JP5468765B2 - Anti-glare hard coat film - Google Patents

Description

  The present invention relates to an antiglare hard coat film. In particular, the present invention relates to an antiglare hard coat film that can be suitably used for flat panel displays such as liquid crystal displays, plasma displays, organic EL displays, field emission displays, and flexible displays such as electronic paper.

  In displays such as a plasma display panel (PDP) and a liquid crystal display (LCD), an antireflection film and an antiglare film are used in order to make it easier to see an image displayed on the screen. The antireflection film is, for example, as disclosed in Patent Document 1, which reduces the intensity of reflected light by laminating layers having different refractive indexes. Thereby, even if light from an external light source such as sunlight or fluorescent light enters the screen, it is possible to prevent the screen from being difficult to see due to the reflected light. Moreover, an anti-glare film is what diffuses incident light in the surface or the inside of an anti-glare film, for example in patent document 2. FIG. Thereby, it is possible to suppress the screen from being glaring and dazzled by the light from the external light source as described above.

  In recent years, such an antiglare film is generally an antiglare hard coat film imparted with an antiglare property to the hard coat film in order to shorten the manufacturing process and reduce the cost. It is disclosed in Patent Documents 3 to 5. In addition, black reproducibility of video has been regarded as important. For example, Patent Documents 6 and 7 have examined improvement of black reproducibility.

JP-A-10-728 JP 2002-182015 A JP 2002-36452 A JP 2003-266582 A JP 2006-137835 A JP 2007-219485 A JP 2007-233374 A

  The antiglare film as described above has been frequently used for LCDs until now, but it has been rarely used for PDP in practice. Generally, since PDP is excellent in black reproducibility, it is used for applications that require such black reproducibility. However, when an anti-glare film that causes light diffusion is used in a PDP, the black reproducibility of the PDP becomes low and cannot be used for applications that require more black reproducibility. Therefore, an antireflection film has been preferably used for PDP, not an antiglare film.

  However, in recent years, it has been required to use an antiglare film having a lower cost in the PDP in order to reduce the cost. Under such circumstances, when an antiglare film as disclosed in Patent Documents 2 to 5 is used for PDP, there is a problem that black reproducibility of PDP becomes insufficient. Further, the antiglare hard coat films disclosed in Patent Documents 6 and 7 also have black reproducibility to some extent, but do not satisfy the level of black reproducibility required for PDPs in recent years.

  An object of the present invention is to provide an antiglare hard coat film excellent in surface hardness, transparency, antiglare property, and black reproducibility. Another object of the present invention is to provide an antiglare hard coat film having both transparency and antiglare properties recently required for PDP, and further having black reproducibility recently required for PDP. There is.

As a result of intensive studies, the present inventors have determined that the total haze and glossiness of the surface are in a specific numerical range in an antiglare hard coat film having an antiglare hard coat layer containing a binder component and organic particles as constituent components. As a result, the inventors have found that the above object can be achieved, and have reached the present invention. That is, the present invention
(1) An antiglare hard coat film having an antiglare hard coat layer containing a binder component and organic particles as constituent components on at least one surface of a transparent resin substrate, wherein the total haze (Hz) is 0. 1% or more and 4.0% or less, 60 degree gloss is 80 or more and less than 120,
The antiglare hard coat layer contains a binder resin and a binder component containing 10% by mass or more and 70% by mass or less of an inorganic filler as a constituent component with respect to the mass of the binder component, and the mass of the binder component is 0.00. A coating liquid obtained by further adding 0.5% by mass or more and 5.0% by mass or less of inorganic fine particles to a solution containing 1% by mass or more and 5.0% by mass or less of organic particles to the mass of the binder component. It is an antiglare hard coat layer formed by curing, and is an antiglare hard coat film having a refractive index difference from the binder resin of less than 0.07 for inorganic fillers and 0.08 or more for inorganic fine particles. .

Furthermore, the present invention provides
(2) and this is the internal haze of the antiglare hard coat layer (Hihc) is 0.5 or less,
(4) The organic particles have a refractive index difference from the binder component of less than 0.03 and an average particle size of 1 μm or more and 10 μm or less.
(5) The film thickness of the antiglare hard coat layer is in the range of 50% to 200% of the average particle diameter of the organic particles,
(6) The half width of the surface protrusion height distribution on the surface of the antiglare hard coat layer is in the range of 0.2 μm or more and 0.7 μm or less,
(7) The centerline average surface roughness (Ra) on the surface of the antiglare hard coat layer is 0.01 μm or more and 0.25 μm or less, and further, by including at least any one aspect, it is further excellent. An antiglare hard coat film can be obtained.

  ADVANTAGE OF THE INVENTION According to this invention, the anti-glare hard coat film excellent in surface hardness, transparency, anti-glare property, and black reproducibility can be provided. Moreover, since the anti-glare hard coat film of this invention is equipped with high transparency and high anti-glare property simultaneously, it can be used especially suitably for PDP. In particular, since black reproducibility is excellent, black reproducibility recently required for PDP can be achieved even if it is used for PDP.

[Anti-glare hard coat film]
The antiglare hard coat film of the present invention has an antiglare hard coat layer described later on at least one surface of a transparent resin substrate described later.
The anti-glare hard coat film of the present invention has a total haze (Hz) of 0.1% to 4.0%. By setting the total haze (Hz) to the above numerical range, the transparency is excellent and the image visibility is excellent on the display screen. Moreover, it is excellent in black reproducibility. When the total haze (Hz) is too high, the transparency is inferior, and the visibility of the image is inferior on the display screen. Moreover, it is inferior to black reproducibility. From such a viewpoint, the upper limit of the total haze (Hz) is preferably 3.5% or less, more preferably 3.0% or less, and particularly preferably 2.5% or less. On the other hand, the total haze (Hz) is preferably low, but if it is too low, the antiglare property tends to be inferior. From such a viewpoint, the substantial lower limit is preferably 0.5% or more, more preferably 1.7% or more, and particularly preferably 2.1% or more.

  The antiglare hard coat film of the present invention preferably has an internal haze (Hi) of 1.5% or less. By setting the internal haze (Hi) of the antiglare hard coat film within the above numerical range, the antiglare property can be increased while maintaining the transparency, and the balance between transparency and antiglare property is more excellent. Can be. Moreover, it is excellent in black reproducibility. Furthermore, black reproducibility can be made more excellent while maintaining antiglare properties. When the internal haze (Hi) of the antiglare hard coat film is too high, it tends to be difficult to increase the antiglare property while maintaining the total haze (Hz). Further, the black reproducibility tends to be inferior. From such a viewpoint, the upper limit of the internal haze (Hi) of the antiglare hard coat film is more preferably 1.4% or less, and particularly preferably 1.3% or less. On the other hand, the lower the internal haze (Hi) of the antiglare hard coat film, the better, and the lower limit is particularly preferably 0% or more.

  The antiglare hard coat film of the present invention preferably has a ratio (Hi / Hz) of internal haze (Hi) to total haze (Hz) of 0.75 or less. By setting the ratio (Hi / Hz) within the above numerical range, the balance between transparency and antiglare property can be further improved. Moreover, it is excellent in black reproducibility. From such a viewpoint, the ratio (Hi / Hz) is more preferably not less than 0.55 and not more than 0.74, and particularly preferably not less than 0.59 and not more than 0.72.

  The antiglare hard coat film of the present invention has a 60 degree glossiness of 80 or more and less than 120 on the surface of the antiglare hard coat layer. By setting the 60-degree glossiness within the above numerical range, not only the antiglare property is excellent, but also the black reproducibility is excellent. When the 60 degree glossiness is too high, the antiglare property and the black reproducibility tend to be inferior. From such a viewpoint, the upper limit of the 60 degree glossiness is preferably 119 or less, more preferably 117 or less. On the other hand, if it is too low, the black reproducibility tends to be inferior. From such a viewpoint, the lower limit of the 60 ° glossiness is preferably 90 or more, more preferably 100 or more, and particularly preferably 108 or more.

  In the present invention, since the total haze (Hz) and the 60 ° glossiness are simultaneously in the above numerical range, the transparency, the antiglare property, and the black reproducibility are improved at the same time. The transparency, antiglare property and black reproducibility can be achieved at the same time.

  In order to achieve the total haze (Hz), internal haze (Hi), and 60 degree gloss as described above, the refractive index of the binder component in the antiglare hard coat layer, the refractive index of organic particles and inorganic fine particles, This can be achieved by appropriately adjusting the average particle diameter, the content, the refractive index of the binder resin and the inorganic filler, the film thickness of the antiglare hard coat layer, and the haze and thickness of the transparent resin substrate. For example, reducing the difference between the refractive index of the binder component and the refractive index of organic particles and inorganic fine particles, reducing the average particle size of organic particles and inorganic fine particles, or reducing the content of organic particles and inorganic fine particles Then, the total haze (Hz) and the internal haze (Hi) tend to be low, and the 60 degree gloss tends to be high.

[Anti-glare hard coat layer]
The antiglare hard coat layer in the invention contains a binder component described later and organic particles as constituent components.
The anti-glare hard coat layer in the present invention preferably has a total haze (Hzhc) of 0.1% to 4.0%. By setting the total haze (Hzhc) of the antiglare hard coat layer in the above numerical range, the transparency and black color reproducibility of the antiglare hard coat film are excellent. When the total haze (Hzhc) of the antiglare hard coat layer is too high, transparency and black reproducibility tend to be inferior. From such a viewpoint, the upper limit of the total haze (Hzhc) of the antiglare hard coat layer is more preferably 3.0% or less, still more preferably 2.5% or less, and particularly preferably 2.0% or less. . On the other hand, the total haze (Hzhc) of the antiglare hard coat layer is preferably low, but if it is too low, the antiglare property tends to be inferior. From such a viewpoint, the substantial lower limit is more preferably 0.2% or more, further preferably 0.5% or more, and particularly preferably 1.0% or more.

  The antiglare hard coat layer in the present invention preferably has an internal haze (Hihc) of 0.5% or less. By setting the internal haze (Hihc) of the antiglare hard coat layer within the above numerical range, the surface haze (Hshc) can be increased while maintaining the total haze (Hzhc), that is, the antiglare property is increased. And the balance between transparency and antiglare property can be further improved. Moreover, it is excellent in black reproducibility. Furthermore, black reproducibility can be made more excellent while maintaining antiglare properties. If the internal haze (Hihc) of the antiglare hard coat layer is too high, the surface haze (Hshc) cannot be increased sufficiently to maintain the total haze (Hzhc), and the antiglare property is increased. Tend to be difficult to do. Further, the black reproducibility tends to be inferior. From such a viewpoint, the upper limit of the internal haze (Hihc) of the antiglare hard coat layer is more preferably 0.4% or less, and particularly preferably 0.3% or less. On the other hand, the lower the internal haze (Hihc) of the antiglare hard coat layer, the better. The lower limit is particularly preferably 0% or more.

  The antiglare hard coat layer in the present invention preferably has a ratio (Hihc / Hzhc) of internal haze (Hihc) to total haze (Hzhc) of 0.60 or less. By setting the ratio (Hihc / Hzhc) within the above numerical range, the balance between transparency and antiglare property can be further improved. Moreover, it is excellent in black reproducibility. From such a viewpoint, the ratio (Hihc / Hzhc) is more preferably 0.10 or more and 0.40 or less, and particularly preferably 0.18 or more and 0.35 or less.

  In order to achieve the total haze (Hzhc) and internal haze (Hihc) of the antiglare hard coat layer as described above, the refractive index of the binder component in the antiglare hard coat layer, the refraction of organic particles and inorganic fine particles. This can be achieved by appropriately adjusting the rate, average particle size, content, refractive index of the binder resin and inorganic filler, and film thickness of the antiglare hard coat layer. For example, reducing the difference between the refractive index of the binder component and the refractive index of organic particles and inorganic fine particles, reducing the average particle size of organic particles and inorganic fine particles, or reducing the content of organic particles and inorganic fine particles Then, the total haze (Hzhc) and internal haze (Hihc) of the antiglare hard coat layer tend to be low.

  The film thickness of the antiglare hard coat layer in the present invention is preferably in the range of 50% to 200% of the average particle diameter of the organic particles. By setting the film thickness of the antiglare hard coat layer within the above mathematical range, transparency and antiglare properties are more excellent. Moreover, it is excellent in balance with transparency and anti-glare property. Moreover, it is excellent in black reproducibility. Furthermore, dropping off of organic particles and inorganic fine particles can be suppressed. When the film thickness of the antiglare hard coat layer is too thin, the height of the protrusions formed by organic particles and inorganic fine particles tends to be too high on the surface of the antiglare hard coat layer, and transparency and black reproducibility Tend to be inferior. In addition, the particles tend to fall off. On the other hand, if it is too thick, the organic particles and inorganic fine particles tend to be difficult to form protrusions on the surface of the antiglare hard coat layer, thereby making it difficult to diffuse light and tend to be inferior in antiglare properties. is there. From such a viewpoint, the film thickness of the antiglare hard coat layer is more preferably in the range of 145% to 160% of the average particle diameter of the organic particles, and particularly preferably 148% to 156 of the average particle diameter of the organic particles. % Or less.

  In the antiglare hard coat layer of the present invention, the half width of the surface protrusion height distribution on the surface thereof is preferably in the range of 0.20 μm or more and 0.70 μm or less. Here, the full width at half maximum of the surface projection height distribution is determined from the surface profile obtained by a non-contact optical roughness meter (manufactured by ZYGO, trade name: NewView 5022), and the projection height (unit: μm) on the horizontal axis by Histogram Plot. ), And the vertical axis represents the half width (the width of the distribution at the half height of the distribution at the peak position) (unit: μm) in the protrusion distribution in which the frequency (unit: Counts) is plotted. By setting the half-value width of the surface protrusion height distribution within the above numerical range, transparency and antiglare properties are more excellent. Moreover, it is excellent in balance with transparency and anti-glare property. Moreover, it is excellent in black reproducibility. When the value of the half width of the surface protrusion height distribution is too large, the transparency and the black reproducibility tend to be inferior. On the other hand, if it is too small, it tends to be inferior in antiglare property. From such a viewpoint, the half-value width of the surface protrusion height distribution is more preferably in the range of 0.40 μm to 0.60 μm, and particularly preferably in the range of 0.43 μm to 0.50 μm.

  The center line average surface roughness (Ra) on the surface of the antiglare hard coat layer in the present invention is preferably 0.01 μm or more and 0.25 μm or less. By setting the centerline average surface roughness (Ra) to the above numerical range, the transparency and antiglare property are more excellent. Moreover, it is excellent in balance with transparency and anti-glare property. Moreover, it is excellent in black reproducibility. When the value of the center line average surface roughness (Ra) is too large, the transparency and the black reproducibility tend to be inferior. On the other hand, if it is too small, it tends to be inferior in antiglare property. From such a viewpoint, the lower limit of the centerline average surface roughness (Ra) is more preferably 0.11 μm or more, and particularly preferably 0.14 μm or more. The upper limit of the center line average surface roughness (Ra) is more preferably 0.22 μm or less, and particularly preferably 0.17 μm or less.

  The half width of the surface protrusion height distribution and the center line average surface roughness (Ra) on the surface of the antiglare hard coat layer as described above are the average particle diameters of the organic particles and the inorganic fine particles in the antiglare hard coat layer, and This is achieved by appropriately adjusting the content. For example, when the average particle size of organic particles and inorganic fine particles is increased, the value of the half-value width of the surface protrusion height distribution tends to increase. Further, when the average particle size of the organic particles and inorganic fine particles contained is increased or the content is increased, the value of the center line average surface roughness (Ra) tends to increase. In addition, a part of the inorganic filler and / or inorganic fine particles, which will be described later, form an appropriately sized aggregate is also a preferred means for making the surface of the antiglare hard coat as described above. is there.

Hereinafter, each component contained in the anti-glare hard coat layer in the present invention will be described.
[Binder component]
The binder component in this invention mainly consists of binder resin mentioned later. The binder component in the present invention preferably contains an inorganic filler as a constituent component.

[Binder resin]
The binder resin in the present invention mainly comprises a radiation curable resin composition.
Such a radiation curable resin composition is a monomer, oligomer, or polymer that can be cured by radiation. As a radiation curable resin composition in the present invention, the crosslinking density after curing can be increased, the effect of improving the surface hardness can be increased, and the effect of improving the transparency can be increased. Therefore, a polyfunctional (meth) acrylate compound such as a polyfunctional (meth) acrylate monomer, a polyfunctional (meth) acrylate oligomer, or a polyfunctional (meth) acrylate polymer is preferable.

  Such a polyfunctional (meth) acrylate compound is a compound containing a (meth) acryloyl group in the molecule, and preferably contains at least two (meth) acryloyl groups in the molecule. As a result, the crosslinking reaction of the radiation curable resin composition is likely to proceed, and the effect of improving the surface hardness can be further increased. Moreover, the polyfunctional (meth) acrylate compound in this invention may contain other polymerizable functional groups other than a (meth) acryloyl group in a molecule | numerator.

  Specific examples of the polyfunctional (meth) acrylate compound containing at least two (meth) acryloyl groups in the molecule include, for example, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri ( (Meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, alkyl-modified dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Alkyl modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (Meth) acrylate, ditrimethylolpropane tetra (meth) acrylate), melamine (meth) acrylate, etc., and oligomers of about 1 to 20 mer consisting of at least one of these, and polymers consisting of at least one of these Can be mentioned. Such polyfunctional (meth) acrylate compounds may be used alone or in combination of two or more.

  Polyfunctional (meth) acrylate compounds containing at least two (meth) acryloyl groups in the molecule as described above are, for example, Aronics M-400, M-450, M-305, M-309, M-310, M-315, M-320, TO-1200, TO-1231, TO-595, TO-756 (above, manufactured by Toagosei), KAYARD D-310, D-330, DPHA, DPHA-2C (above, Nipponization) Such as Nikarac MX-302 (manufactured by Sanwa Chemical Co., Ltd.).

  In the present invention, it is preferable to add a photopolymerization initiator to the binder resin in order to form a more excellent antiglare hard coat layer. Examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, anthraquinone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4- Chlorobenzophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl-1-1 [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine Examples thereof include oxides and bis- (2,6-dimethoxybenzoyl) 2,4,4-trimethylpentylphosphine oxide.

The addition amount of the photopolymerization initiator in the present invention is preferably 0.1% by mass or more and 10% by mass or less based on 100% by mass of the radiation curable resin composition. By making addition amount into the said numerical range, the improvement effect of the surface hardness of an anti-glare hard-coat layer can be made higher. When there is too much addition amount, the added photoinitiator tends to work as a plasticizer, and there exists a possibility that the intensity | strength of an anti-glare hard-coat layer may become low.
A silicone resin can be further added to the binder resin in the present invention, and the effect of improving the strength and surface hardness of the antiglare hard coat layer can be further enhanced.

[Inorganic filler]
The binder component in the present invention preferably contains an inorganic filler for the purpose of enhancing the effect of improving the surface hardness and strength of the antiglare hard coat layer, or for the purpose of suppressing curling.

  As such an inorganic filler, silicon oxide and aluminum oxide are preferable, and the effect of improving the surface hardness and strength of the antiglare hard coat layer can be further increased. Moreover, the improvement effect of transparency and anti-glare property can be made higher. Furthermore, it is excellent in slipperiness. Among these, silicon oxide is preferable, the effect of improving the surface hardness can be particularly increased, and the strength can be particularly increased.

  In the present invention, by adding the inorganic filler as described above, the effect of improving mechanical properties such as strength can be enhanced in the antiglare hard coat layer. It is necessary to select an inorganic filler that does not affect optical properties such as antiglare properties. Specifically, it is preferable that the average particle size and refractive index of the inorganic filler are in a specific numerical range.

  For the above purpose, in the present invention, the average particle size of the inorganic filler is preferably 2 nm or more and 2000 nm or less. When the average particle size is in the above numerical range, the effect of improving the surface hardness and strength can be enhanced while maintaining the transparency of the antiglare hard coat layer. In addition, the internal haze (Hihc) of the antiglare hard coat layer can be further reduced. Moreover, it is excellent in black reproducibility. When the average particle size of the inorganic filler is too large, the transparency and black color reproducibility tend to be inferior. On the other hand, if it is too small, the strength of the inorganic filler itself tends to be low, and the effect of improving the surface hardness and strength tends to be low. From such a viewpoint, the average particle diameter of the inorganic filler is more preferably 3 nm to 200 nm, and particularly preferably 5 nm to 100 nm.

  Moreover, it is preferable to use the inorganic filler which has a specific refractive index, and the inorganic filler whose refractive index difference with the above-mentioned binder resin is less than 0.1 is preferable. When the refractive index difference is in the above numerical range, the effect of improving the surface hardness and strength can be increased while maintaining the transparency of the antiglare hard coat layer. In addition, the internal haze (Hihc) of the antiglare hard coat layer can be further reduced. Moreover, it is excellent in black reproducibility. When the refractive index difference is too large, the transparency and black color reproducibility tend to be inferior. From such a viewpoint, the difference in refractive index is preferably less than 0.08, and more preferably less than 0.07.

As for content of an inorganic filler, 10 mass% or more and 70 mass% or less are preferable in 100 mass% of binder components. By making content into the said numerical range, the improvement effect of surface hardness and intensity | strength can be made high, maintaining the transparency of an anti-glare hard-coat layer. In addition, the internal haze (Hihc) of the antiglare hard coat layer can be further reduced. Moreover, it is excellent in black reproducibility. When there is too much content, it exists in the tendency which is inferior to transparency and black reproducibility. On the other hand, when the content is too small, the effect of improving the surface hardness and strength tends to be low. From such a viewpoint, the content is more preferably 20% by mass or more and 60% by mass or less, and particularly preferably 30% by mass or more and 50% by mass or less.
One kind of inorganic filler as described above may be used alone, or two or more kinds may be used in combination.

  In the present invention, it is preferable to use an inorganic filler that is in the form of a solvent dispersion sol in which a powder or a powdery inorganic filler is dispersed in a solvent to form a sol. When the inorganic filler is in the form of a solvent-dispersed sol, the dispersion medium is preferably an organic solvent from the viewpoint of enhancing compatibility with the binder resin. Examples of the organic solvent include alcohols such as methanol, ethanol, isopropanol, and butanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate And the like; ethers such as propylene glycol monomethyl ether and propylene glycol monomethyl ether; aromatic hydrocarbons such as benzene, toluene and xylene. Of these, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene, and xylene are preferable and have excellent compatibility. Various surfactants and amines can be added to improve the dispersibility of the inorganic filler.

  The inorganic fillers as described above are, for example, solvent-dispersed sol-like silicon oxides such as IPA-ST, MEK-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST- 20, ST-40 (above, manufactured by Nissan Chemical Co., Ltd.) and the like can be obtained and preferably used. Solvent-dispersed sol-like aluminum oxides are available as commercial products such as alumina sol 100, alumina sol 200, alumina sol 500 (above, manufactured by Nissan Kagaku Co., Ltd.), AS-150I, AS-150T (above, made by Sumitomo Osaka Cement). Can be preferably used.

  Furthermore, the inorganic filler in the present invention is used to improve the dispersibility in the binder resin, to improve the dispersion state in the antiglare hard coat layer, or to form a crosslinking point with the binder resin to prevent For the purpose of improving the surface hardness and strength of the dazzling hard coat layer, an embodiment in which the surface is treated with a polymerizable surface treatment agent is preferable.

  Examples of the surface treatment agent include a compound containing a silanol group or generating a silanol group by hydrolysis (hereinafter sometimes referred to as a silane coupling agent), and is preferably used. Furthermore, a silane coupling agent having both a silanol group and a polymerizable functional group other than the silanol group is preferable. In such a silane coupling agent, the silanol group and the hydroxyl group present on the surface of the inorganic filler can be cross-linked by heat or the like, and thereby the silane coupling agent is bonded to the surface of the inorganic filler. The dispersibility in the organic component can be increased. Examples of the polymerizable functional group other than the silanol group include acryloyl group, methacryloyl group, vinyl group, propenyl group, butadienyl group, styryl group, ethynyl group, acrylamide group and hydroxyl group.

  Examples of the silane coupling agent as described above include TSL-8350, TSL-8337, TSL-8370, TSL-8375 (manufactured by GE Toshiba Silicone), A-9530 (manufactured by Shin-Nakamura Chemical), A-187 ( It can be obtained as a commercial product such as Nippon Unicar, and can be preferably used.

  Although the method of obtaining the surface-treated inorganic filler is not specifically limited, For example, it can obtain by the following method. That is, first, the silane coupling agent and the inorganic filler as described above are mixed, and after adding ion-exchanged water, the silane coupling agent is hydrolyzed by allowing it to stand at room temperature. The time required for hydrolysis varies depending on the substance used, but is about 1 to 24 hours. After the hydrolysis of the silane coupling agent has sufficiently progressed, by applying a temperature of 20 ° C. to 150 ° C., the silanol group in the silane coupling agent reacts with the hydroxyl group on the surface of the inorganic filler, and the surface-treated inorganic A filler can be obtained.

  In the present invention, it is possible to use a coating liquid obtained by further adding inorganic fine particles described later to a solution containing a binder component containing a binder resin and an inorganic filler as constituent components and organic particles described later. One preferred means for simultaneously achieving the total haze (Hz) and 60 degree gloss specified by the invention. By setting it as such an aspect, in an anti-glare hard-coat layer, a part of inorganic filler and / or inorganic fine particle form the aggregate of a moderate magnitude | size. With such an aggregate, the surface shape of the antiglare hard coat layer becomes a more preferable embodiment, and the balance between transparency and antiglare property can be further improved, and these can be improved simultaneously. it can. Further, the black reproducibility can be further improved.

[Organic particles]
As organic particles in the present invention, (meth) acrylic resin particles, crosslinked (meth) acrylic resin particles, crosslinked (meth) acrylic-styrene copolymer resin particles, polystyrene resin particles, crosslinked polystyrene resin particles, melamine resin particles, benzoguanamine resin Examples thereof include resin particles such as particles, polycarbonate resin particles, and polyvinyl chloride resin particles. Among these, crosslinked (meth) acrylic resin particles are preferable from the viewpoint that the effect of improving transparency can be enhanced and the antiglare hard coat layer does not easily fall off.

  In the present invention, the difference (refractive index difference) between the refractive index of the organic particles and the refractive index of the binder component is preferably less than 0.03. By making the difference in refractive index within the above numerical range, light diffusion due to organic particles can be reduced inside the antiglare hard coat layer, and the internal haze (Hihc) of the antiglare hard coat layer can be lowered. The transparency improvement effect can be increased. From such a viewpoint, the refractive index difference between the organic particles and the binder component is more preferably less than 0.025.

  The organic particles in the present invention preferably have an average particle size of 1 μm or more and 10 μm or less. By making the average particle size of the organic particles within the above numerical range, the surface of the antiglare hard coat layer is likely to cause light diffusion due to the organic particles, while maintaining transparency and black reproducibility, The improvement effect can be increased. Moreover, it becomes easy to achieve the half-value width of the surface protrusion height distribution and the centerline average surface roughness (Ra) preferably defined by the present invention. When the average particle diameter of the organic particles is too small, the antiglare property tends to be inferior. On the other hand, when it is too large, the effect of improving the antiglare property is enhanced, but the transparency and black color reproducibility tend to be inferior. From such a viewpoint, the average particle size of the organic particles is more preferably 1.5 μm or more and 8 μm or less, further preferably 2 μm or more and 6 μm or less, and particularly preferably 2.5 μm or more and 3.5 μm or less.

  The antiglare hard coat layer in the present invention preferably contains 0.1% by mass or more and 5% by mass or less of such organic particles based on 100% by mass of the binder component. By keeping the content of the organic particles in the above numerical range, it is possible to increase the effect of improving the antiglare property while maintaining transparency and black reproducibility, and to make these balances more excellent. it can. Moreover, it is excellent in transparency and black reproducibility. Moreover, it becomes easy to achieve the centerline average surface roughness (Ra) preferably defined by the present invention. When the content is too small, light diffusion due to organic particles tends to hardly occur on the surface of the antiglare hard coat layer, and the antiglare property tends to be inferior. On the other hand, when the amount is too large, the effect of improving the antiglare property is enhanced, but the transparency and black color reproducibility tend to be inferior. From such a viewpoint, the content of the organic particles is more preferably 0.5% by mass to 3% by mass, and particularly preferably 1% by mass to 2% by mass.

  In the present invention, the organic particles as described above act as large-diameter particles in the antiglare hard coat layer. These large-diameter particles form protrusions on the surface of the antiglare hard coat layer and form a surface that serves as a base for causing light diffusion. On the other hand, it is important not to cause light diffusion inside the antiglare hard coat layer, and by satisfying these simultaneously, the effect of improving transparency and antiglare properties can be enhanced. In addition, the balance between transparency and antiglare property can be further improved. Further, the black reproducibility can be further improved. In order to express such an effect more effectively, and to achieve the total haze (Hz) and 60 degree glossiness in the present invention more effectively, the refractive index and the average particle diameter as described above are set. It is particularly preferable to employ the crosslinked (meth) acrylic resin particles having the above content. Such organic particles are obtained as commercial products such as MX-150, MX-180, MX-300 (above, manufactured by Soken Chemical), XX-10GA, XX-1140Z, XX1141Z (above, manufactured by Sekisui Chemical Co., Ltd.). Can be preferably used.

[Inorganic fine particles]
Examples of the inorganic fine particles in the present invention include silica fine particles, hollow silica fine particles, alumina fine particles, metal fine particles such as TiO ₂ fine particles, and metal oxide fine particles. Among these, silica fine particles are preferable from the viewpoint that the effect of improving transparency and antiglare property can be enhanced.

  In the present invention, the difference (refractive index difference) between the refractive index of the inorganic fine particles and the refractive index of the binder component is preferably 0.03 or more. By setting the refractive index difference within the above numerical range, moderate light diffusion due to the inorganic fine particles is likely to occur inside the antiglare hard coat layer, and the effect of improving the antiglare property can be enhanced. From such a viewpoint, the refractive index difference between the inorganic fine particles and the binder component is more preferably 0.04 or more, and particularly preferably 0.05 or more.

  The inorganic fine particles in the present invention preferably have an average particle size of 1 nm or more and 100 nm or less. By setting the average particle size of the inorganic fine particles within the above numerical range, moderate light diffusion due to the inorganic fine particles is likely to occur inside the anti-glare hard coat layer, and the anti-glare is maintained while maintaining transparency and black reproducibility. The effect of improving the property can be increased. When the average particle size of the inorganic fine particles is too small, the antiglare property tends to be inferior. On the other hand, when it is too large, the effect of improving the antiglare property is enhanced, but the transparency and black color reproducibility tend to be inferior. From such a viewpoint, the average particle size of the inorganic fine particles is more preferably 5 nm to 30 nm, further preferably 10 nm to 27 nm, and particularly preferably 15 nm to 25 nm.

  The antiglare hard coat layer in the present invention preferably contains 0.5 to 5% by mass of such inorganic fine particles based on 100% by mass of the binder component. By making the content of the inorganic fine particles in the above numerical range, it is possible to increase the effect of improving the antiglare property while maintaining transparency and black reproducibility, and to make these balances more excellent. it can. When the content is too small, light diffusion due to inorganic fine particles tends to hardly occur inside the antiglare hard coat layer, and the antiglare property tends to be inferior. On the other hand, when the amount is too large, the effect of improving the antiglare property is enhanced, but the transparency and black color reproducibility tend to be inferior. From such a viewpoint, the content of the inorganic fine particles is more preferably 0.6% by mass to 3% by mass, and particularly preferably 0.8% by mass to 1.2% by mass.

  In the present invention, the inorganic fine particles as described above act as small-diameter particles in the antiglare hard coat layer. It is important that the small diameter particles cause light diffusion inside the antiglare hard coat layer. At the same time, it is important that the transparency is not greatly reduced. By satisfying these simultaneously, the effect of improving transparency and antiglare property can be enhanced. In addition, the balance between transparency and antiglare property can be further improved. Further, the black reproducibility can be further improved. In order to express such an effect more effectively, and to achieve the total haze (Hz) and 60 degree glossiness in the present invention more effectively, the refractive index and the average particle diameter as described above are set. It is particularly preferable to employ the silica fine particles having the above content. Such inorganic fine particles can be obtained, for example, as commercially available products such as SI Tolu (G-240) 10 mass% dispersed slurry (manufactured by C-I Kasei), and can be preferably used.

  As described above, in the antiglare hard coat layer in the present invention, organic particles as large-diameter particles are added to a binder component containing a binder resin and an inorganic filler as constituent components, and further inorganic fine particles are post-added. Embodiments are preferred. By strictly controlling the refractive index, average particle diameter, and content of each particle, both excellent transparency and excellent antiglare properties can be achieved. In particular, it is possible to achieve a balance between transparency and anti-glare properties required for PDPs in recent years. Moreover, it can be excellent in black reproducibility. In particular, the black reproducibility required for PDP in recent years can be achieved.

[Other additives]
In the antiglare hard coat layer in the present invention, in addition to the above-described ones, a photosensitizer, a leveling agent, a plasticizer, an ultraviolet absorber, an antioxidant, an electrifier, as long as the object of the present invention is not impaired. Inhibitors, pigments, dyes and the like can be added.

[Transparent resin substrate]
The transparent resin substrate in the present invention is not particularly limited, and examples thereof include a sheet or film made of polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyethylene, polystyrene triacetyl cellulose, acrylic, or the like. Of these, a film made of polyethylene terephthalate or polyethylene naphthalate is preferable from the viewpoint of good balance between optical properties such as transparency, mechanical properties, heat resistance, and price. These transparent resin base materials can be subjected to a surface treatment such as providing an easy-adhesion layer or performing a corona treatment for the purpose of enhancing the adhesion to the antiglare hard coat layer. The thickness of the transparent resin substrate is not particularly limited, but from the viewpoint of good optical properties and handling properties, it is preferably 25 μm or more and 300 μm or less, more preferably 50 μm or more and 200 μm or less, and particularly preferably 75 μm or more and 188 μm or less. It is.

[Method of forming antiglare hard coat layer]
The antiglare hard coat film of the present invention is obtained by applying a coating liquid for forming an antiglare hard coat layer to the surface on the side where the antiglare hard coat layer on the transparent resin substrate is to be formed. It can be obtained by drying by heating and curing.

  In the present invention, the coating liquid for forming the antiglare hard coat layer is a solvent, the binder component, organic particles, and inorganic particles that may be optionally added, and other additives that may be optionally added It is a solution in which an agent is added and mixed. When adding each component, it may be added as a solid such as a powder, or a solid made into a solution or a simple substance using an appropriate solvent may be added. In the present invention, it is preferable to add inorganic fine particles after adding a binder component containing an inorganic filler as a constituent component, and simultaneously achieve the transparency total haze (Hz) and 60 ° glossiness defined by the present invention. One preferred means for this. The solvent used in the coating solution is not particularly limited, but for example, ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, alcohols such as methanol, ethanol, propanol, n-butanol, secondary butanol, t-butanol, and isopropyl alcohol , Esters such as butyl acetate and ethyl acetate, aromatic hydrocarbons such as toluene and xylene, glycol ethers such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate, etc. As a result, the appearance of the antiglare hard coat layer is improved. Of these, ketones are preferable from the viewpoint of good solubility, and methyl ethyl ketone and methyl isobutyl ketone are particularly preferable. As solid content concentration of a coating liquid, 1-70 mass% is preferable, and defects, such as a smear, can be reduced by setting it as such an aspect.

As a method for applying the coating liquid for forming the antiglare hard coat layer, a method known per se can be employed. For example, the lip direct method, comma coater method, slit reverse method, die coater method, gravure roll coater method, blade coater method, spray coater method, air knife coat method, dip coat method, bar coater method and the like can be preferably mentioned. By these application methods, a coating liquid is applied onto the transparent resin substrate to form a coating film, and the obtained coating film is heated and dried. Heat drying conditions are preferably heating at 50 to 150 ° C. for 10 to 150 seconds, more preferably heating at 50 to 120 ° C. for 20 to 130 seconds, and heating at 50 to 80 ° C. for 30 to 120 seconds. Is particularly preferred. After heat drying, the coating film is cured by ultraviolet irradiation or electron beam irradiation. For UV irradiation, the irradiation amount is preferably 10 to 2000 mJ / cm ^2, more preferably 50~1500mJ / cm ^2, particularly preferably 100~1000mJ / cm ^2, a higher effect of improving surface hardness be able to.

  Hereinafter, the present invention will be described more specifically with reference to examples. In addition, each evaluation in an Example followed the following method.

(1) Total haze and internal haze (1-1) Total haze of antiglare hard coat film (Hz)
The total haze (Hz) of the antiglare hard coat film was measured with a haze meter HCM-2B manufactured by Suga Test Instruments Co., Ltd. according to JIS K7150. Incident light was incident from the antiglare hard coat layer side. Measurement was carried out at arbitrary five locations, and the average value thereof was defined as total haze (Hz) (unit:%).

(1-2) Total haze (Hzhc) and internal haze (Hihc) of antiglare hard coat layer
The total haze (Hzhc) and internal haze (Hihc) of the antiglare hard coat layer were determined by the following methods. First, the total haze (Hzf) of the transparent resin substrate was determined according to the method of (1-1) above. Next, on one side of the transparent resin substrate (the surface on the side where the antiglare hard coat layer is provided), a binder component (manufactured by JSR Corporation, trade name: Z7501) is applied using a Mayer bar, and the coating thickness is dried. Was applied to a thickness of about 10 μm, and sufficiently dried and cured to obtain a transparent resin substrate on which a binder component layer was formed. About the obtained sample, the total haze (Hzfb) was calculated | required according to the method of said (1-1). Here, as described later, since the total haze of the binder component layer is 0%, the surface haze (Hsf) and the internal haze (Hif) of the transparent resin substrate can be obtained by the following formula.
(Hzf) = (Hif) + 2 × (Hsf)
(Hzfb) = (Hif) + (Hsf)
(Hsf) = (Hzf) − (Hzfb)
(Hif) = (Hzf) −2 × (Hsf)

Next, on the antiglare hard coat layer of the antiglare hard coat film, a binder component layer was formed in the same manner as described above to obtain an antiglare hard coat film on which the binder component layer was formed. About this sample, the total haze (Hzb) was calculated | required according to the method of said (1-1). Here, using the total haze (Hz) of the antiglare hard coat film obtained in (1-1) above, the surface haze (Hsf) and internal haze (Hif) of the transparent resin substrate obtained above. The total haze (Hzhc), surface haze (Hshc), and internal haze (Hihc) of the antiglare hard coat layer can be determined by the following formula.
(Hz) = (Hshc) + (Hihc) + (Hif) + (Hsf)
(Hzb) = (Hihc) + (Hif) + (Hsf)
(Hshc) = (Hz) − (Hzb)
(Hihc) = (Hzb) − (Hif) − (Hsf)
(Hzhc) = (Hihc) + 2 × (Hshc)

Furthermore, the internal haze (Hi) of the antiglare hard coat film can be obtained by the following formula.
(Hi) = (Hihc) + (Hif)
The binder component was dried and cured to prepare a plate-like sample consisting of the binder component having a thickness of about 10 μm. When the total haze was measured according to the method (1-1), it was confirmed to be 0%. .

(2) 60 degree glossiness 60 degree glossiness was measured based on JIS K7105 using the Nippon Denshoku Industries Co., Ltd. gloss meter. The measurement was carried out at any 10 locations on the surface of the antiglare hard coat layer of the sample, and the average value thereof was taken as the measurement value.

(3) Refractive index (3-1) Refractive index of binder component and binder resin The refractive index of the binder component and the binder resin was measured by the following method.
First, a resin sample was sampled in a petri dish, allowed to stand at 80 ° C. for 24 hours, and sufficiently dried to prepare a plate-like sample having a thickness of about 1 mm. About the obtained plate-shaped sample, the refractive index was measured in the environment of temperature 23 degreeC and relative humidity 65% RH using the Abbe refractometer which used sodium D line | wire (589 nm) as the light source. The measurement was carried out at arbitrary five locations, and the average value thereof was taken as the refractive index of the resin sample.

(3-2) Refractive Index of Organic Particle, Inorganic Fine Particle, Inorganic Filler The refractive index of the organic particle, inorganic fine particle, and inorganic filler was measured by the following method.
First, the particle sample was left to dry at 80 ° C. for 24 hours, and then suspended in various liquids (25 ° C.) having different refractive indexes. Next, the refractive index of the liquid in which the suspension is most transparent is measured using an Abbe refractometer using sodium D line (589 nm) as a light source in an environment of a temperature of 23 ° C. and a relative humidity of 65% RH. The obtained value was taken as the refractive index of the particle sample.

(4) Average particle size On the sample stage, powder is dispersed so that individual particles do not overlap as much as possible, and a gold thin film deposition layer is formed on this surface with a thickness of 200 to 300 mm by a gold sputtering device. Using a microscope, observe at 10,000 to 30,000 times, determine the area equivalent particle size of at least 1000 particles with Luzex 500 manufactured by Japan Regulator Co., Ltd., and calculate the average value of the average particle size (unit: μm or nm).

(5) Film thickness of the antiglare hard coat layer The sample film was cut with a sharp razor, and the obtained cross section was observed with an optical microscope. On the surface of the antiglare hard coat layer, organic particles and inorganic fine particles were used. The thickness of the portion where no protrusion was formed was measured. The measurement was carried out at 10 arbitrary locations, and the average value thereof was defined as the film thickness (unit: μm) of the antiglare hard coat layer.

(6) Half width of projection height distribution Using a non-contact optical roughness meter (manufactured by ZYGO, trade name: NewView 5022), scanning was performed on a region of 283 μm × 213 μm at a magnification of 25 times to obtain a surface profile. . From the obtained surface profile, a projection distribution in which the height of projections (unit: μm) is plotted on the horizontal axis and the frequency (units: Counts) is plotted on the vertical axis is obtained by Histogram Plot. From the obtained protrusion distribution, the width of the distribution at the half height position of the distribution height at the peak position was read to obtain the half width (unit: μm) of the protrusion height distribution. The measurement was carried out at any five locations on the surface of the antiglare hard coat layer, and the average value thereof was taken as the measurement value.

(7) Centerline average surface roughness (Ra)
Measurement length (Lx) 1 mm, sampling pitch 2 μm, cut-off using a non-contact type three-dimensional roughness meter (Kosaka Laboratories, ET-30HK) with a semiconductor laser with a wavelength of 780 nm and an optical stylus with a beam diameter of 1.6 μm The protrusion profile on the film surface was measured under the conditions of 0.25 mm, thickness direction magnification 10,000 times, lateral direction magnification 200 times, and the number of scanning lines 100 (thus, the measurement length Ly in the Y direction was 0.2 mm). . When the roughness curved surface was represented by Z = f (x, y), the value obtained by the following formula was defined as the center line average surface roughness (Ra, unit: μm) of the film.

(8) Black reproducibility (8-1) Black tape method A sample in which a black tape is attached to the surface of the antiglare hard coat film opposite to the antiglare hard coat layer is prepared, and the antiglare hard The reproducibility of black color was visually confirmed from the coat layer side, and evaluation was performed according to the following criteria.
○: The black tape does not look whitish at all, and the black reproducibility is good.
(Triangle | delta): The difference with the black of black tape itself can be recognized somehow.
X: The black tape looks whitish as a whole, and black reproducibility is insufficient.

(8-2) PDP method The antireflection film is peeled off from the screen surface of a commercially available 50-inch plasma display (resolution XGA), and then the antiglare hard coat film obtained in the present invention is applied on the surface to the antiglare property. The adhesive was used so that the hard cord layer was on the front side. This operation was performed on the screen half of the plasma display, and the other half was kept in a commercial state. The display of the plasma display was displayed in black, the screen was observed in a 500 lux bright room, and the black reproducibility was evaluated by visual comparison with the part as it was on the market. Evaluation was according to the following indicators.
◎: There is no whiteness caused by external light, and the display is very black (pass)
○: Almost no whitening due to external light, black display (pass)
△: Display with whiteness due to external light and low black tightening (failed)
×: Strong whiteness due to external light, no black tightening (failed)

(9) Antiglare property A fluorescent lamp is installed at a position 30 cm above the surface on the antiglare hard coat layer side of the obtained antiglare hard coat film, and light from the fluorescent lamp on the surface of the hard coat film. The anti-glare property was evaluated according to the following criteria.
A: The shape of the fluorescent lamp is not known at all, and the antiglare property is good (pass)
○: The shape of the fluorescent lamp can be recognized somehow, and the anti-glare property is sufficient (pass)
Δ: The shape of the fluorescent lamp can be clearly recognized, and the antiglare property is insufficient (failed)
X: The shape of the fluorescent lamp is seen as a mirror image completely, and there is no anti-glare property (failure)

(10) Pencil hardness It implemented based on JISK5400.
Evaluation was carried out on the surface of the antiglare hard coat layer of the antiglare hard coat film.

[Example 1]
<Preparation of coating liquid for forming an easy-adhesion layer>
Polyester: polyester having an acid component of 65 mol% of 2,6-naphthalenedicarboxylic acid / 30 mol% of isophthalic acid / 5 mol% of 5-sodium sulfoisophthalic acid and a glycol component of 90 mol% of ethylene glycol / 10 mol% of diethylene glycol (Tg = 80 ° C., number average molecular weight 13000) was used.
The polyester was produced as follows according to the method described in Example 1 of JP-A-6-116487. That is, 44 parts of dimethyl 2,6-naphthalenedicarboxylate, 16 parts of dimethyl isophthalate, 4 parts of dimethyl 5-sodiumsulfoisophthalate, 34 parts of ethylene glycol, and 2 parts of diethylene glycol were charged into the reactor. Part was added and heated under a nitrogen atmosphere while controlling the temperature at 230 ° C., and the produced methanol was distilled off to carry out a transesterification reaction. Subsequently, the temperature of the reaction system was gradually raised to 255 ° C., and the inside of the system was reduced to 1 mmHg to carry out a polycondensation reaction to obtain a polyester.
The obtained polyester was used as a water dispersion (solid content concentration: 15% by mass) by a conventional method using tetrahydrofuran as a solution.

Acrylic: Acrylic (Tg = 50 ° C.) composed of 30% by mole of methyl methacrylate / 2% by mole of 2-isopropenyl-2-oxazoline / 10% by mole of polyethylene oxide (n = 10) methacrylate / 30% by mole of acrylamide was used.
The acrylic was produced as follows according to the method described in Production Examples 1 to 3 of JP-A-63-37167. That is, in a four-necked flask, 3 parts of sodium lauryl sulfonate as a surfactant and 181 parts of ion-exchanged water were charged and the temperature was raised to 60 ° C. in a nitrogen stream, and then 0.5 part of ammonium persulfate as a polymerization initiator. , 0.2 part of sodium hydrogen nitrite was added, and 23.3 parts of methyl methacrylate as a monomer, 22.6 parts of 2-isopropenyl-2-oxazoline, 40.7 parts of polyethylene oxide (n = 10) methacrylate A mixture of 13.3 parts of acrylamide was added dropwise over 3 hours while adjusting the liquid temperature to 60 to 70 ° C. The reaction was continued with stirring while maintaining the same temperature range for 2 hours even after the completion of the dropwise addition, and then cooled to obtain an acrylic aqueous dispersion (solid content concentration 35% by mass).
Additive: Silica filler (average particle size 100 nm) (manufactured by Nissan Chemical Co., Ltd., trade name: Snowtex ZL) was used.
Wetting agent: Polyoxyethylene (n = 7) lauryl ether (manufactured by Sanyo Chemical Co., Ltd., trade name: NAROACTY N-70) was used.
Each raw material obtained above was blended so that the solid content ratio would be 60% by weight of polyester, 30% by weight of acrylic, 5% by weight of additive, and 5% by weight of wetting agent, sufficiently stirred, and ion exchange It diluted so that it might become solid content concentration 8 mass% using water, and the coating liquid for forming an easily bonding layer was created.

<Formation of transparent resin substrate and easy adhesion layer>
Molten polyethylene terephthalate ([η] = 0.62 dl / g (25 ° C., orthochlorophenol), Tg = 78 ° C.) was extruded from a die and cooled with a cooling drum by a conventional method to obtain an unstretched film. Subsequently, this unstretched film was stretched 3.4 times in the longitudinal direction to obtain a longitudinally uniaxially stretched film. Then, the coating liquid for forming the easily bonding layer obtained above was uniformly apply | coated with the roll coater on both surfaces of the obtained longitudinally uniaxially stretched film. Next, the film was stretched 3.6 times at 125 ° C. in the transverse direction and heat-set while being shrunk 3% in the width direction at 220 ° C. to obtain a transparent resin base material having a thickness of 188 μm on which an easy adhesion layer was formed. . The thickness of the easy-adhesion layer was 0.04 μm. Moreover, the total haze (Hzf) of the transparent resin base material in which the easily bonding layer was formed was 1.4%, surface haze (Hsf) was 0.2%, and internal haze (Hif) was 1.0%.

<Coating solution for forming antiglare hard coat layer>
Binder resin (refractive index 1.53) mainly composed of dipentaerythritol hexa (meth) acrylate and silicon oxide as an inorganic filler (average particle size 20 nm, refractive index 1.47, surface with silane coupling agent A coating material (trade name: Z7501, manufactured by JSR Corporation, refractive index 1.51 after drying, solid content mass ratio of binder resin and inorganic filler 60:40). Used as a binder component, crosslinked organic resin particles (manufactured by Soken Chemical Co., Ltd., trade name: MX-300) having an average particle size of 3.0 μm and a refractive index of 1.49 are used as organic particles with respect to 100% by mass of the solid content of the binder component. 1.5% by mass added, and then a dispersion of silica fine particles having an average particle diameter of 20 nm and a refractive index of 1.45 as inorganic fine particles (trade name: SITO) G-240) is added so that the solid content of the silica fine particles is 1.0% by mass with respect to 100% by mass of the solid content of the binder component, and this is added to a solid content concentration of 30% by mass using methyl ethyl ketone (MEK). The coating liquid for forming an anti-glare hard coat layer was obtained.

<Formation of antiglare hard coat layer>
The coating liquid for forming the antiglare hard coat layer obtained above is dried and cured on the surface of one side of the transparent resin substrate on which the easy adhesion layer is formed using a roll coater. Was uniformly applied so as to be 4.5 μm, and dried at 70 ° C. for 2 minutes. Next, using an ultraviolet irradiation device (FusionUV Systems Japan Co., Ltd .: trade name Fusion H bulb), ultraviolet rays were irradiated under the condition of a light amount of 200 mJ / cm ² to obtain an antiglare hard coat film. The properties of the obtained antiglare hard coat layer and antiglare hard coat film are shown in Table 1.

[Example 2]
As organic particles, crosslinked acrylic resin particles having an average particle size of 2.6 μm and a refractive index of 1.52 (trade name: XX-1140Z, manufactured by Seiki Water Chemical Industry Co., Ltd.) are used, and the film thickness of the antiglare hard coat layer is 4. An antiglare hard coat film was obtained in the same manner as in Example 1 except that the thickness was 0 μm. The properties of the obtained antiglare hard coat layer and antiglare hard coat film are shown in Table 1.

[Comparative Example 1]
Anti-glare properties in the same manner as in Example 1 except that silicone resin particles having an average particle size of 3.0 μm and a refractive index of 1.43 (made by Momentive Performance Materials Japan G.K., trade name: Tospearl 130) are used as organic particles. A hard coat film was obtained. The properties of the obtained antiglare hard coat layer and antiglare hard coat film are shown in Table 1.

[Comparative Example 2]
Other than using organic particles instead of silica particles having an average particle size of 3.0 μm and a refractive index of 1.45 (manufactured by Fuji Silysia, trade name: SYLOPHOBIC200), the thickness of the antiglare hard coat layer is 5.0 μm. Obtained an antiglare hard coat film in the same manner as in Example 1. The properties of the obtained antiglare hard coat layer and antiglare hard coat film are shown in Table 1.

[Comparative Example 3]
An antiglare hard coat film was obtained in the same manner as in Example 1 except that acrylic fine particles having an average particle size of 80 nm and a refractive index of 1.49 were used instead of the inorganic fine particles. The properties of the obtained antiglare hard coat layer and antiglare hard coat film are shown in Table 1.

  As can be seen from Table 1, the antiglare hard coat films obtained in Examples 1 and 2 realize low haze and low gloss, and as a result, excellent transparency, antiglare and black reproducibility. Can be achieved at the same time.

Claims (6)

An antiglare hard coat film having an antiglare hard coat layer containing a binder component and organic particles as constituent components on at least one surface of a transparent resin substrate, and has a total haze (Hz) of 0.1% or more 4.0% or less, 60 degree gloss is 80 or more and less than 120,
The antiglare hard coat layer contains a binder resin and a binder component containing 10% by mass or more and 70% by mass or less of an inorganic filler as a constituent component with respect to the mass of the binder component, and the mass of the binder component is 0.00. A coating liquid obtained by further adding 0.5% by mass or more and 5.0% by mass or less of inorganic fine particles to a solution containing 1% by mass or more and 5.0% by mass or less of organic particles to the mass of the binder component. An anti-glare hard coat layer cured, and
An anti-glare hard coat film having a refractive index difference from the binder resin of less than 0.07 for inorganic fillers and 0.08 or more for inorganic fine particles.   2. The antiglare hard coat film according to claim 1, wherein the internal haze (Hihc) of the antiglare hard coat layer is 0.5% or less.   3. The antiglare hard coat film according to claim 1, wherein the organic particles have a refractive index difference from the binder component of less than 0.03 and an average particle size of 1 μm to 10 μm.   The antiglare hard coat film according to any one of claims 1 to 3, wherein the film thickness of the antiglare hard coat layer is in the range of 50% to 200% of the average particle diameter of the organic particles.   The antiglare hard coat film according to any one of claims 1 to 4, wherein the half width of the surface protrusion height distribution on the surface of the antiglare hard coat layer is in the range of 0.2 µm to 0.7 µm.   The antiglare hard coat film according to any one of claims 1 to 5, wherein a center line average surface roughness (Ra) on the surface of the antiglare hard coat layer is 0.01 µm or more and 0.25 µm or less.