of the hard coat layer can be 3H or more. Yes, more preferably 4H, and even more preferably 5H.

  Hereinafter, the transparent base film and the hard coat layer, which are constituent elements of the hard coat film according to the present invention, will be described in order.

1. Transparent substrate film The transparent substrate film is a plastic film or sheet having high transparency (light transmittance) and is not particularly limited as long as it satisfies the physical properties that can be used as the transparent substrate of the optical laminate. Can be selected and used as appropriate.
Usually, the base film used for the optical layered body is transparent, semi-transparent, colorless, or colored, but is required to have light transmittance. 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 transparent substrate film can be appropriately selected and used, but a transparent substrate having a thickness of 10 to 200 μm is used from the viewpoint of hardly cracking the surface of the hard coat film and imparting hardness. It is preferable that it is 30-150 micrometers.

  Preferable materials for the transparent substrate film 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 Co., Ltd. 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 methyl poly (meth) acrylate, poly (meth) ethyl acrylate, methyl (meth) acrylate-butyl (meth) acrylate, and the like.
Specific examples of the polyester include polyethylene terephthalate and polyethylene naphthalate.

As the transparent substrate film used in the present invention, the material having the highest transparency is cellulose acylate, and among them, triacetyl cellulose is preferably used.
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 film 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 cellulose and esters. There may be. These triacetyl celluloses may be added with other cellulose lower fatty acid esters such as diacetyl cellulose or various additives such as a plasticizer, an antistatic agent, and an ultraviolet absorber as required.

  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 transparent base film in the present invention includes those including the surface treatment and the primer layer. Accordingly, the case where the specific resin penetrates only into the primer layer is also included when the specific resin penetrates into the transparent base film.

2. Hard coat layer The hard coat layer of the present invention is a layer provided on one side of the transparent substrate film, and has a grain size of 40 to 15000 of an abrasive as defined in JIS R6001 on the side opposite to the transparent substrate film. It has the surface roughness of the number. The hard coat layer is composed of a cured product of a curable resin composition for a hard coat layer containing a photocurable binder component, and in addition to the binder component, the hard coat layer is provided with functionality such as hardness. Therefore, additives such as fine particles, antifouling agents and antistatic agents, and other components such as solvents may be contained.

  The film thickness of the hard coat layer is preferably 3 to 30 μm, and more preferably 5 to 20 μm. If it is thinner than 3 μm, the hardness may be insufficient, which is not preferable. If it exceeds 30 μm, curling and cracking may occur, which is not preferable.

  Hereinafter, other components such as a binder component contained in the curable resin composition for a hard coat layer that is cured to form a hard coat layer, fine particles, a solvent, and a polymerization initiator that are appropriately used as necessary will be described.

(Binder component)
The binder component includes a photocurable binder component having a photocurable group, and the photocurable group undergoes a crosslinking reaction by light, and a network structure is formed between the binder component and reactive inorganic fine particles described later, and is cured. To do. In addition, the binder component of the hard coat layer includes at least the photocurable binder component, and may include a thermosetting binder component in addition to the component as long as it does not depart from the spirit of the present invention.
The binder component contained in the curable resin composition for the hard coat layer is a cured product of the curable resin composition for the hard coat layer because part or all of the photocurable group is used for the crosslinking reaction and is cured. Strictly different from the binder component contained in a hard coat layer.

  In order to obtain sufficient crosslinkability, the binder component preferably has three or more photocurable groups per molecule. The photocurable group is 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 photocurable group may be the same as or different from the reactive functional group of the reactive inorganic fine particles described later as long as it has photocurability.

  The binder component is preferably a curable organic resin such as a monomer, oligomer, prepolymer, or polymer having a photocurable group, and preferably a translucent material that transmits light when formed into a coating film. An ionizing radiation curable resin, which is a resin curable by ionizing radiation represented by the above, and other known curable resins may be appropriately employed depending on the required performance. Examples of the ionizing radiation curable resin include acrylate-based, oxetane-based, and silicone-based resins.

  As the binder component, one or more binder components can be used.

Examples of the photocurable binder component include pentaerythritol triacrylate (PETA), dipentaerythritol hexaacrylate (DPHA), dipentaerythritol pentaacrylate (DPPA), trimethylolpropane triacrylate (TMPTA), and trimethylolpropane hexaacrylate. , 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 dipentaerythritol hexaacrylate are particularly preferable.

  Examples of the thermosetting binder component include melamine resin, epoxy resin, and polyimide.

(Other ingredients)
In addition to the above-mentioned components, fine particles, a solvent, a polymerization initiator, an antistatic agent, and an antiglare agent can be appropriately added to the curable resin composition for the hard coat layer. Furthermore, various additives, such as a reactive or non-reactive leveling agent and various sensitizers, may be mixed. In the case of containing an antistatic agent and / or an antiglare agent, antistatic properties and / or antiglare properties can be further imparted to the hard coat layer of the present invention.

(Fine particles)
By containing fine particles in the curable resin composition for hard coat layers, hardness can be imparted to the hard coat layer obtained by curing the curable resin composition for hard coat layers.

  The fine particles preferably have an average particle diameter of 1 to 100 nm from the viewpoint of transparency. If the average particle size is within this range, the fine particles may be aggregated particles, and if they are aggregated particles, the secondary particle size may be within the above range. By setting the average particle size of the fine particles to 1 to 100 nm, it is possible to impart hardness to the hard coat layer while ensuring transparency.

  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.

  The content of the fine particles in the curable resin composition for the hard coat layer may be appropriately adjusted in accordance with the binder component to be used, but is 30 to 70 with respect to the total solid content of the curable resin composition for the hard coat layer. The weight percentage is preferable from the viewpoint of improving hardness.

  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 within 1 to 100 nm, and the total weight percent of each particle relative to the total solid content of the hard coat layer curable resin composition is 30 to 70 weight percent. 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 order to impart antistatic properties and electrical 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.
The surface of the inorganic fine particles usually has groups that cannot exist in this form in the inorganic fine particles. These surface groups are usually relatively reactive functional groups. For example, in the case of metal oxides, for example, hydroxyl groups and oxy groups, for example in the case of metal sulfides, thiol groups and thio groups, or in the case of nitrides, for example, amino groups, amide groups and imides. Has a group.

  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 particles are reactive inorganic fine particles 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. Is preferred. 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.

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.

  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.

  Similarly to the binder component, the reactive inorganic fine particles are partly or wholly used for the crosslinking reaction and cured, so that the hard coat layer is a cured product of the curable resin composition for the hard coat layer. Strictly different from the reactive inorganic fine particles contained in.

  Examples of the reactive group functional group include those similar to the photocurable group described for the binder component, and the reactive functional group and the photocurable group may be the same or different.

  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.

(solvent)
Specific examples of the solvent include methanol, ethanol, isopropanol (IPA), butanol, isobutanol, methyl glycol, propylene glycol monomethyl ether (PGME), methyl glycol acetate, methyl cellosolve, ethyl cellosolve, butyl cellosolve and other alcohols; acetone, Ketones such as methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclohexanone, diacetone alcohol; esters such as methyl formate, methyl acetate, ethyl acetate, ethyl lactate, butyl acetate; nitromethane, N-methylpyrrolidone, N, Nitrogen-containing compounds such as N-dimethylformamide; ethers such as diisopropyl ether, tetrahydrofuran, dioxane, dioxolane; methylene chloride, chloroform, Li chloroethane, halogenated hydrocarbons such as tetrachloroethane; dimethylsulfoxide, other objects, such as propylene carbonate; or mixtures thereof.
MIBK, IPA, normal butanol and PGME are preferably used from the viewpoint of improving the hardness of the hard coat film.
Moreover, when a transparent base film is a TAC film, MEK, methyl acetate, ethyl acetate, cyclohexanone, and acetone are preferably used from the point which can improve adhesiveness.

(Polymerization initiator)
In the present invention, 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 are appropriately selected as necessary. May be used. 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 name Irgacure 651, Ciba Japan Co., Ltd.) 1-hydroxy-cyclohexyl-phenyl- T (trade name Irgacure 184, manufactured by Ciba Japan Co., Ltd.), 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.

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 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.

(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.

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 weight, preferably about 10 to 25 parts by weight with respect to 100 parts by weight of the curable resin composition for the hard coat layer.

3. Other Layers The hard coat film according to the present invention is basically composed of the transparent base film and the hard coat layer as described above. However, in the range not departing from the gist of the present invention, in addition to the hard coat layer, in addition to the hard coat layer, one or more other layers as described below are further added to the transparent substrate in consideration of the function or application as the hard coat film. You may provide between the film and a hard-coat layer, or the surface on the opposite side to the transparent base film of a hard-coat layer.
When the other layer is provided on the surface of the hard coat layer opposite to the transparent substrate film, the film thickness of the other layer is 1 μm or less in order to maintain the surface roughness of the hard coat layer surface. It is preferable.

3-1. Antistatic layer The antistatic layer comprises a cured product of a curable resin composition for an antistatic layer containing an antistatic agent and a curable resin.

  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.

3-2. Antiglare 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.

3-3. Antifouling 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.

3-4. Low Refractive Index Layer The low refractive index layer is a layer having a lower refractive index than the layer adjacent to the base film 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.

II. Manufacturing method of hard coat film The manufacturing method of the 1st hard coat film which concerns on this invention is a manufacturing method of the said hard coat film, Comprising: The particle size 40 of the abrasive | polishing material prescribed | regulated to one side of a transparent base film, or JISR6001 A process of applying a curable resin composition for a hard coat layer containing a photocurable binder component to the abrasive side of an abrasive sheet having ~ 15000 number to form a coating film,
While drying the coating film, or after drying, a polishing sheet having a grain size of No. 40 to 15000 of the abrasive specified in JIS R6001 on the side opposite to the transparent substrate film or polishing sheet of the coating film Bonding the surface on the abrasive side or one surface of the transparent substrate film to a three-layer structure of transparent substrate film / dried coating film / polishing sheet;
Irradiating the dried coating film with light from the transparent substrate film side after the three-layer structure formation, curing the dried coating film, and forming a hard coat layer;
Including a step of peeling the abrasive sheet from the hard coat layer and imparting a surface roughness of No. 40 to 15000 of the abrasive defined in JIS R6001 on the surface of the hard coat layer opposite to the transparent substrate film. It is characterized by that.

(Polished sheet)
In the present invention, the abrasive sheet is a group consisting of a polishing cloth of JIS R6251 having a surface roughness of a grain size of No. 40 to 15000 defined in JIS R6001, an abrasive paper of JIS R6252, and a water-resistant abrasive paper of JIS R6253. Means at least one selected from
As long as the abrasive has a particle size of 40 to 15000 as defined in JIS R6001, the material of the abrasive can be used without any particular limitation. Moreover, a particle size can be used 1 type or in combination of 2 or more types.

  Examples of the abrasive sheet include Plain back HV 30-800 Grit 80, 120, 180, 220, 320, 500, 800, 1000, 1200, Plain back HV 30-400 Grit 2400, 4000, PSA HV 30-800, manufactured by Struers. Grit 80, 120, 180, 220, 320, 500, 800, 1000, 1200, manufactured by Sankyori Chemical Co., Ltd., water resistant paper grain size 60, 80, 100, 120, 150, 180, 220, 240, 280, 320, 360, 400, 500, 600, 700, 800, 1000, 1200, 1500, 2000 and Noritake Coated Abrasive, AH-XMD or AH-XMS particle size 60, 80, 120, 150, 180, 200, 2 0, 320, 400, 600, 800, 1000, 1200, 1500, 2000, 3000, 6000, 9000, Sankyori Chemical Co., Ltd., 40, 120, 3000, 8000, 10,000, 15000, etc. Can be used.

  The curable resin composition for a hard coat layer is usually prepared by mixing and dispersing a fine particle, a polymerization initiator, and the like in a solvent according to a general preparation method in addition to the binder component described in the hard coat layer. The A paint shaker or a bead mill can be used for mixing and dispersing. Moreover, when the binder component has fluidity, a curable resin composition for a hard coat layer may be prepared without using a solvent.

The method for applying the curable resin composition for the hard coat layer is not particularly limited as long as the method can uniformly apply the curable composition for the hard coat layer to the surface of the transparent substrate film or the polishing sheet. Various methods such as a spin coating method, a dip method, a spray method, 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 pea coater method can be used.
The coating amount of the curable resin composition for the hard coat layer varies depending on the performance required of the obtained hard coat film, but the thickness of the hard coat layer after drying is in the range of 3 to 30 μm. It is preferable that it is within, and 3-40 g / m < ² > is preferable.

  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 of the curable resin composition for the hard coat layer, it is usually room temperature to 80 ° C., preferably 40 ° C. to 60 ° C., preferably 20 seconds to 3 minutes, preferably The drying process is performed in a time of about 30 seconds to 1 minute.

  Depending on the photocurable group of the binder component contained in the curable composition and the reactive functional group of the fine particles, the coating film obtained by applying and drying the curable resin composition for the hard coat layer is irradiated with light. By curing the dried coating film, a hard coat layer made of a cured product of the curable resin composition for hard coat layer is formed.

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.
When heating, it processes at the temperature of 40 to 120 degreeC normally. Moreover, you may react by leaving it to stand for 24 hours or more at room temperature (25 degreeC).

  When the curable resin composition for a hard coat layer contains a thermosetting binder component in addition to the photocurable binder component, the thermosetting binder component is cured by heating in addition to the light irradiation, and hard A coat layer may be obtained.

The manufacturing method of the 2nd hard coat film which concerns on this invention is a manufacturing method of the said hard coat film, Comprising: Of the abrasive sheet which has the particle size of No. 40-15000 of the abrasives prescribed | regulated to the one surface side of a base material or JISR6001 A process of applying a transfer mold curable resin composition on the abrasive side to form a coating film,
Then, after drying the coating film or after drying, the surface of the abrasive sheet side of the abrasive sheet or one surface of the substrate is bonded to the opposite side of the substrate or abrasive sheet of the coating film, A process of forming a three-layer structure of a substrate / dried coating film / abrasive sheet;
Next, the dried coating film after the formation of the three-layer structure is cured, the abrasive sheet is peeled off from the cured coating film, and the surface of the coating film opposite to the substrate is defined in JIS R6001. A surface roughness transfer layer having a surface roughness of the abrasive grain size 40 to 15000 defined in JIS R6001 is provided on the base material by providing the surface roughness of the abrasive grain size 40 to 15000. Obtaining a transfer mold,
Next, a step of applying a curable resin composition for a hard coat layer containing a photocurable binder component to one surface side of the transparent substrate film or the surface roughness transfer layer side of the transfer mold to form a coating film,
Next, while drying or drying the coating film of the curable resin composition for the hard coat layer, on the side of the coating film opposite to the transparent base film or the transfer mold, the transfer mold Bonding the surface on the surface roughness transfer layer side or one surface of the transparent substrate film to a transparent substrate film / dried coating film / transfer type three-layer structure;
Next, the step of irradiating the dried coating film from the transparent substrate film side after the formation of the three-layer structure including the transfer mold, curing the dried coating film, and forming a hard coat layer,
Subsequently, the transfer mold is peeled from the hard coat layer, and the surface roughness of the abrasive grain size of 40 to 15000 specified in JIS R6001 is applied to the surface of the hard coat layer opposite to the transparent substrate film. It is characterized by including.

  Considering the durability of the abrasive sheet, in the second method for producing a hard coat film, a transfer mold is first obtained instead of the hard coat film using the abrasive sheet, and a hard coat film is obtained from the transfer mold. The second method for producing a hard coat film has the advantage that it can be industrially mass-produced by using a transfer mold.

As the transfer type curable resin composition, the hard coat layer composition described in the hard coat layer can be used, and a known molding resin or the like may be used.
It is preferable to add a fluorine compound to the curable resin composition for transfer mold so that the abrasive sheet and the transfer mold can be easily peeled off and the transfer mold component is less likely to adhere to the surface of the abrasive sheet on the abrasive side. As the fluorine compound, for example, OPTOOL DSX manufactured by Daikin Industries, Ltd. can be used.

Further, for the purpose of improving the durability of the obtained transfer mold, it is preferable to form a nickel film having a thickness of 0.1 to 1 μm on the surface of the transfer mold. It is preferable to treat the nickel surface with a release agent because the durability can be further improved.
As nickel, conventionally known nickel may be used. For example, pure nickel manufactured by DOWA Metanics Co., Ltd. may be used.
A conventionally known release agent may be used as the mold release agent. For example, Fleas 50 manufactured by Neos Co., Ltd. can be used.

  As the transfer-type substrate, the transparent substrate film may be used, or a metal or glass other than the transparent substrate film may be used.

The third method for producing a hard coat film according to the present invention is a method for producing the above hard coat film, which is an abrasive sheet having a grain size of No. 40 to 15000 of the abrasive as defined in one side of the substrate or JIS R6001. A process of applying a transfer mold curable resin composition on the abrasive side to form a coating film,
Then, after drying the coating film or after drying, the surface of the abrasive sheet side of the abrasive sheet or one surface of the substrate is bonded to the opposite side of the substrate or abrasive sheet of the coating film, A process of forming a three-layer structure of a substrate / dried coating film / abrasive sheet;
Next, the dried coating film after forming the three-layer structure of the substrate / dried coating film / polishing sheet is cured, the polishing sheet is peeled off from the cured coating film, and the coating film substrate The surface roughness of the abrasive grain size No. 40-15000 specified in JIS R6001 is given to the surface opposite to that of the abrasive grain size No. 40-15000 No. 40-15000 specified in JIS R6001 on the base material. Obtaining a first generation transfer mold having a surface roughness transfer layer having a thickness;
Next, the same or different transfer as the transfer type curable resin composition on the one surface side of the second substrate or the surface roughness transfer layer side of the first generation transfer mold Applying the mold curable resin composition to form a coating film, while drying or drying the coating film, on the opposite side of the coating film from the second substrate or the first generation transfer mold The surface of the first generation transfer mold on the surface roughness transfer layer side or one surface of the second substrate, and the second substrate / dried coating / first generation transfer mold three-layer structure And curing the dried coating film after the formation of the three-layer structure including the first generation transfer mold, peeling the first generation transfer mold from the cured coating film, By giving the surface roughness of the grain size 40-15000 of the abrasive defined in JIS R6001 to the surface opposite to the material, the second A step of obtaining a second generation transfer mold comprising a surface roughness transfer layer having a surface roughness of a grain size of 40 to 15000 of an abrasive defined in JIS R6001 on a substrate;
If necessary, the same process as the second generation transfer mold is repeated to obtain the latest generation transfer mold,
Applying a curable resin composition for a hard coat layer containing a photocurable binder component to one surface side of the transparent substrate film or the surface roughness transfer layer side of the latest generation transfer type including the second generation, and a coating film The process of
Next, while drying or drying the coating film of the curable resin composition for the hard coat layer, the latest generation is provided on the opposite side of the coating to the transparent substrate film or the latest generation transfer mold. Bonding the surface of the transfer mold on the surface roughness transfer layer side or one surface of the transparent substrate film to form a three-layer structure of transparent substrate film / dried coating film / latest generation transfer type;
Next, the step of irradiating the dried coating film with light from the transparent substrate film side after the formation of the three-layer structure including the latest generation transfer mold, curing the dried coating film, and forming a hard coat layer,
Next, the latest generation transfer mold is peeled off from the hard coat layer, and the surface roughness of the abrasive grain size of 40 to 15000 specified in JIS R6001 is given to the surface of the hard coat layer opposite to the transparent substrate film. Including the step of:

Further, as shown in the third method for producing a hard coat film, the second generation or the second generation or later transfer mold is obtained from the first generation transfer mold, and the second generation or the second generation or later transfer mold is obtained. From this, a hard coat film can be obtained.
An even number transfer type such as the second generation or the fourth generation may be obtained, and a hard coat film may be obtained from the even number transfer type. In this case, it is possible to obtain a hard coat film in which the surface unevenness of the polishing sheet used first is reversed.
An odd number transfer type such as a third generation or a fifth generation may be obtained, and a hard coat film may be obtained from the odd number transfer type. In this case, it is possible to obtain a hard coat film in which the surface unevenness of the polishing sheet used first is transferred as it is.

FIG. 2 is a schematic view showing an example of a method for producing a first hard coat film according to the present invention.
First, as shown in FIG. 2A, a curable resin composition for a hard coat layer containing a photocurable binder component is applied to one side of the transparent substrate film 10 to form a coating film 30.
Subsequently, as shown in FIGS. 2B and 2C, after the coating film 30 is dried to obtain a dried coating film 40, the dried coating film 40 is placed on the side opposite to the transparent substrate film 10. The surface on the abrasive 60 side of the abrasive sheet 50 having an abrasive particle size of 40 to 15000 specified in JIS R6001 is bonded to form a three-layer structure of transparent substrate film / dried coating film / abrasive sheet.
Next, as shown in FIG. 2D, the coating film 40 dried from the transparent base film 10 side having the three-layer structure is irradiated with light 70 and cured to form the hard coat layer 20.
Next, as shown in FIG. 2 (e), the abrasive sheet 50 is peeled from the hard coat layer 20, and the surface roughness of the abrasive grain size No. 40-15000 specified in JIS R6001 is given to the surface of the hard coat layer. .

Drawing 3 is a mimetic diagram showing other examples of the manufacturing method of the 1st hard coat film concerning the present invention.
First, as shown in FIG. 3A, a curable resin composition for a hard coat layer containing a photocurable binder component is applied to the abrasive 60 side of the polishing sheet 50 to form a coating film 30.
Subsequently, as shown in FIGS. 3 (b) and 3 (c), while drying the coating film 30, one surface of the transparent substrate film 10 is bonded to the side opposite to the polishing sheet 50 of the coating film 80 being dried, A three-layer structure of abrasive sheet / dried coating film / transparent substrate film is formed.
Next, as shown in FIG. 3D, the coating film 40 dried from the transparent base film 10 side having the three-layer structure is irradiated with light 70 and cured to form the hard coat layer 20.
Next, as shown in FIG. 3 (e), the abrasive sheet 50 is peeled from the hard coat layer 20, and the surface roughness of the abrasive grain size 40-15000 specified in JIS R6001 is given to the surface of the hard coat layer. .

4A and 4B are schematic views showing an example of a method for producing a second hard coat film according to the present invention.
First, as shown in FIG. 4A (a), the transfer type curable resin composition is applied to one side of the transparent substrate 11 to form a coating film 90.
Subsequently, as shown in FIGS. 4A and 4C, the coating film 90 is dried, and the surface of the polishing sheet 50 on the side of the abrasive 60 on the side opposite to the transparent substrate 11 of the dried coating film 100. To form a three-layer structure of transparent substrate / dried coating film / polishing sheet.
Next, as shown in FIG. 4A (d), the coating film 100 dried from the transparent substrate 11 side having a three-layer structure is irradiated with light 70 to obtain a cured coating film 110.
Next, as shown in FIG. 4A (e), the abrasive sheet 50 is peeled off from the cured coating film 110, and the surface of the cured coating film 110 has a grain size of No. 40 to 15000 as defined in JIS R6001. A transfer mold 130 is obtained in which a roughness is applied and a surface roughness transfer layer 120 having a surface roughness of the abrasive grain size of No. 40 to 15000 as defined in JIS R6001 is provided on the substrate 11.
Next, as shown in FIG. 4B (f), a hard coat layer curable resin composition containing a photocurable binder component is applied to the surface roughness transfer layer 120 side of the transfer mold 130 to form a coating film 30. .
Subsequently, as shown in FIG. 4B (g), after the coating film 30 is dried to obtain a dried coating film 40, the transparent substrate film 10 is formed on the opposite side of the dried coating film 40 from the transparent substrate 11. Are bonded together to form a transparent base film / dried coating film / transfer type three-layer structure.
Next, as shown in FIG. 4B (h), the coating 40 dried from the transparent base film 10 side having a three-layer structure is irradiated with light 70 and cured to form the hard coat layer 20.
Next, as shown in FIG. 4B (i), the transfer mold 130 is peeled from the hard coat layer 20, and the surface roughness of the abrasive grain size No. 40 to 15000 specified in JIS R6001 is given to the surface of the hard coat layer. .

5A to 5C are schematic views showing an example of a method for producing a third hard coat film according to the present invention.
First, as shown in FIG. 5A (a), a transfer type curable resin composition is applied to one surface side of the transparent substrate 11 to form a coating film 90.
Subsequently, as shown in FIGS. 5A (b) and 5 (c), the coating film 90 is dried, and the surface on the abrasive 60 side of the polishing sheet 50 on the side opposite to the transparent substrate 11 of the dried coating film 100. To form a three-layer structure of transparent substrate / dried coating film / polishing sheet.
Next, as shown in FIG. 5A (d), the coating film 100 dried from the transparent base material 11 side having the three-layer structure is irradiated with light 70 to obtain a cured coating film 110.
Next, as shown in FIG. 5A (e), the abrasive sheet 50 is peeled off from the cured coating film 110, and the surface of the abrasive particle size 40-15000 defined in JIS R6001 is applied to the surface of the cured coating film 110. A first-generation transfer mold 130 is obtained in which a roughness is imparted and a surface roughness transfer layer 120 having a surface roughness of the abrasive grain size No. 40 to 15000 defined in JIS R6001 is provided on the substrate 11.
Next, as shown in FIG. 5B (f), the transfer mold curable resin composition is applied to the surface roughness transfer layer 120 side of the transfer mold 130 to form a coating film 91.
Subsequently, as shown in FIG. 5B (g), after the coating film 91 is dried to obtain a dried coating film 101, one surface of the transparent substrate 12 is placed on the side of the dried coating film 101 opposite to the transfer mold 130. The sides are bonded to form a three-layer structure of transparent substrate / dried coating / first generation transfer type.
Next, as shown in FIG. 5B (h), the coating film 101 dried from the transparent base material 11 side having a three-layer structure is irradiated with light 70 to be cured, thereby obtaining a cured coating film 111.
Next, as shown in FIG. 5B (i), the transfer mold 130 is peeled from the cured coating film 111, and the surface of the abrasive particle size of 40 to 15000 specified in JIS R6001 is applied to the surface of the cured coating film 111. A second generation transfer mold 131 is obtained in which a roughness is applied and a surface roughness transfer layer 121 having a surface roughness of the abrasive grain size No. 40 to 15000 defined in JIS R6001 is provided on the substrate 12.
Next, as shown in FIG. 5C (j), a curable resin composition for a hard coat layer containing a photocurable binder component is applied to the surface roughness transfer layer 121 side of the transfer mold 131 to form a coating film 30. .
Subsequently, as shown in FIG. 5C (k), after the coating film 30 is dried to obtain a dried coating film 40, the transparent substrate film 10 is formed on the opposite side of the dried coating film 40 from the transparent substrate 12. The three-sided structure of transparent substrate film / dried coating film / second generation transfer type is formed by bonding one surface side of each other.
Next, as shown in FIG. 5C (l), the coating film 40 dried from the transparent substrate film 10 side having a three-layer structure is irradiated with light 70 and cured to form the hard coat layer 20.
Next, as shown in FIG. 5C (m), the second generation transfer mold 131 is peeled from the hard coat layer 20, and the surface roughness of the abrasive grain size No. 40 to 15000 specified in JIS R6001 on the surface of the hard coat layer. Is granted.

  In the third method for producing a hard coat film, the steps of FIGS. 5B (f) to (i) may be repeated odd times or even times.

Moreover, the manufacturing method of the said hard coat film contains not only the batch system which manufactures the hard coat film of 1 sheet of sheets but the continuous system which manufactures a continuous strip-shaped hard coat film.
When producing a hard coat film by a continuous method, for example, an abrasive sheet is wound around a roller so that the abrasive side becomes the surface. By using a conveyor or the like, the transparent substrate film flows in a continuous band shape. Moreover, the curable resin composition for hard coat layers is continuously supplied and formed on the transparent substrate film. The dried film is dried or dried, and then the roller around which the abrasive sheet is wound is brought into contact with the film surface to form a three-layer structure of transparent substrate film / dried film / abrasive sheet. Next, light irradiation is performed from the transparent substrate film side, and the dried film is cured to form a hard coat layer. When the transparent base film and the hard coat layer formed on the one side flow, the abrasive sheet wrapped around the roller is peeled off, and the surface is given a surface roughness of abrasive grain size 40-15000 specified in JIS R6001. A hard coat film having the hard coat layer thus obtained is obtained.
In addition to the above, known methods can be applied as long as the surface shape of the polishing sheet can be transferred to the hard coat layer.
When a hard coat film is produced by a continuous method, it can be produced more efficiently than when produced by a batch method, and the production cost per hard coat film can be reduced, which is preferable.

FIG. 6 is a schematic view showing an example of a method for producing a hard coat film by the above-described continuous process.
The hard coat layer curable resin composition 150 is discharged and applied to the continuous belt-shaped transparent substrate film 10 from the nozzle 140, and is formed into a coating film 30 by using a roller 160. The coating film 30 is dried using a drying unit 170. The dried film 40 is dried, and the dried film 40 is brought into contact with a roller 180 around which the abrasive sheet 50 is wound to form a three-layer structure of transparent substrate film / dried coating film / abrasive sheet. The hard coat layer 20 is hardened by the roller 180, and the roller 180 around which the polishing sheet 50 is wound is peeled from the hard coat layer 20, and the surface of the hard coat layer has a grain size of No. 40 to 15000 as defined in JIS R6001. A hard coat film 1 is obtained.

What is necessary is just to adjust suitably the conditions of application | coating of the curable resin composition for hard-coat layers, drying, and light irradiation based on the said batch system.
The shape of the roller is not particularly limited and is not limited to a cylindrical shape, but can be appropriately set so that the contact area with a coating film or a dried film is widened, and a roller having an elliptical, rectangular or square cross section is used. May be.

Hereinafter, the present invention will be described more specifically with reference to examples. These descriptions do not limit the present invention.
As a photocurable binder component, pentaerythritol triacrylate, Nippon Kayaku Co., Ltd. product name PET30 was used.
As photopolymerization initiators, 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by Ciba Japan Co., Ltd., product name: Irgacure 184), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Ciba Japan Co., Ltd. product name: Irgacure 819) was used.
As a fluorine compound, Daikin Industries, Ltd. product name: OPTOOL DSX was used.
As nickel, DOWA Metanics Co., Ltd., product name: pure nickel was used.
Methyl ethyl ketone was used as the solvent.
As the transparent substrate film, a TAC film (thickness 40 μm, triacetyl cellulose resin film, product name: KC4UY, manufactured by Konica Corporation) was used.
As the abrasive sheet, # 120, 240, 1200, 4000, manufactured by Struers, Silicon Carbide Pattern FEPA P, and No. 120, 3000, 8000, 10000, 15000, manufactured by Sankyo Rikagaku Co., Ltd. were used. (# Is the particle size of the abrasive specified in JIS R6001).
As the ultraviolet irradiation apparatus, a conveyor type ultraviolet irradiation apparatus manufactured by Fusion was used.
As an electron beam irradiation device, EC250 / 15 / 180L manufactured by Iwasaki Electric Co., Ltd. was used.
As a pencil hardness tester, a pencil scratch coating film hardness tester manufactured by Toyo Seiki Seisakusho Co., Ltd. was used.
Mitsubishi Pencil Co., Ltd. Uni, hardness 3H was used as a recording pencil.
Mono PE07 manufactured by Dragonfly Pencil Co., Ltd. was used as an eraser.
Abbreviations for each compound are as follows.
PETA: Pentaerythritol triacrylate MEK: Methyl ethyl ketone TAC: Triacetyl cellulose Hereinafter, “part” means “part by weight” unless otherwise specified.

(Preparation of curable resin composition for hard coat layer)
Components of the composition shown below were blended to prepare curable resin compositions 1 to 3 for hard coat layers, respectively.

(Curable resin composition for hard coat layer 1)
PET30: 96 parts Irgacure 184: 2 parts Irgacure 819: 2 parts MEK: 100 parts

(Curable resin composition for hard coat layer 2)
PET30: 96 parts Irgacure 184: 2 parts Irgacure 819: 2 parts Optool DSX: 5 parts MEK: 100 parts

(Curable resin composition 3 for hard coat layer)
PET30: 96 parts MEK: 100 parts

Example 1
The hard coat layer curable resin composition 1 was applied to the surface of the polishing sheet (particle size 120) on the abrasive side, and then dried at a temperature of 70 ° C. for 60 seconds to evaporate the solvent in the coating film. . Next, a TAC film was bonded to the surface of the dried coating film to obtain a three-layer structure of TAC film / dried coating film / polishing sheet.
Subsequently, with the TAC film as the upper surface, ultraviolet rays were irradiated with an ultraviolet irradiation device so that the integrated light amount was 50 mJ / cm ² , the coating film was cured, and a hard coat layer was formed.
Next, the abrasive sheet was peeled from the formed hard coat layer to obtain a hard coat film having a surface roughness of the abrasive grain size No. 120 specified in JIS R6001 on the surface of the hard coat layer.

(Examples 2 to 4)
In Example 1, except that the abrasive sheet (No. 120) was replaced with an abrasive sheet having the particle size shown in Table 1, the surface roughness of the abrasive specified in JIS R6001 was imparted to the hard coat layer surface. The hard coat film of Examples 2-4 was obtained.

(Examples 5 to 8)
In Example 1, the abrasive sheet (No. 120) was replaced with an abrasive sheet having the particle size shown in Table 1, and the hard coat layer curable resin composition 2 was used instead of the hard coat layer curable resin composition 2. The hard coat film of Examples 5-8 which gave the surface roughness of the abrasive | polishing material prescribed | regulated to JISR6001 to the hard-coat layer surface similarly except having used it was obtained.

Example 9
In Example 3, instead of the curable resin composition 1 for hard coat layer, the abrasive material specified in JIS R6001 on the surface of the hard coat layer was used in the same manner except that the curable resin composition 2 for hard coat layer was used. A hard coat film having a surface roughness of particle size 1200 was obtained.

(Example 10)
1 μm of nickel was formed on the surface of the hard coat film obtained in Example 9, and the hard coat film was wound around a roller so that the TAC film was inside and the hard coat layer was outside (surface side).
The continuous belt-like TAC film continuously passes at a speed of 10 m / min, and the continuous belt-like TAC film is continuously supplied with the curable resin composition 1 for hard coat layer, and is formed with a roller. A roller on which a hard coat film is wound on a film, and a hard coat film is wound by contacting the roller with a hard coat film and further irradiating with an ultraviolet ray irradiation device so that the integrated light quantity is 50 mJ / cm ^2. The hard coat film wound around the roller by rotating the TAC film and the hard coat layer is peeled off, and the hard coat layer has a surface roughness of the abrasive grain size No. 1200 defined in JIS R6001 on the hard coat layer surface. A film was obtained.

(Example 11)
In Example 10, curable resin composition 3 for hard coat layer was used instead of curable resin composition 1 for hard coat layer, and electron beam irradiation (3 mega rads, 166 kV, 1.0 mA) was used instead of ultraviolet irradiation. In the same manner except that the conveying speed was set to 5 m / min, a continuous belt-like hard coat film having a surface roughness of the abrasive grain size No. 1200 defined in JIS R6001 was obtained on the hard coat layer surface.

(Comparative Example 1)
In Example 1, a hard coat film in which a smooth shape of the glass plate surface was imparted to the surface of the hard coat layer was obtained in the same manner except that a glass plate having a surface roughness Ra of 0.2 nm was used instead of the polishing sheet.

(Evaluation of hard coat film)
About the produced hard coat films of Examples 1 to 11 and Comparative Example 1, pencil hardness, light transmittance, steel wool resistance, and recording and erasing with a pencil were evaluated as follows. The results are shown in Table 1.
(1) Pencil hardness A pencil hardness test with a load of 500 g as defined in JISK5600-5-4 (1999) was performed, and the pencil hardness with the highest hardness that was not damaged was measured.
(2) Light transmission The hard coat film was placed on the newspaper with the TAC film side down and the newspaper, the TAC film and the hard coat layer were placed from the lower side, and in this state, the following criteria were evaluated.
A: Vividly readable characters B: Slightly illegible but readable characters (3) Steel wool resistance The resulting hard coat film uses # 0000 steel wool and 10 reciprocations at a speed of 100 mm / sec while applying a load of 200 g The presence or absence of scratches was confirmed visually. The evaluation criteria were as follows.
○: No scratches are observed ×: Scratches are observed (4) Recording and erasing with a pencil Using a pencil with a hardness of 3H, writing is performed on the surface of the hard coat layer and recording is possible. It was investigated whether it could be erased with an eraser.
○: Recording and erasing were possible ×: Recording and erasing were not possible

From Table 1, Example 8 which gave the surface roughness of the abrasive | polishing material 15000 prescribed | regulated to JISR6001 using an abrasive sheet was set to 4H in the pencil hardness test, and other Examples 1-7, 9- No. 11 was evaluated with a pencil hardness test of 5H, and an excellent pencil hardness was obtained.
Regarding the light transmittance, Examples 1 and 2 having a small number of abrasive grain sizes were unclear but had light-transmitting properties, and Examples 3 to 11 were clearly readable. It had good light transmittance.
Regarding steel wool resistance, Examples 1 to 3 having a small number of abrasive grains had no scratches, and had good steel wool resistance.
In Examples 1 to 11, recording and erasing with a pencil were possible.

  In Comparative Example 1 in which a hard coat film was produced using a glass plate having a surface roughness Ra of 0.2 nm instead of the abrasive sheet, the light transmission was good, but the pencil hardness was as low as 2H, and the steel wool resistance In the evaluation of sex, scratches were recognized, and it was impossible to record and erase with a pencil.

FIG. 1 is a cross-sectional view schematically showing an example of a hard coat film according to the present invention. Drawing 2 is a figure showing typically an example of the manufacturing method of the 1st hard coat film concerning the present invention. FIG. 3 is a view schematically showing another example of the method for producing the first hard coat film according to the present invention. FIG. 4A is a diagram schematically showing an example of a method for producing a second hard coat film according to the present invention. Drawing 4B is a figure showing typically an example of the manufacturing method of the 2nd hard coat film concerning the present invention. FIG. 5A is a diagram schematically showing an example of a method for producing a third hard coat film according to the present invention. FIG. 5B is a diagram schematically showing an example of a method for producing a third hard coat film according to the present invention. FIG. 5C is a diagram schematically showing an example of a method for producing a third hard coat film according to the present invention. FIG. 6 is a view schematically showing another example of the method for producing the first hard coat film according to the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Hard coat film 10 Transparent base film 20 Hard coat layer 30 Coating film 40 Dried coating film 50 Polishing sheet 60 Abrasive material 70 Light irradiation 80 Coating film 90, 91 Coating film 100, 101 Dried coating film 110, 111 Cured coating film 120, 121 Surface roughness transfer layer 130, 131 Transfer mold 140 Nozzle 150 Hard coat layer curable resin composition 160 Roller or cylinder 170 Drying means 180 Roller

Claims (7)

A hard coat film provided with a hard coat layer on one side of the transparent substrate film,
The hard coat film is characterized in that the surface of the hard coat layer opposite to the transparent base film has a surface roughness of the abrasive grain size of 40 to 15000 as defined in JIS R6001.   The hard coat film according to claim 1, wherein the hardness of the hard coat layer is 3H or more in a pencil hardness test (500 g load) defined in JIS K5600-5-4 (1999). A method for producing a hard coat film according to claim 1 or 2,
The hard coat layer-containing curable resin composition containing a photo-curable binder component is applied to one side of the transparent base film or the abrasive side of the abrasive sheet having a grain size of 40 to 15000 as defined in JIS R6001. , The process of coating
While drying the coating film, or after drying, a polishing sheet having a grain size of No. 40 to 15000 of the abrasive specified in JIS R6001 on the side opposite to the transparent substrate film or polishing sheet of the coating film Bonding the surface on the abrasive side or one surface of the transparent substrate film to a three-layer structure of transparent substrate film / dried coating film / polishing sheet;
Irradiating the dried coating film with light from the transparent substrate film side after the three-layer structure formation, curing the dried coating film, and forming a hard coat layer;
Including a step of peeling the abrasive sheet from the hard coat layer and imparting a surface roughness of No. 40 to 15000 of the abrasive defined in JIS R6001 on the surface of the hard coat layer opposite to the transparent substrate film. A method for producing a hard coat film, comprising: A method for producing a hard coat film according to claim 1 or 2,
A step of applying a curable resin composition for a transfer mold on one side of a substrate or an abrasive side of an abrasive sheet having an abrasive grain size of 40 to 15000 as defined in JIS R6001 to form a coating film;
Then, after drying the coating film or after drying, the surface of the abrasive sheet side of the abrasive sheet or one surface of the substrate is bonded to the opposite side of the substrate or abrasive sheet of the coating film, A process of forming a three-layer structure of a substrate / dried coating film / abrasive sheet;
Next, the dried coating film after the formation of the three-layer structure is cured, the abrasive sheet is peeled off from the cured coating film, and the surface of the coating film opposite to the substrate is defined in JIS R6001. A surface roughness transfer layer having a surface roughness of the abrasive grain size 40 to 15000 defined in JIS R6001 is provided on the base material by providing the surface roughness of the abrasive grain size 40 to 15000. Obtaining a transfer mold,
Next, a step of applying a curable resin composition for a hard coat layer containing a photocurable binder component to one surface side of the transparent substrate film or the surface roughness transfer layer side of the transfer mold to form a coating film,
Next, while drying or drying the coating film of the curable resin composition for the hard coat layer, on the side of the coating film opposite to the transparent base film or the transfer mold, the transfer mold Bonding the surface on the surface roughness transfer layer side or one surface of the transparent substrate film to a transparent substrate film / dried coating film / transfer type three-layer structure;
Next, the step of irradiating the dried coating film from the transparent substrate film side after the formation of the three-layer structure including the transfer mold, curing the dried coating film, and forming a hard coat layer,
Subsequently, the transfer mold is peeled from the hard coat layer, and the surface roughness of the abrasive grain size of 40 to 15000 specified in JIS R6001 is applied to the surface of the hard coat layer opposite to the transparent substrate film. A method for producing a hard coat film, comprising: A method for producing a hard coat film according to claim 1 or 2,
A step of applying a curable resin composition for a transfer mold on one side of a substrate or an abrasive side of an abrasive sheet having an abrasive grain size of 40 to 15000 as defined in JIS R6001 to form a coating film;
Then, after drying the coating film or after drying, the surface of the abrasive sheet side of the abrasive sheet or one surface of the substrate is bonded to the opposite side of the substrate or abrasive sheet of the coating film, A process of forming a three-layer structure of a substrate / dried coating film / abrasive sheet;
Next, the dried coating film after forming the three-layer structure of the substrate / dried coating film / polishing sheet is cured, the polishing sheet is peeled off from the cured coating film, and the coating film substrate The surface roughness of the abrasive grain size No. 40-15000 specified in JIS R6001 is given to the surface opposite to that of the abrasive grain size No. 40-15000 No. 40-15000 specified in JIS R6001 on the base material. Obtaining a first generation transfer mold having a surface roughness transfer layer having a thickness;
Next, the same or different transfer as the transfer type curable resin composition on the one surface side of the second substrate or the surface roughness transfer layer side of the first generation transfer mold Applying the mold curable resin composition to form a coating film, while drying or drying the coating film, on the opposite side of the coating film from the second substrate or the first generation transfer mold The surface of the first generation transfer mold on the surface roughness transfer layer side or one surface of the second substrate, and the second substrate / dried coating / first generation transfer mold three-layer structure And curing the dried coating film after the formation of the three-layer structure including the first generation transfer mold, peeling the first generation transfer mold from the cured coating film, By giving the surface roughness of the grain size 40-15000 of the abrasive defined in JIS R6001 to the surface opposite to the material, the second A step of obtaining a second generation transfer mold comprising a surface roughness transfer layer having a surface roughness of a grain size of 40 to 15000 of an abrasive defined in JIS R6001 on a substrate;
If necessary, the same process as the second generation transfer mold is repeated to obtain the latest generation transfer mold,
Applying a curable resin composition for a hard coat layer containing a photocurable binder component to one surface side of the transparent substrate film or the surface roughness transfer layer side of the latest generation transfer type including the second generation, and a coating film The process of
Next, while drying or drying the coating film of the curable resin composition for the hard coat layer, the latest generation is provided on the opposite side of the coating to the transparent substrate film or the latest generation transfer mold. Bonding the surface of the transfer mold on the surface roughness transfer layer side or one surface of the transparent substrate film to form a three-layer structure of transparent substrate film / dried coating film / latest generation transfer type;
Next, the step of irradiating the dried coating film with light from the transparent substrate film side after the formation of the three-layer structure including the latest generation transfer mold, curing the dried coating film, and forming a hard coat layer,
Next, the latest generation transfer mold is peeled off from the hard coat layer, and the surface roughness of the abrasive grain size of 40 to 15000 specified in JIS R6001 is given to the surface of the hard coat layer opposite to the transparent substrate film. The manufacturing method of the hard coat film characterized by including the process to do. As the latest generation transfer type including the second generation, obtain an odd number generation transfer type,
Next, the method for producing a hard coat film according to claim 5, wherein a hard coat film is obtained using the odd number generation transfer mold. As the latest generation transfer type including the second generation, obtain even-number generation transfer type,
Then, a hard coat film is obtained using the said even number generation transfer type | mold, The manufacturing method of the hard coat film of Claim 5 characterized by the above-mentioned.

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