WO2015080281A1 - Film anti-reflets - Google Patents

Film anti-reflets Download PDF

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Publication number
WO2015080281A1
WO2015080281A1 PCT/JP2014/081671 JP2014081671W WO2015080281A1 WO 2015080281 A1 WO2015080281 A1 WO 2015080281A1 JP 2014081671 W JP2014081671 W JP 2014081671W WO 2015080281 A1 WO2015080281 A1 WO 2015080281A1
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Prior art keywords
film
mold
antiglare
meth
less
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PCT/JP2014/081671
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English (en)
Japanese (ja)
Inventor
勉 古谷
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住友化学株式会社
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Application filed by 住友化学株式会社 filed Critical 住友化学株式会社
Priority to CN201480064327.3A priority Critical patent/CN105765416A/zh
Priority to KR1020167016825A priority patent/KR20160091954A/ko
Publication of WO2015080281A1 publication Critical patent/WO2015080281A1/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133502—Antiglare, refractive index matching layers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements
    • G02B5/0205—Diffusing elements; Afocal elements characterised by the diffusing properties
    • G02B5/021—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures
    • G02B5/0221—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures the surface having an irregular structure
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements
    • G02B5/0273—Diffusing elements; Afocal elements characterized by the use
    • G02B5/0284—Diffusing elements; Afocal elements characterized by the use used in reflection

Definitions

  • the present invention relates to an antiglare film having excellent antiglare properties.
  • Image display devices such as liquid crystal display, plasma display panel, cathode ray tube (CRT) display, organic electroluminescence (EL) display, etc.
  • An antiglare film is disposed on the display surface.
  • As an antiglare film a transparent film having an uneven surface shape is mainly studied.
  • Such an anti-glare film exhibits anti-glare properties by reducing reflection by scattering and reflecting external light (external light scattered light) due to the uneven surface shape.
  • external light scattering light is strong, so-called “whiteness” may occur in which the entire display surface of the image display device becomes whitish or the display becomes cloudy.
  • Patent Document 1 discloses an anti-glare film that does not generate glare even when placed in a high-definition image display device and that is sufficiently prevented from being whitish.
  • the surface irregularity shape is fine, and the average length PSm in the arbitrary sectional curve of the surface irregularity shape is 12 ⁇ m or less, and the ratio Pa / PSm of the arithmetic average height Pa to the average length PSm in the sectional curve is An anti-glare film having a surface ratio of 0.005 or more and 0.012 or less, the surface irregularity shape having an inclination angle of 2 ° or less, and a surface ratio having an inclination angle of 6 ° or less is 90% or more. It is disclosed.
  • the antiglare film disclosed in Patent Document 1 has a surface irregularity shape with a period of about 50 ⁇ m that makes it easy to generate glare by making the average length PSm in an arbitrary cross-sectional curve very small, Glare can be effectively suppressed.
  • the anti-glare film disclosed in Patent Document 1 tries to make the haze smaller (to make it low haze)
  • the anti-glare film when the display surface of the image display device on which the anti-glare film is arranged is observed obliquely. There was a case where the dazzle was reduced. Therefore, the antiglare film disclosed in Patent Document 1 has room for improvement in terms of antiglare properties at a wide observation angle.
  • the present invention provides an anti-glare film that has excellent anti-glare properties at a wide viewing angle even at low haze, and can sufficiently suppress the occurrence of whitish and glare when placed in an image display device.
  • the purpose is to do.
  • the present invention An anti-glare film comprising a transparent support and an anti-glare layer having fine surface irregularities formed thereon, The total haze is 0.1% or more and 3% or less, The antiglare film has a surface haze of 0.1% to 2%, The ratio R SCE / R SCI of the luminous reflectance R SCI measured by the regular reflection light including method and the luminous reflectance R SCE measured by the regular reflected light removal method is 0.1 or less, The surface uneven shape is an antiglare film characterized in that the power spectrum of the altitude satisfies all the following conditions (1) to (3).
  • the intensity I (0.01) at a spatial frequency of 0.01 ⁇ m ⁇ 1 is 2 ⁇ m 4 or more and 10 ⁇ m 4 or less; (2) The intensity I (0.02) at a spatial frequency of 0.02 ⁇ m ⁇ 1 is 0.1 ⁇ m 4 or more and 1.5 ⁇ m 4 or less; and (3) the intensity I at a spatial frequency of 0.1 ⁇ m ⁇ 1 (0. 1) is 0.0001 ⁇ m 4 or more and 0.01 ⁇ m 4 or less.
  • the sum Tc of transmitted sharpness measured using five types of optical combs in which the widths of the dark part and the bright part are 0.125 mm, 0.25 mm, 0.5 mm, 1.0 mm, and 2.0 mm, respectively, is 375%. That's it, Rc of reflection sharpness Rc measured at an incident angle of 45 ° using four types of optical combs having a dark portion and a bright portion width of 0.25 mm, 0.5 mm, 1.0 mm, and 2.0 mm, respectively.
  • (45) is 180% or less, Rc of reflection sharpness Rc measured at an incident angle of light of 60 ° using four types of optical combs in which the widths of the dark part and the bright part are 0.25 mm, 0.5 mm, 1.0 mm and 2.0 mm, respectively.
  • (60) is preferably 240% or less.
  • the specular reflection measured luminous reflectance by light removing system R SCE is 0.5% or less.
  • an anti-glare film having sufficient anti-glare property at a wide observation angle even with low haze and sufficiently suppressed generation of whitish and glare when placed in an image display device. Can be provided.
  • FIG. 4 is a diagram showing a part of a pattern A used in Examples 1 to 3 and Comparative Example 1.
  • 10 is a diagram illustrating a part of a pattern B used in Comparative Example 2.
  • FIG. 4 is a diagram showing a part of a pattern A used in Examples 1 to 3 and Comparative Example 1.
  • the anti-glare film of the present invention has a ratio R SCE / R SCI of 0.1 or less of the luminous reflectance R SCI measured by the specular reflection light incorporating method and the luminous reflectance R SCE measured by the regular reflected light removal method. And the intensity at the spatial frequencies of 0.01 ⁇ m ⁇ 1 , 0.02 ⁇ m ⁇ 1 , and 0.1 ⁇ m ⁇ 1 of the power spectrum of the elevation of the surface uneven shape is in the above-mentioned range.
  • FIG. 1A is a diagram schematically showing an optical system for measuring the luminous reflectance RSCI by the regular reflection light-incorporating method
  • FIG. 1B is the luminous reflection by the regular reflection light removing method. It is a figure which shows typically the optical system for measuring rate R SCE .
  • FIGS. 1A and 1B show a diffuse illumination optical system.
  • the diffuse illumination method is a method of uniformly illuminating a measurement sample from all directions using an integrating sphere. In FIGS.
  • an integrating sphere 12 (sulfuric acid that diffuses and reflects light almost completely is used.
  • a ball with an inner surface coated with white paint such as barium) is installed.
  • the light emitted from the light source 13 is diffused inside the integrating sphere 12 and reflected by the surface of the measurement sample 14.
  • a light trap 15 (in FIG. 1B, a jig having a conical cavity is attached to the position of the integrating sphere 12 in the regular reflection direction with respect to the light receiving portion.
  • the light that has entered the shaped cavity is absorbed in the cavity and does not return into the integrating sphere 12.) is installed, and the light in the regular reflection direction with respect to the light receiving portion is measured sample. It does not hit the surface.
  • an optical system using a light trap as shown in FIG. 1B is called a regular reflection light removal mode (SCE mode).
  • the luminous reflectance calculated according to the method described in JIS Z 8722 from the reflection spectra of the samples measured in both modes is the luminous reflectance R SCI measured by the regular reflection light insertion method and the visual reflectance measured by the regular reflection light removal method. Reflectivity R SCE .
  • the ratio R SCE / R SCI of the luminous reflectance R SCI measured by the regular reflection light inclusion method and the luminous reflectance R SCE measured by the regular reflection light removal method exceeds 0.1, an anti-glare film On the surface, the reflected light toward the user of the ambient light in the usage environment is strong, and as a result, the image display device provided with such an antiglare film is whitish. In addition, the image display device tends to cause a decrease in bright place contrast.
  • the ratio R SCE / R SCI is more preferably 0.08 or less, and further preferably 0.06 or less.
  • FIG. 2 is a cross-sectional view schematically showing the surface of the antiglare film of the present invention.
  • the antiglare film 1 of the present invention has a transparent support 101 and an antiglare layer 102 formed thereon, and the antiglare layer 102 is opposite to the transparent support 101.
  • the antiglare layer 102 is opposite to the transparent support 101.
  • the “elevation of the surface uneven shape” as used in the present invention means an arbitrary point P on the surface of the film 1 and a virtual plane 103 having the height at the average height of the surface uneven shape (the altitude is used as a reference).
  • 0 ⁇ m means a linear distance in the main normal direction 5 (normal direction in the virtual plane 103) of the film.
  • the antiglare film has an antiglare layer having fine irregularities formed on a two-dimensional plane. Therefore, as shown in FIG. 3, the elevation of the surface irregularity shape is expressed as a two-dimensional function h (x, y) of coordinates (x, y) when orthogonal coordinates in the film plane are displayed as (x, y). Can be represented.
  • the elevation of the surface of the fine irregularities can be obtained from three-dimensional information of the surface shape measured by an apparatus such as a confocal microscope, an interference microscope, an atomic force microscope (AFM).
  • the horizontal resolution required for the measuring instrument is at least 5 ⁇ m or less, preferably 2 ⁇ m or less, and the vertical resolution is at least 0.1 ⁇ m or less, preferably 0.01 ⁇ m or less.
  • Examples of the non-contact three-dimensional surface shape / roughness measuring apparatus suitable for this measurement include New View 5000 series (manufactured by Zygo Corporation), three-dimensional microscope PL ⁇ 2300 (manufactured by Sensofar), and the like.
  • the measurement area is preferably at least 200 ⁇ m ⁇ 200 ⁇ m, and more preferably 500 ⁇ m ⁇ 500 ⁇ m or more.
  • a method for obtaining an altitude power spectrum from a two-dimensional function h (x, y) will be described.
  • a two-dimensional function H (f x , f y ) is obtained from the two-dimensional function h (x, y) by a two-dimensional Fourier transform defined by equation (1). Wherein each the f x and f y, the frequency of the x and y directions, with the dimensions of the reciprocal of length.
  • ⁇ is a pi and i is an imaginary unit.
  • the two-dimensional power spectrum I (f x , f y ) can be obtained by equation (2).
  • the two-dimensional power spectrum I (f x, f y) represents the spatial frequency distribution of the surface irregularities of the antiglare film has. Since the antiglare film is isotropic, the two-dimensional function I (f x , f y ) representing the two-dimensional power spectrum of the elevation of the surface irregularity shape depends only on the distance f from the origin (0, 0). It can be represented by a one-dimensional function I (f).
  • I (f x, f y) is a two-dimensional power spectrum of the altitude of the equation (3).
  • ⁇ is a declination angle in Fourier space.
  • the one-dimensional function I (f) can be obtained by calculating the rotating average of the two-dimensional function I (fcos ⁇ , fsin ⁇ ) displayed in polar coordinates based on the equation (4).
  • the antiglare film of the present invention has an intensity I (0.01) at a spatial frequency of 0.01 ⁇ m ⁇ 1 and a spatial frequency of 0.02 ⁇ m ⁇ 1 of a one-dimensional power spectrum I (f) calculated from the elevation of the surface irregularity shape.
  • the intensity I (0.02) in is characterized in that and the intensity I (0.1) in the spatial frequency 0.1 [mu] m -1 is within a specific range.
  • FIG. 4 is a schematic diagram showing a state where functions h (x, y) representing altitude are obtained discretely. As shown in FIG. 4, orthogonal coordinates in the film plane are displayed as (x, y), and a line divided on the film projection plane 3 for each ⁇ x in the x-axis direction and a line divided for each ⁇ y in the y-axis direction.
  • the elevation of the surface uneven shape is obtained as a discrete elevation value for each area ⁇ x ⁇ ⁇ y divided by the broken lines on the film projection surface 3.
  • the number of elevation values obtained is determined by the measurement range and ⁇ x and ⁇ y.
  • the obtained elevation is The number of values is M ⁇ N.
  • the coordinates of the point of interest A on the film projection plane 3 are (m ⁇ x, n ⁇ y) [where m is 0 or more and M ⁇ 1 or less, and n is 0 or more and N ⁇ 1 or less.
  • the altitude of the point P on the film surface corresponding to the point of interest A can be expressed as h (m ⁇ x, n ⁇ y).
  • the measurement intervals ⁇ x and ⁇ y depend on the horizontal resolution of the measuring device, and in order to accurately evaluate the fine uneven surface, both ⁇ x and ⁇ y are preferably 5 ⁇ m or less, and preferably 2 ⁇ m or less. More preferred.
  • the measurement ranges X and Y are both preferably 200 ⁇ m or more, and more preferably 500 ⁇ m or more.
  • the function representing the elevation of the surface irregularity shape is obtained as a discrete function h (x, y) having M ⁇ N values.
  • the two-dimensional function H (f x , f y ) obtained by the two-dimensional Fourier transform of the two-dimensional function h (x, y) of the elevation of the fine uneven surface is also a discrete Fourier obtained by discretely calculating the expression (1).
  • j in the formula (5) is an integer of ⁇ M / 2 or more and M / 2 or less
  • k is an integer of ⁇ N / 2 or more and N / 2 or less.
  • ⁇ f x and ⁇ f y are frequency intervals in the x and y directions, respectively, and are defined by equations (6) and (7).
  • Two-dimensional power spectrum I (f x, f y) is a discrete function H (f x, f y) obtained by the equation (5) by squaring the absolute value of, determined as shown in equation (8) It is done.
  • 2 in equation (8) is divided by MN ⁇ x ⁇ y is to normalize that the integration range differs depending on the measurement area in the actual measurement.
  • the two-dimensional power spectrum I (f x , f y ) obtained as a discrete function also represents the spatial frequency distribution of the uneven surface shape of the antiglare film.
  • two-dimensional discrete function I (f x, f y) representing the two-dimensional power spectrum of the altitude of the surface unevenness shape only at a distance f from the origin (0, 0) It can be expressed by a dependent one-dimensional discrete function I (f).
  • the rotational average may be calculated in the same manner as in the equation (4).
  • Two-dimensional discrete function I (f x, f y) discrete rotational average can be calculated by Equation (9).
  • the function ⁇ (f jk ⁇ (l ⁇ 1 / 2) ⁇ f) is 0 when f jk is less than (l ⁇ 1 / 2) ⁇ f, and 1 when f jk is equal to or greater than (l ⁇ 1 / 2) ⁇ f.
  • the function ⁇ (f jk ⁇ (l + 1/2) ⁇ f) is 0 when f jk is less than (l + 1/2) ⁇ f, and is 1 when f jk is equal to or greater than (l + 1/2) ⁇ f.
  • f jk is (l-1/2) ⁇ f or more (l-1/2) less than Delta] f 1 only in the case of, and 0 otherwise.
  • f jk is the frequency space
  • the denominator of Equation (9) is the distance f jk from the origin O (l-1/2 )
  • the number of all points (black circle points in FIG. 5) located at or above ⁇ f and less than (l + 1/2) ⁇ f is calculated.
  • the numerator of the formula (9) is the sum of I (f x , f y ) of all points whose distance f jk from the origin O is located at (l ⁇ 1 / 2) ⁇ f or more and less than (l + 1/2) ⁇ f. the fact that computes the value (total value of I for definitive by the black points in FIG. 5 (f x, f y) ).
  • the one-dimensional power spectrum obtained by the above-described method includes noise in measurement. To determine the one-dimensional power spectrum here, in order to eliminate the influence of this noise, the elevation of the surface irregularities at multiple locations on the antiglare film is measured, and the one-dimensionality obtained from the elevation of each surface irregularity shape.
  • the average value of the power spectrum is preferably used as the one-dimensional power spectrum I (f).
  • the number of locations for measuring the elevation of the surface unevenness on the antiglare film is preferably 3 or more, more preferably 5 or more.
  • FIG. 6 shows I (f) of the one-dimensional power spectrum of the elevation of the surface unevenness obtained in this way.
  • the one-dimensional power spectrum I (f) in FIG. 6 is an average of the one-dimensional power spectra obtained from the elevations of the surface irregularities at five different locations on the antiglare film.
  • the intensity I (0.01) at a spatial frequency of 0.01 ⁇ m ⁇ 1 of the one-dimensional power spectrum I (f) calculated from the elevation of the surface uneven shape is 2 ⁇ m 4 or more and 10 ⁇ m 4 or less.
  • the intensity I (0.02) at a spatial frequency of 0.02 ⁇ m ⁇ 1 is 0.1 ⁇ m 4 or more and 1.5 ⁇ m 4 or less, and the intensity I (0.1) at a spatial frequency of 0.1 ⁇ m ⁇ 1 is 0.0001 ⁇ m 4. It is 0.01 ⁇ m 4 or more.
  • the intensity I (f 1 ) at a specific spatial frequency f 1 can be obtained by interpolation as shown in the equation (12). .
  • the anti-glare film of the present invention is whitish due to the synergistic effect of the haze described later and the average value of the inclination angle of the above-described surface unevenness by setting the intensity at the specific spatial frequency within a predetermined range. In addition, excellent antiglare properties are exhibited while preventing the occurrence of glare.
  • the strength I (0.01) is preferably 2.5 ⁇ m 4 or more and 9 ⁇ m 4 or less, more preferably 3 ⁇ m 4 or more and 8 ⁇ m 4 or less.
  • the intensity I (0.02) is preferably 0.2 [mu] m 4 or more 1.2 [mu] m 4 or less, more preferably 0.25 [mu] m 4 or more 1 [mu] m 4 or less, the intensity I (0.1) is 0.0003Myuemu 4 more 0.0075Myuemu 4 or less, and further preferably 0.0005 4 or 0.005 .mu.m 4 or less.
  • I (0.01) When I (0.01) is less than the above range, a swell of about 100 ⁇ m (corresponding to 0.01 ⁇ m ⁇ 1 in spatial frequency) contributing to the antiglare effect when the antiglare film is observed obliquely. Therefore, the antiglare property is insufficient.
  • I (0.01) exceeds the above range, the undulation with a period of about 100 ⁇ m becomes too large, the fine unevenness of the antiglare film becomes rough, and the haze tends to increase, which is not preferable.
  • I (0.02) When I (0.02) is less than the above range, a swell of a period of about 50 ⁇ m (corresponding to 0.02 ⁇ m ⁇ 1 in spatial frequency) contributing to the antiglare effect when the antiglare film is observed from the front.
  • the antiglare property is insufficient.
  • I (0.02) exceeds the above range, the undulation with a period of about 50 ⁇ m becomes too large and glare occurs.
  • I (0.1) is less than the above range, the short-period uneven shape of about 10 ⁇ m (corresponding to 0.1 ⁇ m ⁇ 1 in spatial frequency) is very small, and the surface uneven shape of the antiglare film is long-period. It is not preferable because the surface texture of the antiglare film becomes rough.
  • I (0.1) exceeds the above range, scattering due to surface irregularities having a short period of about 10 ⁇ m becomes strong, and whitening tends to occur.
  • the antiglare film of the present invention exhibits antiglare properties and prevents whitishness, so that the total haze with respect to normal incident light is in the range of 0.1% to 3%, and the surface haze is 0.1. % Or more and 2% or less.
  • the total haze of the antiglare film can be measured by a method based on the method described in JIS K7136. An image display device in which an antiglare film having a total haze or surface haze of less than 0.1% is not preferable because it does not exhibit sufficient antiglare properties.
  • the antiglare film is not preferable because the image display device on which the antiglare film is disposed will generate whiteness. .
  • such an image display device has a disadvantage that the contrast becomes insufficient.
  • the image display apparatus in which the antiglare film having the internal haze exceeding 2.5% has a tendency to decrease the contrast.
  • the antiglare film of the present invention preferably has a transmission clarity sum Tc of 375% or more determined under the following measurement conditions.
  • the sum Tc of transmitted sharpness is calculated by measuring the image sharpness using an optical comb having a predetermined width by a method based on JIS K 7105, and calculating the sum thereof. Specifically, five types of optical combs are used in which the ratio of the width of the dark part to the bright part is 1: 1 and the width is 0.125 mm, 0.25 mm, 0.5 mm, 1.0 mm, and 2.0 mm. The image definition is then measured, and the total is obtained as Tc.
  • the antiglare film of the present invention preferably has a reflection definition Rc (45) measured by incident light having an incident angle of 45 ° of 180% or less.
  • the reflection definition Rc (45) is measured by a method based on JIS K 7105, as in the case of Tc.
  • the width is 0.25 mm, 0.5 mm,
  • the image sharpness measured using four types of optical combs of 1.0 mm and 2.0 mm is measured, and the sum thereof is obtained as Rc (45).
  • Rc (45) is 180% or less, an image display device in which such an antiglare film is disposed is preferable because the antiglare property when observed from the front and oblique directions becomes better.
  • the lower limit of Rc (45) is not particularly limited, but is preferably 80% or more, for example, in order to satisfactorily suppress the occurrence of whitishness and glare.
  • the antiglare film of the present invention preferably has a reflection definition Rc (60) of 240% or less as measured with incident light having an incident angle of 60 °.
  • the reflection definition Rc (60) is measured by a method based on the same JIS K 7105 as the reflection definition Rc (45) except that the incident angle is changed.
  • Rc (60) is 240% or less, an image display device in which the antiglare film is disposed is preferable because the antiglare property when observed obliquely becomes better.
  • the lower limit of Rc (60) is not particularly limited, but is preferably, for example, 150% or more in order to better suppress the occurrence of whitish or glare.
  • the antiglare film of the present invention is produced, for example, as follows.
  • the first method is to prepare a fine unevenness forming mold in which a surface unevenness shape based on a predetermined pattern is formed on a molding surface, transfer the shape of the uneven surface of the mold to a transparent support, In this method, the transparent support on which the shape of the surface is transferred is peeled off from the mold.
  • the second method is to prepare a composition containing fine particles, a resin (binder) and a solvent, in which the fine particles are dispersed in a resin solution, apply the composition onto a transparent support, and dry as necessary. This is a method of curing the coating film (coating film containing fine particles) formed in (1).
  • the coating film thickness and the aggregation state of the fine particles are adjusted according to the composition of the composition, the drying conditions of the coating film, etc., thereby exposing the fine particles to the surface of the coating film, and transparent random irregularities. Form on the support.
  • the 1st method preferable as a manufacturing method of the anti-glare film of this invention is explained in full detail.
  • a prepared fine unevenness forming mold hereinafter sometimes abbreviated as “mold” is important.
  • the surface irregularity shape of the mold (hereinafter, sometimes referred to as “mold irregular surface”) is formed based on a predetermined pattern, and this predetermined pattern is the one-dimensional power spectrum.
  • the “pattern” means image data for forming the surface uneven shape of the antiglare layer of the antiglare film, a mask having a light transmitting part and a light shielding part, etc. ".
  • a method for defining a pattern for forming the surface irregularity shape of the antiglare layer of the antiglare film of the present invention will be described.
  • a method for obtaining a two-dimensional power spectrum of a pattern will be described, for example, when the pattern is image data.
  • the gradation is expressed by a two-dimensional function g (x, y).
  • the obtained two-dimensional function g (x, y) is Fourier-transformed as shown in the following formula (13) to calculate a two-dimensional function G (f x , f y ), and as shown in the following formula (14), the resulting two-dimensional function G (f x, f y) by squaring the absolute value of the obtained two-dimensional power spectrum ⁇ (f x, f y) .
  • x and y represent orthogonal coordinates in the image data plane.
  • f x and f y respectively represent the frequencies of the x and y directions, with the dimensions of the reciprocal of length.
  • ⁇ is a pi
  • i is an imaginary unit.
  • This two-dimensional power spectrum ⁇ (f x , f y ) represents the spatial frequency distribution of the pattern.
  • the pattern for anti-glare film manufacture of this invention also becomes isotropic. Therefore, two-dimensional function representing the two-dimensional power spectrum of the pattern gamma (f x, f y) can be represented by one-dimensional functions that depend only on the distance f from the origin (0,0) ⁇ (f).
  • two-dimensional function is a two-dimensional power spectrum of the gradation pattern ⁇ a (f x, f y) is displayed in polar coordinates by the equation (15).
  • ⁇ is a declination angle in Fourier space.
  • the one-dimensional function ⁇ (f) can be obtained by calculating the rotational average of the two-dimensional function ⁇ (fcos ⁇ , fsin ⁇ ) displayed in polar coordinates as shown in equation (16).
  • Two-dimensional function ⁇ (f x, f y) is a two-dimensional power spectrum of the gradation pattern one-dimensional function is determined from the rotational mean of gamma and (f), also referred to as a one-dimensional power spectrum gamma (f) in the following.
  • the intensity in the intensity gamma (0.01) and the spatial frequency 0.02 [mu] m -1 in the spatial frequency 0.01 [mu] m -1 of the one-dimensional power spectrum of the pattern gamma (0. 02) ratio ⁇ (0.02) / ⁇ (0.01) is 0.05 or more and 1.2 or less, and the intensity ⁇ (0.01) and the spatial frequency 0.1 ⁇ m at the spatial frequency 0.01 ⁇ m ⁇ 1 .
  • the ratio ⁇ (0.1) / ⁇ (0.01) of the intensity ⁇ (0.1) at ⁇ 1 is preferably 4 or more and 25 or less.
  • the two-dimensional function g (x, y) of gradation is usually obtained as a discrete function.
  • a two-dimensional power spectrum may be calculated by discrete Fourier transform.
  • the one-dimensional power spectrum of the pattern is obtained in the same manner from the two-dimensional power spectrum of the pattern.
  • the average value of the two-dimensional function g (x, y) is the maximum value of the two-dimensional function g (x, y) and the two-dimensional function. It is preferably 30 to 70% of the difference from the minimum value of g (x, y).
  • the two-dimensional function g (x, y) is a pattern aperture ratio.
  • the pattern aperture ratio here is defined.
  • the aperture ratio when the resist used in the lithography method is a positive resist means the ratio of the exposed area to the entire surface area of the coating film when image data is drawn on the coating film of the positive resist.
  • the aperture ratio when the resist used in the lithography method is a negative resist means the ratio of the unexposed area to the entire surface area of the coating film when image data is drawn on the coating film of the negative resist.
  • the aperture ratio when the lithography method is batch exposure means the ratio of the light-transmitting portion of the mask having the light-transmitting portion and the light-shielding portion.
  • each of the intensity ratios ⁇ (0.02) / ⁇ (0.01) and ⁇ (0.1) / ⁇ (0.01) of the one-dimensional power spectrum of the pattern is In this range, a desired mold can be manufactured, and the first method using the mold can be manufactured.
  • a random brightness distribution whose density is determined by a pattern created by randomly arranging dots or a random number or a pseudo-random number generated by a computer is used.
  • a pattern (preliminary pattern) having the predetermined spatial frequency range is removed from the preliminary pattern.
  • the preliminary pattern may be passed through a band pass filter.
  • a mold uneven surface for transferring the surface uneven shape formed based on the predetermined pattern to a transparent support. is manufactured.
  • the first method using such a mold is an embossing method characterized by producing an antiglare layer on a transparent support. Examples of the embossing method include a photoembossing method using a photocurable resin and a hot embossing method using a thermoplastic resin.
  • the photo-embossing method is preferable from the viewpoint of productivity.
  • a photocurable resin layer is formed on a transparent support (the surface of the transparent support), and the photocurable resin layer is cured while being pressed against the uneven surface of the mold.
  • This is a method of transferring the shape of the uneven surface of the mold to the photocurable resin layer. Specifically, in a state in which a photocurable resin layer formed by applying a photocurable resin on a transparent support is in close contact with the uneven surface of the mold, light is emitted from the transparent support side (the light is photocurable).
  • a photocurable resin (photocurable resin contained in the photocurable resin layer) is cured by irradiating with a resin that can cure the resin, and then the cured photocurable resin layer is formed.
  • the support is peeled from the mold.
  • the cured photocurable resin layer becomes an antiglare layer.
  • an ultraviolet curable resin is preferable as the photocurable resin, and when the ultraviolet curable resin is used, ultraviolet light is used as the irradiation light (the ultraviolet curable resin is used as the photocurable resin).
  • the embossing method using a functional resin is hereinafter referred to as “UV embossing method”).
  • a polarizing film may be used as a transparent support, and the transparent support may be replaced with a polarizing film in the embossing method described here.
  • the kind of the ultraviolet curable resin used for the UV embossing method is not particularly limited, and an appropriate one can be used from commercially available resins according to the kind of transparent support to be used and the kind of ultraviolet light.
  • Such an ultraviolet curable resin is a concept including a monomer (polyfunctional monomer), an oligomer and a polymer that are photopolymerized by ultraviolet irradiation, and a mixture thereof.
  • a resin that can be cured even with visible light having a wavelength longer than that of ultraviolet rays can be used by using a combination of photoinitiators appropriately selected according to the type of the ultraviolet curable resin.
  • a description of suitable examples of the ultraviolet curable resin will be given later.
  • the transparent support used in the UV embossing method for example, glass or plastic film can be used. Any plastic film can be used as long as it has appropriate transparency and mechanical strength.
  • These transparent resin films may be solvent cast films or extruded films.
  • the thickness of the transparent support is, for example, 10 to 500 ⁇ m, preferably 10 to 100 ⁇ m, and more preferably 10 to 60 ⁇ m. When the thickness of the transparent support is within this range, an antiglare film having sufficient mechanical strength tends to be obtained, and the image display device provided with the antiglare film is more unlikely to cause glare. .
  • the hot embossing method a transparent resin film formed of a thermoplastic resin is pressed against a mold uneven surface while being heated and softened, and the surface uneven shape of the mold uneven surface is transferred to the transparent resin film. Is the method.
  • the transparent resin film used for the hot embossing method may be any material as long as it is substantially optically transparent. Specifically, examples include those exemplified as the transparent resin film used for the UV embossing method. Can do.
  • a method for manufacturing a mold used for the embossing method will be described. As for the mold manufacturing method, the molding surface of the mold can transfer the surface uneven shape formed based on the above-described predetermined pattern onto the transparent support (the surface uneven shape formed based on the predetermined pattern). In order to produce the anti-glare layer having an uneven surface with high accuracy and good reproducibility, a lithography method is preferred.
  • the lithography method includes [1] first plating step, [2] polishing step, [3] photosensitive resin film forming step, [4] exposure step, [5] development step, and [6]. It is preferable to include an etching step, a [7] photosensitive resin film peeling step, and an [8] second plating step.
  • FIG. 7 is a view schematically showing a preferred example of the first half of the mold manufacturing method. FIG. 7 schematically shows a cross section of the mold in each step.
  • die for anti-glare film manufacture of this invention is demonstrated in detail, referring FIG.
  • a base material (mold base material) used for mold production is prepared, and copper plating is applied to the surface of the mold base material.
  • copper plating has a high covering property and a strong smoothing action, so that a flat and glossy surface can be formed by filling minute irregularities and voids of the mold base. Therefore, by performing copper plating on the mold substrate surface in this way, even if chromium plating is performed in the second plating step described later, it is caused by minute irregularities and voids existing on the substrate.
  • the rough surface of the chrome plating that appears is eliminated, and the occurrence of fine cracks is reduced due to the high coverage of the copper plating. Therefore, even if a surface irregularity shape (fine irregularity surface shape) based on a predetermined pattern is created on the mold substrate molding surface, the influence of the surface (mold substrate) surface such as minute irregularities, voids, cracks, etc. Can be prevented sufficiently.
  • As copper used for the copper plating in the first plating step pure copper metal or an alloy containing copper as a main component (copper alloy) may be used. Therefore, “copper” used for copper plating is a concept including copper and a copper alloy.
  • the copper plating may be electrolytic plating or electroless plating, but the copper plating in the first plating step is preferably electrolytic plating.
  • the preferable plating layer in the first plating step is not limited to a copper plating layer but may be a laminate of a copper plating layer and a plating layer made of a metal other than copper. If the plating layer formed by applying copper plating on the surface of the mold base is too thin, the influence of the underlying surface (fine irregularities, voids, cracks, etc.) cannot be eliminated, so the thickness is 50 ⁇ m. The above is preferable.
  • the upper limit of the plating layer thickness is not critical, but is preferably about 500 ⁇ m or less in consideration of cost and the like.
  • the mold base is preferably a base made of a metal material.
  • the metal material is preferably aluminum or iron.
  • a lightweight aluminum base is particularly preferable as the mold base.
  • aluminum and iron here do not need to be a pure metal, respectively, and may be an alloy containing aluminum or iron as a main component.
  • the shape of the base material for molds should just be an appropriate shape according to the manufacturing method of the anti-glare film of this invention. Specifically, it is selected from a flat substrate, a columnar substrate, a cylindrical (roll shape) substrate, and the like. When manufacturing the anti-glare film of this invention continuously, it is preferable in a metal mold
  • Such a mold is manufactured from a roll-shaped mold substrate.
  • Polishing Step In the subsequent polishing step, the surface (plating layer) of the mold base that has been subjected to copper plating in the first plating step described above is polished.
  • polish In the manufacturing method of the metal mold
  • Commercial products such as flat and roll-shaped substrates used as mold substrates are often subjected to machining such as cutting and grinding to achieve the desired accuracy. Fine processed marks remain on the substrate surface. Therefore, even if a plating (preferably copper plating) layer is formed by the first plating step, the processed marks may remain.
  • the surface of the mold base is not always completely smooth. That is, even when the mold substrate having a surface with such deep processed marks remaining thereon is subjected to the steps [3] to [8] described later, the surface irregularity shape of the obtained mold surface is obtained. May differ from the surface uneven shape based on the predetermined pattern, or may include unevenness derived from the processed eyes.
  • the target optical characteristics such as anti-glare property cannot be sufficiently exhibited, and there is a possibility of unexpected influence.
  • the polishing method applied in the polishing step is not particularly limited, and a polishing method according to the shape and properties of the mold base material to be polished is selected.
  • Specific examples of the polishing method applicable to the polishing step include a mechanical polishing method, an electrolytic polishing method, and a chemical polishing method.
  • the mechanical polishing method any of super finishing method, lapping, fluid polishing method, buff polishing method and the like can be used.
  • the surface of the base material for molds as a mirror surface by carrying out mirror surface cutting using a cutting tool in a grinding
  • the surface roughness after polishing is preferably 0.1 ⁇ m or less, and more preferably 0.05 ⁇ m or less, expressed as a centerline average roughness Ra based on JIS B 0601.
  • the center line average roughness Ra after polishing is larger than 0.1 ⁇ m, there is a possibility that the influence of the surface roughness remains on the mold uneven surface of the finally obtained mold.
  • the lower limit of the center line average roughness Ra is not particularly limited. Therefore, the lower limit may be determined from the viewpoint of processing time (polishing time) and processing cost in the polishing process.
  • FIG. 7 schematically shows a state in which the photosensitive resin film 50 is formed on the surface 41 of the mold base 40 (FIG. 7B).
  • the photosensitive resin conventionally known photosensitive resins can be used, and those already marketed as resists can be used as they are or after being purified by filtration or the like as necessary.
  • a negative photosensitive resin having a property of curing a photosensitive part a monomer or prepolymer of a (meth) acrylic acid ester having an acryloyl group or a methacryloyl group in a molecule, a mixture of bisazide and a diene rubber Polyvinyl cinnamate compounds and the like can be used.
  • a positive photosensitive resin having a property that a photosensitive portion is eluted by development and only an unexposed portion remains a phenol resin type or a novolac resin type can be used.
  • Such a positive or negative photosensitive resin can also be easily obtained from the market as a positive resist or a negative resist.
  • the photosensitive resin solution may contain various additives such as a sensitizer, a development accelerator, an adhesion modifier, and a coating property improver, if necessary. What mixed with the commercially available resist can also be used as a photosensitive resin solution.
  • an optimum solvent is selected to form a smoother photosensitive resin film, and the photosensitive resin is dissolved in the solvent.
  • a photosensitive resin solution obtained by dilution is preferable to use. Such a solvent is further selected depending on the type of the photosensitive resin and its solubility.
  • a cellosolve solvent, a propylene glycol solvent, an ester solvent, an alcohol solvent, a ketone solvent, a highly polar solvent, or the like is selected.
  • an optimal resist may be selected and used as a photosensitive resin solution depending on the type of the solvent contained in the resist or by conducting an appropriate preliminary experiment.
  • the method of applying the photosensitive resin solution to the mirror-polished surface of the mold base is as follows: meniscus coating, fountain coating, dip coating, spin coating, roll coating, wire bar coating, air knife coating, blade coating, curtain The method is selected from known methods such as coating and ring coating according to the shape of the mold base.
  • the thickness of the photosensitive resin film after coating is preferably in the range of 1 to 10 ⁇ m, more preferably in the range of 6 to 9 ⁇ m, as the thickness after drying.
  • Exposure Step is a step of transferring the target pattern to the photosensitive resin film 50 by exposing the photosensitive resin film 50 formed in the above-described photosensitive resin film forming step. is there.
  • the light source used in the exposure process may be appropriately selected according to the photosensitive wavelength and sensitivity of the photosensitive resin contained in the photosensitive resin film. For example, the g-line (wavelength: 436 nm) and h-line (wavelength: high-pressure mercury lamp).
  • the exposure method may be a batch exposure method using a mask corresponding to a target pattern, or a drawing method.
  • the target pattern is the spatial frequency intensity ratio ⁇ (0.02) / ⁇ (0.01) and ⁇ (0.1) / ⁇ (0.01) of the one-dimensional power spectrum. Is set to a predetermined preferable range.
  • the mold manufacturing method it is preferable to expose the target pattern on the photosensitive resin film in a precisely controlled state in order to form the surface uneven shape of the mold with higher accuracy.
  • a target pattern is created as image data on a computer, and a pattern based on the image data is formed on the photosensitive resin film by laser light emitted from a computer-controlled laser head. It is preferable to draw (laser drawing).
  • FIG. 7C schematically shows a state in which the pattern is exposed to the photosensitive resin film 50.
  • the photosensitive resin film 50 contains a negative photosensitive resin (for example, when a negative resist is used as the photosensitive resin solution)
  • the exposed region 51 receives the exposure energy and receives the photosensitive resin.
  • the crosslinking reaction proceeds and the solubility in the developer described later is lowered.
  • the unexposed area 52 in the development process is dissolved by the developer, and only the exposed area 51 remains on the surface of the base material to become the mask 60.
  • the photosensitive resin film 50 contains a positive photosensitive resin (for example, when a positive resist is used as the photosensitive resin solution)
  • the exposed region 51 receives the exposure energy and is exposed to light.
  • the bonding of the functional resin is broken, it is easily dissolved in the developer described later. Therefore, the area 51 exposed in the development process is dissolved by the developer, and only the unexposed area 52 remains on the substrate surface to become the mask 60.
  • the developer includes inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; primary amines such as ethylamine and n-propylamine; Secondary amines such as n-butylamine; tertiary amines such as triethylamine and methyldiethylamine; alcohol amines such as dimethylethanolamine and triethanolamine; tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylhydroxyethylammonium Quaternary ammonium compounds such as hydroxide; alkaline aqueous solutions such as cyclic amines such as pyrrole and pihelidine; and organic solvents such as xylene and toluene.
  • inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous
  • FIG. 7D schematically shows a state after the development process is performed using a negative type photosensitive resin.
  • the unexposed region 52 is dissolved by the developer, and only the exposed region 51 remains on the substrate surface, and the photosensitive resin film in this region becomes the mask 60.
  • FIG. 7E schematically shows a state after the development process is performed using a positive type photosensitive resin. In FIG. 7E, the exposed region 51 is dissolved by the developer, and only the unexposed region 52 remains on the substrate surface, and the photosensitive resin film in this region becomes the mask 60.
  • FIG. 8 is a diagram schematically showing a preferred example of the latter half of the mold manufacturing method.
  • FIG. 8A schematically shows a state after the plating layer mainly having no mask is etched by the etching process.
  • the plating layer under the mask 60 is not etched because the photosensitive resin film functions as the mask 60, but the etching from the region 45 without the mask proceeds with the progress of etching.
  • the plating layer under the mask 60 is also etched.
  • the etching of the plating layer under the mask 60 in the vicinity of the boundary between the region with the mask 60 and the region 45 without the mask is called side etching.
  • Etching treatment in the etching step is usually performed using an etching solution such as ferric chloride (FeCl 3 ) solution, cupric chloride (CuCl 2 ) solution, alkaline etching solution (Cu (NH 3 ) 4 Cl 2 ), This is mainly performed by corroding a plating layer (metal surface) in a region where the mask 60 is not provided on the surface of the mold base.
  • etching treatment a strong acid such as hydrochloric acid or sulfuric acid can be used as an etching solution.
  • a strong acid such as hydrochloric acid or sulfuric acid
  • reverse electrolytic etching is performed by applying a potential opposite to that at the time of electrolytic plating.
  • Etching treatment can also be performed using.
  • the surface irregularities formed on the mold base material when the etching process is performed are the constituent material (metal material) or plating layer type of the mold base material, the type of photosensitive resin film, and the etching process. Since it differs depending on the type of etching process, etc., it cannot be generally stated.
  • the etching amount is 10 ⁇ m or less, the etching is performed approximately isotropically from the surface of the mold substrate in contact with the etching solution.
  • the etching amount here is the thickness of the plating layer that is scraped off by etching.
  • the etching amount in the etching step is preferably 1 to 12 ⁇ m, more preferably 5 to 8 ⁇ m.
  • the etching amount exceeds 12 ⁇ m, the unevenness of the surface formed on the mold has a large unevenness of the unevenness.
  • the ratio R SCE / R SCI may exceed 0.1.
  • the etching amount in the etching process is 12 ⁇ m or less, and the mold is manufactured through the process described later, and further, the occurrence of whitening is sufficiently prevented by manufacturing the antiglare film using the mold. Can be obtained.
  • the etching amount is less than 1 ⁇ m, the surface unevenness shape is hardly formed on the mold, and the mold has a substantially flat surface. Therefore, an antiglare film is manufactured using the mold. However, since such an antiglare film has almost no surface irregularity shape, a sufficient antiglare film cannot be obtained.
  • the etching process in the etching step may be performed by one etching process, or the etching process may be performed twice or more.
  • Photosensitive resin film peeling step is a step of acting as a mask 60 in the etching step to remove the photosensitive resin film remaining on the mold substrate. It is preferable to completely remove the photosensitive resin film remaining on the mold base. In the photosensitive resin film peeling step, it is preferable to dissolve the photosensitive resin film using a peeling solution.
  • the stripper those prepared by changing the concentration and pH of the developer exemplified as the developer can be used.
  • FIG. 8B schematically shows a state where the photosensitive resin film used as the mask 60 in the etching process is completely dissolved and removed by the photosensitive resin film peeling process.
  • the first surface uneven shape 46 is formed on the surface of the mold base by the mask 60 made of the photosensitive resin film and the etching process.
  • Second plating step The final stage of the mold production is a second step in which plating (preferably, chromium plating described later) is performed on the surface of the mold substrate that has undergone the steps [6] and [7]. It is a plating process.
  • plating preferably, chromium plating described later
  • the uneven surface shape 46 of the mold base can be blunted, and the mold surface can be protected by the plating.
  • dulling the uneven surface shape of the mold base is referred to as “shape blunting”.
  • FIG. 8 (c) the surface uneven shape is blunted by forming the chromium plating layer 71 on the first surface uneven shape 46 formed by the etching process as described above (mold uneven surface 70). Shows the state.
  • the plating layer formed by the second plating step is preferably chromium plating in that it has gloss, high hardness, a low friction coefficient, and good release properties.
  • chromium platings chromium plating that expresses good gloss, so-called glossy chromium plating or decorative chromium plating, is particularly preferable.
  • Chromium plating is usually carried out by electrolysis, and as the plating bath, an aqueous solution containing chromic anhydride (CrO 3 ) and a small amount of sulfuric acid is used as the plating solution. By adjusting the current density and electrolysis time, the thickness of the chromium plating layer can be controlled.
  • die for glare-proof film manufacture of this invention is obtained by performing the metal plating in a 2nd plating process, Preferably chromium plating.
  • a 2nd plating process Preferably chromium plating.
  • chrome plating on the surface irregularities on the surface of the mold substrate after the etching treatment, the mold can be blunted and a mold whose surface hardness is increased can be obtained.
  • the greatest factor in controlling the degree of shape blunting is the thickness of the chromium plating layer. If the thickness is small, the degree of shape blunting becomes insufficient, and the antiglare film obtained using such a mold may be whitish.
  • the thickness of the chromium plating layer is preferably in the range of 10 to 20 ⁇ m, and more preferably in the range of 12 to 16 ⁇ m.
  • the chromium plating layer formed in the second plating step is preferably formed so as to have a Vickers hardness of 800 or more, and more preferably 1000 or more.
  • the chrome plating layer has a Vickers hardness of less than 800, when the antiglare film is produced using the mold, the durability of the mold tends to decrease.
  • the said photoembossing method preferable as a method for manufacturing the anti-glare film of this invention is demonstrated.
  • the UV embossing method is particularly preferable as the photoembossing method.
  • the embossing method using an active energy ray-curable resin will be specifically described.
  • [P1] A coating process in which a coating liquid containing an active energy ray-curable resin is coated on a transparent support that is continuously conveyed to form a coating layer
  • [P2] a coating layer It is preferable to include a main curing step of irradiating active energy rays from the transparent support side with the surface of the mold pressed against the surface of the mold.
  • FIG. 9 is a diagram schematically showing a preferred example of a production apparatus used in the method for producing an antiglare film of the present invention.
  • the arrow in FIG. 9 shows the conveyance direction of a film, or the rotation direction of a roll.
  • a coating liquid containing an active energy ray-curable resin is coated on a transparent support to form a coating layer.
  • a coating liquid containing an active energy ray-curable resin composition is applied in the coating zone 83 to the transparent support 81 that is fed from the feed roll 80.
  • Coating of the coating liquid on the transparent support 81 can be performed by, for example, a gravure coating method, a micro gravure coating method, a rod coating method, a knife coating method, an air knife coating method, a kiss coating method, a die coating method, or the like. .
  • the transparent support 81 only needs to be translucent, and for example, glass or plastic film can be used.
  • the plastic film only needs to have appropriate transparency and mechanical strength. Specifically, any of those already exemplified as the transparent support for use in the UV embossing method can be used. Further, in order to continuously produce the antiglare film of the present invention by the photoembossing method, an appropriate flexibility is obtained. Those having sex are selected.
  • the surface of the transparent support 81 (surface on the coating layer side) may be subjected to various surface treatments. Good.
  • the surface treatment examples include corona discharge treatment, glow discharge treatment, acid surface treatment, alkali surface treatment, and ultraviolet irradiation treatment. Further, another layer such as a primer layer may be formed on the transparent support 81, and a coating solution may be applied on the other layer.
  • the surface (coating layer and Is preferably hydrophilized by various surface treatments. This surface treatment may be performed after the production of the antiglare film.
  • the coating liquid contains an active energy ray-curable resin and usually further contains a photopolymerization initiator (radical polymerization initiator).
  • Active energy ray curable resin As an active energy ray curable resin, what contains a polyfunctional (meth) acrylate compound can be used preferably, for example.
  • the polyfunctional (meth) acrylate compound is a compound having at least two (meth) acryloyloxy groups in the molecule.
  • polyfunctional (meth) acrylate compound examples include, for example, ester compounds of polyhydric alcohol and (meth) acrylic acid, urethane (meth) acrylate compounds, polyester (meth) acrylate compounds, epoxy (meth) acrylate compounds, and the like. And a polyfunctional polymerizable compound containing two or more (meth) acryloyl groups.
  • polyhydric alcohol examples include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, polypropylene glycol, propanediol, butanediol, and pentanediol.
  • Hexanediol Hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, 2,2'-thiodiethanol, divalent alcohols such as 1,4-cyclohexanedimethanol; trimethylolpropane, glycerol, pentaerythritol , Trihydric or higher alcohols such as diglycerol, dipentaerythritol and ditrimethylolpropane.
  • esterified products of polyhydric alcohol and (meth) acrylic acid include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and neopentyl glycol.
  • Examples of the urethane (meth) acrylate compound include a urethanization reaction product of an organic isocyanate having a plurality of isocyanate groups in one molecule and a (meth) acrylic acid derivative having a hydroxyl group.
  • Examples of organic isocyanates having a plurality of isocyanate groups in one molecule include two isocyanates in one molecule such as hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, naphthalene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, and dicyclohexylmethane diisocyanate.
  • Organic isocyanate having a group organic isocyanate having three isocyanate groups in one molecule obtained by subjecting these organic isocyanates to isocyanurate modification, adduct modification, biuret modification, and the like.
  • examples of the (meth) acrylic acid derivative having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2- Examples include hydroxy-3-phenoxypropyl (meth) acrylate and pentaerythritol triacrylate.
  • a preferable polyester (meth) acrylate compound is a polyester (meth) acrylate obtained by reacting a hydroxyl group-containing polyester with (meth) acrylic acid.
  • the hydroxyl group-containing polyester preferably used is a hydroxyl group-containing polyester obtained by an esterification reaction of a polyhydric alcohol, a carboxylic acid, a compound having a plurality of carboxyl groups, and / or an anhydride thereof.
  • the polyhydric alcohol include the same compounds as those described above.
  • bisphenol A etc. are mentioned as phenols other than a polyhydric alcohol.
  • the carboxylic acid include formic acid, acetic acid, butyl carboxylic acid, benzoic acid and the like.
  • the compounds having a plurality of carboxyl groups and / or anhydrides thereof include maleic acid, phthalic acid, fumaric acid, itaconic acid, adipic acid, terephthalic acid, maleic anhydride, phthalic anhydride, trimellitic acid, cyclohexanedicarboxylic anhydride Thing etc. are mentioned.
  • polyfunctional (meth) acrylate compounds as described above hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, diethylene glycol di (meta) from the viewpoint of improving the strength of the cured product and availability.
  • Ester compounds such as acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate; hexamethylene diisocyanate and 2-hydroxyethyl Adduct of (meth) acrylate; adduct of isophorone diisocyanate and 2-hydroxyethyl (meth) acrylate; of tolylene diisocyanate and 2-hydroxyethyl (meth) acrylate Adducts; adduct adduct modified isophorone diisocyanate with 2-hydroxyethyl (meth) acrylate; and adducts with biuret of isophorone diisocyanate and 2-hydroxyethyl (meth) acrylate.
  • the active energy ray curable resin may contain a monofunctional (meth) acrylate compound in addition to the polyfunctional (meth) acrylate compound.
  • the monofunctional (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) ) Acrylate, 2-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycidyl (meth) acrylate, acryloylmorpholine , N-vinylpyrrolidone, tetrahydrofurfuryl (
  • the active energy ray-curable resin may contain a polymerizable oligomer.
  • the polymerizable oligomer is, for example, the polyfunctional (meth) acrylate compound, that is, an ester compound of a polyhydric alcohol and (meth) acrylic acid, a urethane (meth) acrylate compound, a polyester (meth) acrylate compound, or an epoxy (meth). It can be an oligomer such as a dimer, trimer or the like such as an acrylate.
  • polymerizable oligomers include urethane (meth) acrylate oligomers obtained by reacting polyisocyanates having at least two isocyanate groups in the molecule with polyhydric alcohols having at least one (meth) acryloyloxy group.
  • polyisocyanate examples include hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, and a polymer of xylylene diisocyanate.
  • the polyhydric alcohol having at least one (meth) acryloyloxy group includes Hydroxyl group-containing (meth) acrylic acid ester obtained by esterification reaction of alcohol and (meth) acrylic acid, and as polyhydric alcohol, for example, 1,3-butanediol, 1,4-butanediol, 1,6 -Hexanediol, diethylene glycol, triethylene glycol, neopentyl glycol, polyethylene glycol, polypropylene glycol, trimethylolpropane, glycerin, pentaerythritol, What is pentaerythritol.
  • this polyhydric alcohol having at least one (meth) acryloyloxy group a part of the alcoholic hydroxyl group of the polyhydric alcohol is esterified with (meth) acrylic acid, and the alcoholic hydroxyl group is present in the molecule. It remains.
  • a polyester (meta) obtained by reacting a compound having a plurality of carboxyl groups and / or an anhydride thereof with a polyhydric alcohol having at least one (meth) acryloyloxy group.
  • Acrylate oligomers a polyester (meta) obtained by reacting a compound having a plurality of carboxyl groups and / or an anhydride thereof with a polyhydric alcohol having at least one (meth) acryloyloxy group.
  • Examples of the compound having a plurality of carboxyl groups and / or anhydrides thereof are the same as those described for the polyester (meth) acrylate of the polyfunctional (meth) acrylate compound.
  • Examples of the polyhydric alcohol having at least one (meth) acryloyloxy group include those described for the urethane (meth) acrylate oligomer.
  • further examples of urethane (meth) acrylate oligomers are obtained by reacting isocyanates with hydroxyl groups of a hydroxyl group-containing polyester, a hydroxyl group-containing polyether or a hydroxyl group-containing (meth) acrylic acid ester.
  • the hydroxyl group-containing polyester preferably used is a hydroxyl group-containing polyester obtained by an esterification reaction of a polyhydric alcohol, a carboxylic acid, a compound having a plurality of carboxyl groups, and / or an anhydride thereof.
  • Examples of the polyhydric alcohol and the compound having a plurality of carboxyl groups and / or anhydrides thereof are the same as those described for the polyester (meth) acrylate compound of the polyfunctional (meth) acrylate compound.
  • the hydroxyl group-containing polyether preferably used is a hydroxyl group-containing polyether obtained by adding one or more alkylene oxides and / or ⁇ -caprolactone to a polyhydric alcohol.
  • the polyhydric alcohol may be the same as that which can be used for the hydroxyl group-containing polyester.
  • the hydroxyl group-containing (meth) acrylic acid ester preferably used include the same as those described for the polymerizable oligomeric urethane (meth) acrylate oligomer.
  • isocyanates compounds having one or more isocyanate groups in the molecule are preferable, and divalent isocyanate compounds such as tolylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate are particularly preferable. These polymerizable oligomer compounds can be used alone or in combination of two or more.
  • Photoinitiator A photoinitiator can be suitably selected according to the kind of active energy ray applied to anti-glare film manufacture of this invention. Moreover, when using an electron beam as an active energy ray, the coating liquid which does not contain a photoinitiator may be used for anti-glare film manufacture of this invention.
  • the photopolymerization initiator include acetophenone photopolymerization initiator, benzoin photopolymerization initiator, benzophenone photopolymerization initiator, thioxanthone photopolymerization initiator, triazine photopolymerization initiator, and oxadiazole photopolymerization initiator. An initiator or the like is used.
  • photopolymerization initiator examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2 '-Biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compound and the like can also be used.
  • the amount of the photopolymerization initiator used is usually 0.5 to 20 parts by weight, preferably 1 to 5 parts by weight with respect to 100 parts by weight of the active energy ray-curable resin.
  • the coating liquid may contain a solvent such as an organic solvent in order to improve the coating property on the transparent support.
  • organic solvents examples include aliphatic hydrocarbons such as hexane, cyclohexane, and octane; aromatic hydrocarbons such as toluene and xylene; alcohols such as ethanol, 1-propanol, isopropanol, 1-butanol, and cyclohexanol; methyl ethyl ketone, methyl isobutyl Ketones such as ketone and cyclohexanone; esters such as ethyl acetate, butyl acetate and isobutyl acetate; glycols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether Ethers; ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, etc.
  • aliphatic hydrocarbons such
  • Stealted glycol ethers such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol; 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol, 2- (2- It can be selected from carbitols such as butoxyethoxy) ethanol in consideration of viscosity and the like.
  • These solvents may be used alone or as a mixture of several kinds as required. After coating, it is necessary to evaporate the organic solvent. Therefore, the boiling point is desirably in the range of 60 ° C to 160 ° C.
  • the saturated vapor pressure at 20 ° C. is preferably in the range of 0.1 kPa to 20 kPa.
  • a coating liquid contains a solvent
  • the drying temperature is appropriately selected depending on the solvent used and the type of transparent support. Generally, it is in the range of 20 ° C. to 120 ° C., but is not limited thereto. When there are a plurality of drying furnaces, the temperature may be changed for each drying furnace.
  • the thickness of the coating layer after drying is preferably 1 to 30 ⁇ m. Thus, a laminate in which the transparent support and the coating layer are laminated is formed.
  • Curing step This step is performed by irradiating the surface of the coating layer with active energy rays from the transparent support side in a state where the mold uneven surface (molded surface) having a desired surface uneven shape is pressed. It is a step of forming a cured resin layer on the transparent support by curing the work layer. Thereby, the coating layer is cured, and the surface irregularity shape of the mold irregularity surface is transferred to the coating layer surface.
  • the mold used here is of a roll shape, and is manufactured by using a roll-shaped mold substrate in the mold manufacturing method already described. For example, as shown in FIG.
  • this step is performed by a coating zone 83 (in the case of drying, a drying zone 84, and in the case of performing a pre-curing step described later, the active energy ray irradiation device 86 is further irradiated. Irradiating the laminated body having the coating layer that has passed through the pre-curing zone) with an active energy ray using an active energy ray irradiating device 86 such as an ultraviolet ray irradiating device disposed on the transparent support 81 side. Can be performed.
  • a roll-shaped mold 87 is pressed against the surface of the coating layer of the laminate that has undergone the curing process using a crimping device such as a nip roll 88, and in this state, the active energy ray irradiation device 86 is used to make the transparent
  • the coating layer 82 is cured by irradiating active energy rays from the support 81 side.
  • curing the coating layer means that the active energy ray-curable resin contained in the coating layer receives the energy of the active energy ray to cause a curing reaction.
  • the use of the nip roll is effective in preventing air bubbles from being mixed between the coating layer of the laminate and the mold.
  • One or a plurality of active energy ray irradiation apparatuses can be used. After irradiation with the active energy ray, the laminate is peeled from the mold 87 with the nip roll 89 on the outlet side as a fulcrum. In the obtained transparent support and the cured coating layer, the cured coating layer becomes an antiglare layer, and the antiglare film of the present invention is obtained.
  • the obtained antiglare film is usually wound up by a film winding device 90. At this time, for the purpose of protecting the antiglare layer, it may be wound up while a protective film made of polyethylene terephthalate, polyethylene or the like is adhered to the surface of the antiglare layer through a pressure-sensitive adhesive layer having removability.
  • the active energy ray used in this step is appropriately selected from ultraviolet rays, electron beams, near ultraviolet rays, visible light, near infrared rays, infrared rays, X-rays and the like according to the type of the active energy ray curable resin contained in the coating liquid.
  • ultraviolet rays and electron beams are preferable, and ultraviolet rays are particularly preferable because they are easy to handle and high energy is obtained (as described above, the UV embossing method is preferable).
  • a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, an electrodeless lamp, a metal halide lamp, a xenon arc lamp, or the like can be used.
  • An ArF excimer laser, a KrF excimer laser, an excimer lamp, synchrotron radiation, or the like can also be used.
  • an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, an electrodeless lamp, a xenon arc lamp, and a metal halide lamp are preferably used.
  • the electron beam 50 to 1000 keV emitted from various electron beam accelerators such as Cockloft Walton type, Bande graph type, resonance transformation type, insulation core transformation type, linear type, dynamitron type, and high frequency type, preferably 100
  • An electron beam having an energy of ⁇ 300 keV can be mentioned.
  • the active energy ray is ultraviolet
  • the integrated amount of light at UVA ultraviolet is preferably at 100 mJ / cm 2 or more 3000 mJ / cm 2 or less, more preferably at 200 mJ / cm 2 or more 2000 mJ / cm 2 or less.
  • the transparent support may absorb ultraviolet rays on the short wavelength side, irradiation is performed so that the integrated light quantity of ultraviolet rays UVV (395 to 445 nm) in the wavelength region including visible light is preferable for the purpose of suppressing the absorption.
  • the amount may be adjusted.
  • Integrated light intensity in such UVV is preferably at 100 mJ / cm 2 or more 3000 mJ / cm 2 or less, and more preferably 200 mJ / cm 2 or more 2000 mJ / cm 2 or less.
  • an end region 82b in the width direction of the coating layer is a region having a predetermined width from the end portion including the end portion of the coating layer.
  • the end region is cured in advance, thereby further improving the adhesion with the transparent support 81 in the end region, and part of the cured resin is peeled off in the step after the curing step. It can prevent falling and contaminating the process.
  • the end region 82b can be a region from 5 mm to 50 mm from the end of the coating layer 82, for example.
  • the irradiation of the active energy ray to the end region of the coating layer is performed, for example, with reference to FIGS. 9 and 10, for example, the coating layer that has passed through the coating zone 83 (drying zone 84 when drying).
  • This is performed by irradiating the transparent support 81 having 82 with active energy rays using an active energy ray irradiating device 85 such as an ultraviolet ray irradiating device installed in the vicinity of both ends on the coating layer 82 side.
  • the active energy ray irradiation device 85 may be any device as long as it can irradiate the end region 82b of the coating layer 82 with active energy rays, and may be installed on the transparent support 81 side.
  • the type of active energy ray and the light source are the same as in the main curing step.
  • the integrated amount of light at UVA ultraviolet is preferably at 10 mJ / cm 2 or more 400 mJ / cm 2 or less, and more preferably 50 mJ / cm 2 or more 400 mJ / cm 2 or less.
  • the antiglare film of the present invention obtained as described above is used for an image display device or the like, and is usually used by being bonded to a polarizing film as a viewing side protective film of a viewing side polarizing plate (that is, an image). Placed on the surface of the display device).
  • an antiglare film integrated with a polarizing film is obtained. Therefore, such an antiglare film integrated with a polarizing film may be used for an image display device. it can.
  • the image display device provided with the antiglare film of the present invention has sufficient antiglare properties at a wide viewing angle, and can well prevent both whitening and glare.
  • an optically transparent pressure-sensitive adhesive was used, and the surface opposite to the antiglare layer of the measurement sample was bonded to a glass substrate, and then subjected to measurement.
  • the objective lens was measured at a magnification of 10 times.
  • the horizontal resolutions ⁇ x and ⁇ y were both 1.66 ⁇ m and the measurement area was 1270 ⁇ m ⁇ 950 ⁇ m.
  • Sampling 512 ⁇ 512 data (measured area 850 ⁇ m ⁇ 850 ⁇ m) from the center of the obtained measurement data, the elevation of the surface uneven shape (surface uneven shape of the antiglare layer) of the antiglare film is two-dimensional
  • the function h (x, y) was obtained.
  • Two-dimensional function h (x, y) of the discrete Fourier transform to two-dimensional function H (f x, f y) was determined.
  • Two-dimensional function H (f x, f y) of a two-dimensional function I (f x, f y) of the absolute value squared by the two-dimensional power spectrum to calculate the one-dimensional power is a function of the distance f from the origin
  • a one-dimensional function I (f) of the spectrum was calculated.
  • the elevation is measured for five surface irregularities for each sample, and the average value of the one-dimensional function I (f) of the one-dimensional power spectrum calculated from the data is obtained as the one-dimensional function I of the one-dimensional power spectrum of each sample. (F).
  • the internal haze was measured in the same manner as the total haze after a triacetyl cellulose film having a haze of approximately 0 was attached to the antiglare layer surface of the measurement sample after measuring the total haze with glycerin.
  • Transparency definition By the method based on JIS K 7105, the transmission clarity of the anti-glare film was measured using the image clarity measuring device “ICM-1DP” manufactured by Suga Test Instruments Co., Ltd. Also in this case, in order to prevent the sample from warping, the surface opposite to the antiglare layer of the measurement sample was bonded to the glass substrate using an optically transparent adhesive, and then used for the measurement. In this state, light was incident from the glass substrate side and measurement was performed.
  • the measured values here are values measured using five types of optical combs in which the widths of the dark part and the bright part are 0.125 mm, 0.25 mm, 0.5 mm, 1.0 mm, and 2.0 mm, respectively. Is the sum of (Reflection sharpness measured at 45 ° light incident angle)
  • the reflection clarity of the antiglare film was measured using an image clarity measuring device “ICM-1DP” manufactured by Suga Test Instruments Co., Ltd.
  • the surface opposite to the antiglare layer of the measurement sample was bonded to the black acrylic substrate using an optically transparent adhesive, and then subjected to measurement. .
  • the measured values are the total values of the values measured using four types of optical combs in which the widths of the dark part and the bright part are 0.25 mm, 0.5 mm, 1.0 mm and 2.0 mm, respectively. is there. (Reflection sharpness measured at 60 ° light incident angle)
  • the reflection clarity of the antiglare film was measured using an image clarity measuring device “ICM-1DP” manufactured by Suga Test Instruments Co., Ltd.
  • the surface opposite to the antiglare layer of the measurement sample was bonded to the black acrylic substrate using an optically transparent adhesive, and then subjected to measurement. .
  • light was incident at 60 ° from the antiglare layer surface side, and measurement was performed.
  • the measured values are the total values of the values measured using four types of optical combs in which the widths of the dark part and the bright part are 0.25 mm, 0.5 mm, 1.0 mm and 2.0 mm, respectively. is there.
  • Luminous reflectance R SCI and luminous reflectance R SCE Luminous reflectance R SCI and luminous reflectance R SCE .
  • spectrocolorimeter CM 2002 manufactured by Konica Minolta Sensing
  • the reflection from the side opposite to the antiglare layer of the measurement sample was removed.
  • an optically transparent pressure-sensitive adhesive was used, and the surface opposite to the antiglare layer of the measurement sample was bonded to a black acrylic plate, and then subjected to measurement.
  • Glare was evaluated according to the following procedure. That is, first, a photomask having a unit cell pattern as shown in a plan view in FIG. 11 was prepared. In this figure, a unit cell 100 has a key-shaped chrome light-shielding pattern 101 having a line width of 10 ⁇ m formed on a transparent substrate, and a portion where the chrome light-shielding pattern 101 is not formed is an opening 102.
  • a unit cell having a size of 211 ⁇ m ⁇ 70 ⁇ m (vertical ⁇ horizontal in the figure) and an opening having a dimension of 201 ⁇ m ⁇ 60 ⁇ m (vertical ⁇ horizontal in the figure) was used.
  • a large number of unit cells shown in the figure are arranged vertically and horizontally to form a photomask.
  • the chrome light-shielding pattern 111 of the photomask 113 is placed on the light box 115 and the antiglare film 110 is attached to the glass plate 117 with an adhesive on the antiglare layer.
  • the sample bonded to the surface is placed on the photomask 113.
  • a light source 116 is disposed in the light box 115.
  • Level 1 corresponds to a state where no glare is observed
  • level 7 corresponds to a state where severe glare is observed
  • level 4 refers to a state where only slight glare is observed.
  • the polarizing plates on both the front and back surfaces were peeled off from a commercially available liquid crystal television (“KDL-32EX550” manufactured by Sony Corporation). Instead of these original polarizing plates, both the back side and the display side are polarizing plates "Sumikaran SRDB831E” manufactured by Sumitomo Chemical Co., Ltd.
  • the antiglare film shown in each of the following examples was laminated on the display surface side polarizing plate via an adhesive such that the concavo-convex surface was the surface.
  • the liquid crystal television thus obtained was activated in a dark room, and the luminance in the black display state and the white display state was measured using a luminance meter “BM5A” manufactured by Topcon Corporation, and the contrast was calculated.
  • the contrast is represented by the ratio of the luminance in the white display state to the luminance in the black display state.
  • the result showed the contrast measured in the state which bonded the anti-glare film in the ratio of the contrast measured in the state which does not bond an anti-glare film.
  • Two-dimensional function G (f x, f y) of a two-dimensional function gamma (f x, f y) of the absolute value squared by the two-dimensional power spectrum to calculate the one-dimensional power is a function of the distance f from the origin
  • a one-dimensional function ⁇ (f) of the spectrum was calculated.
  • Example 1> (Production of molds for the production of anti-glare films)
  • Copper ballad plating consists of a copper plating layer / thin silver plating layer / surface copper plating layer, and the thickness of the entire plating layer was set to be about 200 ⁇ m.
  • the copper plating surface was mirror-polished, and a photosensitive resin was applied to the polished copper plating surface and dried to form a photosensitive resin film.
  • a pattern in which the pattern A shown in FIG. 13 was repeatedly arranged was exposed on a photosensitive resin film with a laser beam and developed. Laser beam exposure and development were performed using Laser Stream FX (manufactured by Sink Laboratories).
  • the photosensitive resin film a film containing a positive photosensitive resin was used.
  • the pattern A is created by passing a plurality of Gaussian function type band pass filters from a pattern having a random brightness distribution, the aperture ratio is 45%, and the spatial frequency of the one-dimensional power spectrum is 0.
  • the chromium plating thickness was set to 13 ⁇ m.
  • Each of the following components was dissolved in ethyl acetate at a solid content concentration of 60%, and an ultraviolet curable resin composition A capable of forming a film having a refractive index of 1.53 after curing was prepared.
  • Pentaerythritol triacrylate 60 parts Multifunctional urethanated acrylate 40 parts (Reaction product of hexamethylene diisocyanate and pentaerythritol triacrylate) 5 parts of diphenyl (2,4,6-trimethoxybenzoyl) phosphine oxide
  • TAC triacetyl cellulose
  • this UV curable resin composition A is dried to have a thickness of 5 ⁇ m. And dried in a dryer set at 60 ° C. for 3 minutes. The dried film was brought into close contact with the molding surface of the mold A obtained previously (the surface having an uneven surface shape) with a rubber roll so that the coating layer after drying was on the mold side.
  • an anti-glare film is manufactured by irradiating light from a high-pressure mercury lamp with an intensity of 20 mW / cm 2 from the TAC film side so that the amount of light converted to h-ray is 200 mJ / cm 2 and curing the coating layer. did. Thereafter, the obtained antiglare film was peeled off from the mold to produce a transparent antiglare film A having an antiglare layer on the TAC film.
  • Example 2> Except that the etching amount in the etching process was set to 5 ⁇ m, the mold B was manufactured in the same manner as the mold A of Example 1, and the mold A was replaced with the mold B.
  • Example 1 In the same manner as above, an antiglare film was produced.
  • This antiglare film is designated as an antiglare film B.
  • Example 3> Except that the etching amount in the etching process was set to 7 ⁇ m, the mold C was manufactured in the same manner as the mold A in Example 1, and the mold A was replaced with the mold C in Example 1. In the same manner as above, an antiglare film was produced. This antiglare film is designated as an antiglare film C.
  • ⁇ Comparative Example 1> Except that the etching amount in the etching process was set to 9 ⁇ m, the mold D was prepared in the same manner as the mold A in Example 1, and the mold A was replaced with the mold D.
  • Example 1 In the same manner as above, an antiglare film was produced. This antiglare film is designated as an antiglare film D.
  • a mold E was prepared in the same manner as the mold A in Example 1 except that a pattern in which the patterns B shown in FIG. 14 were repeatedly arranged was exposed on the photosensitive resin film with laser light.
  • An antiglare film was produced in the same manner as in Example 1 except that the mold E was used. This antiglare film is designated as an antiglare film E.
  • the pattern B is created by passing a plurality of Gaussian function type bandpass filters from a pattern having a random brightness distribution, has an aperture ratio of 45.0%, and has a one-dimensional power spectrum space.
  • the ratio ⁇ (0.02) / ⁇ (0.01 ) is 2.69 of the intensity in the intensity gamma (0.01) and the spatial frequency 0.02 [mu] m -1 in the frequency 0.01 ⁇ m -1 ⁇ (0.02)
  • the ratio gamma (0.1) of the intensity in the intensity gamma (0.01) and the spatial frequency 0.1 [mu] m -1 in the spatial frequency 0.01 ⁇ m -1 ⁇ (0.1) / ⁇ (0.01) 278 .67.
  • the electroless nickel plating thickness was set to 15 ⁇ m.
  • An antiglare film was produced in the same manner as in Example 1 except that the mold A was replaced with the mold F. This antiglare film is designated as an antiglare film F.
  • a 200 mm diameter aluminum roll (A5056 according to JIS) was prepared by applying copper ballad plating to the surface. Copper ballad plating consists of a copper plating layer / thin silver plating layer / surface copper plating layer, and the thickness of the entire plating layer was about 200 ⁇ m.
  • the copper plating surface is mirror-polished, and the blasting device (manufactured by Fuji Seisakusho Co., Ltd.) is used on the polished surface, and zirconia beads “TZ-SX-17” (manufactured by Tosoh Corp., average particle diameter: 20 ⁇ m) was blasted at a blast pressure of 0.05 MPa (gauge pressure, the same applies hereinafter) and a bead usage of 6 g / cm 2 , and the aluminum roll surface was uneven.
  • the resulting copper-plated aluminum roll with unevenness was subjected to chrome plating to produce a mold G. At this time, the chromium plating thickness was set to 6 ⁇ m.
  • Example 1 An antiglare film was produced in the same manner as in Example 1 except that the mold A was replaced with the mold G.
  • This antiglare film is designated as an antiglare film G.
  • Table 1 shows the results of evaluating the above antiglare films for the above Examples and Comparative Examples.
  • the antiglare films A to C Examples 1 to 3 satisfying the requirements of the present invention have low haze, they have excellent antiglare properties regardless of whether the observation angle is front or oblique. In addition, the effect of suppressing whitishness and glare was sufficient.
  • the antiglare film D Comparative Example 1 was whitish.
  • Anti-glare film E (Comparative Example 2) had insufficient anti-glare properties when observed obliquely.
  • the antiglare film F (Comparative Example 3) was easily glaring.
  • the antiglare film G (Comparative Example 4) had insufficient antiglare properties when observed from an oblique direction.
  • mold substrate 41
  • the antiglare film of the present invention is useful for an image display device such as a liquid crystal display.

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  • Optics & Photonics (AREA)
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  • Mathematical Physics (AREA)
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Abstract

La présente invention porte sur un film anti-reflets qui présente d'excellentes propriétés anti-reflets à un angle d'observation large même avec un trouble faible, et qui peut supprimer de manière suffisante l'apparition de turbidité blanche et de reflets lorsqu'il est agencé sur un dispositif d'affichage d'image. Le film anti-reflets comprend un corps de support transparent, et une couche anti-reflets formée sur ce dernier et ayant de fines irrégularités de surface, le trouble total étant de 0,1 % à 3 % inclus ; le trouble de surface étant de 0,1 % to 2 % inclus ; le rapport RSCE/RSCI entre la réflectance lumineuse RSCI mesurée selon le mode à composante spéculaire inclue et la réflectance lumineuse RSCE mesurée selon le mode à composante spéculaire exclue étant de 0,1 au maximum ; et des intensités I (0,01), I (0,02), et I (0,1) à une fréquence spatiale de 0,01 µm-1, une fréquence spatiale de 0,02 µm-1, et une fréquence spatiale de 0,1 µm-1, respectivement, dans un spectre de puissance de la hauteurs desdites irrégularités de surface étant dans des plages prédéterminées respectives.
PCT/JP2014/081671 2013-11-29 2014-11-25 Film anti-reflets WO2015080281A1 (fr)

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