WO2015046047A1 - ハードコートフィルム及び表面部材付き表示素子 - Google Patents
ハードコートフィルム及び表面部材付き表示素子 Download PDFInfo
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- WO2015046047A1 WO2015046047A1 PCT/JP2014/074819 JP2014074819W WO2015046047A1 WO 2015046047 A1 WO2015046047 A1 WO 2015046047A1 JP 2014074819 W JP2014074819 W JP 2014074819W WO 2015046047 A1 WO2015046047 A1 WO 2015046047A1
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
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- the present invention includes a hard coat film such as a display element front film suitable for use on a surface member or the like disposed on the screen of various display elements, and a surface member on which the surface member including the film is disposed on the screen.
- the present invention relates to a display element.
- An antiglare film may be disposed on the screen of various display elements (liquid crystal display elements, plasma display elements, etc.).
- the surface of the antiglare film is subjected to surface unevenness treatment, and the surface of the antiglare film is formed by providing a hard coat layer containing particles as a matting agent on the substrate as an antiglare layer. Can be applied.
- a matting agent is necessary for developing antiglare properties and Newton ring preventing properties.
- sparkle is generated by a lens formed around the matting agent, and antiglare properties or Newtonian properties are generated. It was difficult to satisfy both the ring prevention property and the sparkle prevention property at the same time.
- Patent Document 1 a technique for adding a resin component other than the ionizing radiation curable resin to the Newton ring prevention layer (Patent Document 1), a technique for increasing the coefficient of variation of the particle size distribution of the matting agent in the Newton ring prevention layer (Patent Document) 2) has been proposed, but there is a need for a technique capable of further preventing the occurrence of sparkle for color display elements that have been further refined in recent years. From the viewpoint of preventing scratches, it is desirable that the coating film hardness is as high as possible.
- a technology capable of simultaneously satisfying both antiglare properties, Newton ring prevention properties, and sparkle prevention properties, and can increase coating film hardness.
- the present inventors include a specific resin component (one or more of a thermoplastic resin and a thermosetting resin into which a reactive functional group is introduced) in a composition containing a matting agent and an ionizing radiation curable resin, In the process of curing the composition, the flow of the ionizing radiation curable resin is further suppressed. As a result, it was found that the occurrence of undulation of the resin after curing was further suppressed, and thereby it was possible to prevent the occurrence of sparkle more effectively, and the coating film hardness could be increased, thereby completing the present invention. It was.
- a specific resin component one or more of a thermoplastic resin and a thermosetting resin into which a reactive functional group is introduced
- the hard coat film of this invention can be utilized for the use arrange
- the hard coat film which concerns on the 1st viewpoint of this invention is comprised with the hardened
- the curable composition further includes one or more of the following (a) and (b) as a resin component: Content ratio in total resin content is ionizing radiation curable resin: 50% by weight or more and less than 85% by weight, and the following (a) and (b): more than 15% by weight and 50% by weight or less .
- the hard coat film which concerns on the 2nd viewpoint of this invention is comprised by the hardened
- the curable composition further includes one or more of the following (a) and (b) as a resin component: The aspect ratio of the convex part is adjusted to 0.043 or more.
- the display element with a surface member according to the first aspect of the present invention is characterized in that the surface member is disposed on the display element, and the surface member includes the hard coat film of the present invention in at least a part thereof. .
- the surface member is arranged on the display element, and the surface member is used as an optical functional layer as at least one of an antiglare layer and a Newton ring prevention layer. It is characterized by comprising the hard coat film of the present invention.
- the curable composition of the present invention is used to form an optical functional layer that exhibits at least one optical function of an antiglare effect and suppression of occurrence of interference fringes, Contains resin and matting agent
- the resin component includes an ionizing radiation curable resin and one or more of the following (a) and (b): Content ratio in total resin content is ionizing radiation curable resin: 50% by weight or more and less than 85% by weight, and the following (a) and (b): more than 15% by weight and 50% by weight or less .
- the reactive functional group introduced into the compound is preferably a photocurable unsaturated group.
- the matting agent can be constituted with an average particle size of 0.1 to 10 ⁇ m.
- the matting agent may be composed of a single matting agent having a predetermined average particle diameter, but it is preferable to use a combination of a plurality of matting agents having different average particle diameters.
- at least a first matting agent having an average particle size of 0.1 to 4.0 ⁇ m and a second matting agent having an average particle size of 3.0 to 10.0 ⁇ m can be included.
- the matting agent can be used in combination of only the first matting agent and the second matting agent. In this case, those having a variation coefficient of the particle size distribution of 15% or less can be used.
- the weight ratio of the first matting agent to the second matting agent in all matting agents to be contained is 8: 2 to 6: 4 regardless of whether or not the third and subsequent matting agents are contained. be able to. Regardless of whether the use of the matting agent is single or plural, the matting agent as a whole can be contained in the range of 0.05 to 5 parts by weight with respect to 100 parts by weight of the resin.
- the optical functional layer can be used as an antiglare layer that exhibits an antiglare effect or a Newton ring prevention layer that suppresses the generation of interference fringes.
- a (meth) acryloyl group can be used as a reactive functional group of at least one of the thermoplastic resin (a) and the thermosetting resin (b). .
- a hard coat film can be utilized for the use arrange
- the aspect ratio of the plurality of convex portions arranged on the surface of the optical functional layer due to the matting agent is preferably adjusted to 0.043 or more.
- the hard coat film of the present invention using the optical functional layer as an antiglare layer can be included on the surface side of the surface member.
- the hard coat film of this invention which utilized the optical function layer as a Newton ring prevention layer can be included in the back surface side of a surface member.
- a surface member can be comprised with a protective plate, a touch panel, or a polarizing film.
- the surface member can be formed of a protective plate, a touch panel, or a polarizing film.
- the surface member is arranged on the display element, the surface member is a touch panel, and the outermost surface member of the touch panel uses the optical functional layer as an antiglare layer. It can be comprised with the hard coat film of invention.
- the surface member is disposed on the display element, the surface member is a touch panel, and at least one of the outermost surface member, the intermediate member, and the rearmost member of the touch panel, It can be comprised with the hard coat film of this invention using the optical function layer as a Newton ring prevention layer.
- the composition containing the matting agent and the ionizing radiation curable resin that forms the optical functional layer contains a specific resin component (one or more of Compound A1 and Compound A2 described below). Further, the occurrence of undulation of the resin after curing is further suppressed. As a result, the resulting coating film can satisfy both the antiglare property, the Newton ring prevention property, and the sparkle prevention property at the same time.
- the reactive functional group is introduced into the specific resin component, the bond with the ionizing radiation curable resin is strengthened. As a result, the coating film hardness can be further increased as compared with the case where the reactive functional group is not introduced.
- a coating film (optical functional layer) having both the antiglare property, the Newton ring prevention property and the sparkle prevention property at the same time and having an enhanced coating film hardness is obtained.
- the hard coat film and the display element with a surface member of the present invention have an optical functional layer composed of a cured product of the curable composition of the present invention, both antiglare and Newton ring preventive properties and sparkle preventive properties are provided. Is satisfied at the same time, and the coating film hardness is increased.
- FIG. 1 is a cross-sectional view showing a display element front film as an example of the present invention.
- FIG. 2 is a cross-sectional view showing an example of a conventional display element front film.
- FIG. 3 is a cross-sectional view showing an example of the display element with a surface member of the present invention.
- FIG. 4 is a sectional view showing another example of the display element with a surface member of the present invention.
- FIG. 5 is a cross-sectional view showing another example of the display element with a surface member of the present invention.
- FIG. 6 is a cross-sectional view showing another example of the display element with a surface member of the present invention.
- SYMBOLS 1 Display element front film (hard coat film), 11 ... Transparent base material, 12 ... Optical functional layer, 121 ... Resin component (binder), 122 ... Matting agent, 2 ... Surface member, 2a ... Protection plate, 2b ... Touch panel, 2c ... polarizing plate, 3 ... display element, 4, 4a, 4b, 4c ... display element with surface member.
- the hard coat film of this invention is used as a film for display element front surfaces arrange
- an optical functional layer 12 is laminated on a transparent substrate 11.
- the transparent substrate 11 examples include a transparent film formed of a material such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyethylene, polypropylene, polystyrene, triacetyl cellulose, and acrylic.
- a polyethylene terephthalate film that has been stretched, in particular biaxially stretched, is preferred because of its excellent mechanical strength and dimensional stability.
- the thickness of the transparent substrate 11 is generally 6 to 500 ⁇ m, preferably 23 to 200 ⁇ m.
- optical functional layer 12 examples include an antiglare layer that exhibits an antiglare effect and a Newton ring prevention layer that suppresses the occurrence of interference fringes (Newton rings).
- the optical functional layer 12 includes a resin component 121 and a matting agent 122, and is composed of a cured product of a curable composition (curable resin precursor), and includes a plurality of convex portions due to the matting agent 122 on the surface. Become.
- the curable composition of this example contains a resin component and a matting agent.
- the resin component referred to in this example includes a curable resin and a thermoplastic resin.
- the cured product in this example refers to curing of a polymerization initiator, a polymerization accelerator (such as an ultraviolet sensitizer), and a curing agent necessary for curing the curable resin together with a curable resin as a curing main agent. It is used in the concept including auxiliary agents.
- the resin component in this example includes at least an ionizing radiation curable resin.
- the ionizing radiation curable resin those that are cross-linked and cured by irradiation with ionizing radiation (ultraviolet rays or electron beams) are used.
- ionizing radiation ultraviolet rays or electron beams
- photocationically polymerizable resin examples include epoxy resins such as bisphenol epoxy resins, novolac epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins, and vinyl ether resins.
- an acrylic prepolymer having two or more acryloyl groups in one molecule and having a three-dimensional network structure by crosslinking and curing is particularly preferably used.
- the acrylic prepolymer urethane acrylate, polyester acrylate, epoxy acrylate, melamine acrylate, polyfluoroalkyl acrylate, silicone acrylate and the like can be used.
- these acrylic prepolymers can be used alone, but it is preferable to add a photopolymerizable monomer in order to improve the cross-linking curability and further improve the hardness of the functional layer.
- photopolymerizable monomers examples include monofunctional acrylic monomers such as 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and butoxyethyl acrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and diethylene glycol.
- bifunctional acrylic monomer such as diacrylate, polyethylene glycol diacrylate, hydroxypivalate ester neopentyl glycol diacrylate, etc.
- polyfunctional acrylic monomer such as dipentaerythritol hexaacrylate, trimethylpropane triacrylate, pentaerythritol triacrylate, or the like Two or more are used.
- the ionizing radiation curable resin is a curing aid such as a photopolymerization initiator or an ultraviolet sensitizer when cured by ultraviolet irradiation. It is preferable to contain an agent.
- Photopolymerization initiators include photo-radical polymerization initiators such as acetophenones, benzophenones, Michler's ketone, benzoin, benzylmethyl ketal, benzoylbenzoate, ⁇ -acyloxime esters, thioxanthones, onium salts, sulfonate esters, organometallics
- photocationic polymerization initiators such as complexes.
- the ultraviolet sensitizer include n-butylamine, triethylamine, and tri-n-butylphosphine.
- the photopolymerization accelerator can reduce the polymerization obstacle due to air at the time of curing and increase the curing speed.
- examples thereof include p-dimethylaminobenzoic acid isoamyl ester and p-dimethylaminobenzoic acid ethyl ester. Can be mentioned.
- an ionizing radiation curable organic-inorganic hybrid resin may be used as the ionizing radiation curable resin.
- ionizing radiation curable organic-inorganic hybrid resins are organic and inorganic. The mixture is intimately mixed, and the dispersion state is at or close to the molecular level. By irradiation with ionizing radiation, the inorganic component and the organic component react to form a film.
- Examples of the inorganic component in the organic-inorganic hybrid resin include metal oxides such as silica and titania, and silica is preferable.
- Examples of the silica include reactive silica in which a photosensitive group having photopolymerization reactivity is introduced on the surface.
- the content of the inorganic component in the organic-inorganic hybrid resin is preferably 10% by weight or more, more preferably 20% by weight, preferably 65% by weight or less, more preferably 40% by weight or less.
- the organic component in the organic-inorganic hybrid resin is a compound having a polymerizable unsaturated group polymerizable with the inorganic component (preferably reactive silica) (for example, having two or more polymerizable unsaturated groups in the molecule). And polyunsaturated organic compounds or unit price unsaturated organic compounds having one polymerizable unsaturated group in the molecule).
- one or more specific compounds A1 and A2 are contained in the curable composition together with the ionizing radiation curable resin described above.
- Ionizing radiation curable resin has the property of curing while flowing during the curing process. Therefore, when trying to obtain a cured product using a curable composition containing a matting agent and an ionizing radiation curable resin, the ionizing radiation curable resin flows during curing of the curable composition, As shown in FIG. 2, “swell 121 a ′” of the resin portion 121 a centering on the matting agent 122 a is generated and a lens shape is formed. Due to this, sparkle is generated in the conventional film 1a having the optical function layer 12a including the matting agent 122a and the resin component 121a.
- a specific amount of one or more of compound A1 and compound A2 is included, thereby further suppressing the flow of the ionizing radiation curable resin during the curing process.
- the occurrence of “swell” of the resin portion 121 after curing is further suppressed (what substantially corresponds to the swell 121 a ′ in FIG. 2 is not seen. The same applies hereinafter).
- the occurrence of sparkles in the optical functional layer 12 after curing can be more effectively prevented.
- thermoplastic resins include polyester resins, acrylic resins, polycarbonate resins, cellulose resins, acetal resins, vinyl resins, polyethylene resins, polystyrene resins, polypropylene resins, polyamide resins, and polyimide resins. Examples thereof include resins and fluorine resins.
- thermosetting resin include polyester acrylate resins, polyurethane acrylate resins, epoxy acrylate resins, epoxy resins, melamine resins, phenol resins, and silicone resins.
- a photocurable unsaturated group is preferably used, and preferably an ionizing radiation curable unsaturated group.
- an ethylenically unsaturated bond such as a (meth) acryloyl group, a styryl group, a vinyl group and an allyl group, and an epoxy group. More preferred is a (meth) acryloyl group.
- a compound having a glass transition temperature (Tg) of 45 ° C. or higher, preferably 80 ° C. or higher, more preferably 90 ° C. or higher is used as compound A1 and / or compound A2.
- Tg glass transition temperature
- the compound A1 and / or the compound A2 having a Tg of 45 ° C. or more together with the ionizing radiation curable resin it is possible to easily suppress the flow of the ionizing radiation curable resin during the curing process.
- Tg of compound A2 in this example is that before curing.
- compound A1 and / or compound A2 those having a weight average molecular weight (Mw) of 70,000 or more, preferably 80,000 or more are used.
- Mw weight average molecular weight
- one or more of the following (a) and (b) are included together with the ionizing radiation curable resin.
- the value of the weight average molecular weight (Mw) is obtained by measuring the molecular weight distribution of the compound by a gel permeation chromatograph (GPC) equipped with a differential refractive index detector (RID), for example. Chart) can be calculated using standard polystyrene as a calibration curve.
- GPC gel permeation chromatograph
- RID differential refractive index detector
- the weight ratio between the ionizing radiation curable resin and the compound A1 and / or the compound A2 is preferably 50% by weight to less than 85% by weight of the former, more than 15% by weight and 50% by weight or less of the latter. More preferably, the former is 60% to 80% by weight, the latter is 20% to 40% by weight, more preferably the former is 60% to 75% by weight, and the latter is 25% to 40% by weight. And By setting the compound A1 and / or the compound A2 to an amount exceeding 15% by weight, the occurrence of swell can be sufficiently suppressed and sparkle can be easily prevented. By making compound A1 and / or compound A2 50 weight% or less, it can be made easy to prevent the coating-film intensity fall by containing compound A1 and / or compound A2 more than necessary.
- the dispersibility of the matting agent is improved, thereby appropriately adjusting the surface properties of the coating film.
- the aspect ratio of the convex portion due to the matting agent formed on the coating film surface is adjusted to a range of 0.043 or more.
- the aspect ratio of the convex part is out of this range, the effect of preventing sparkle due to suppression of the occurrence of waviness while maintaining the coating film strength cannot be obtained.
- the “aspect ratio of the convex portion” is preferably 0.2 or less, more preferably 0.18 or less, and still more preferably 0.8 or less, from the viewpoint of preventing the matting agent from falling off the coating film surface. 16 or less.
- the “aspect ratio of the convex portion” means the ratio (H / L) of the height H of the convex portion to the base length L (both see FIG. 2).
- the “convex portion” means a portion where the matting agent 122 protrudes on the surface of the coating film (optical functional layer 12a), and the height (height of the projecting portion) H is a coating where the matting agent 122 does not exist. It means the shortest distance ( ⁇ m) between the tangent line drawn on the smooth part of the film and the tangent line drawn on the upper end part of the convex part.
- “Span” means the bottom surface of a circular area with a gradient of 0.1 ⁇ m in height, which is a portion of the coating film that touches the periphery of the convex portion when viewed in plan, and its length (base length) L means the diameter ( ⁇ m) of the bottom surface of the circular region.
- the height H of the convex portion is preferably 0.3 ⁇ m or more, more preferably 0.4 ⁇ m or more in consideration of Newton ring prevention.
- the thickness is preferably 8 ⁇ m or less, more preferably 6 ⁇ m or less.
- the skirt length L is preferably 80 ⁇ m or less, more preferably 60 ⁇ m or less, still more preferably 40 ⁇ m or less, and most preferably 37 ⁇ m or less in consideration of sparkle prevention.
- the thickness is preferably 3 ⁇ m or more, more preferably 4 ⁇ m or more.
- the height H and skirt length L of the convex portion can be obtained from the cross-sectional shape of the coating film photographed using, for example, a confocal laser microscope (VK-9710, manufactured by Keyence Corporation). Moreover, it can also obtain
- a confocal microscope an interference microscope
- AFM atomic force microscope
- Matting agents include inorganic particles (eg, calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, silica, kaolin, clay, talc, etc.) and resin particles (eg, acrylic resin particles, polystyrene resin particles, polyurethane resin particles). Polyethylene resin particles, benzoguanamine resin particles, epoxy resin particles, etc.). Among these, spherical fine particles are preferable from the viewpoint of handleability and ease of control of the surface shape. Moreover, the resin particles are suitable in that they easily bring the difference in refractive index from that of the resin, easily prevent the occurrence of sparkle, and are difficult to hinder transparency.
- inorganic particles eg, calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, silica, kaolin, clay, talc, etc.
- resin particles eg, acrylic resin particles, polystyrene resin particles, polyurethane resin particles.
- the average particle diameter of the matting agent varies depending on the thickness of the optical functional layer 12, it cannot be generally stated, but is preferably 0.1 ⁇ m or more, more preferably 1 ⁇ m or more, preferably 10 ⁇ m or less, more preferably 8 ⁇ m or less. And By making the average particle size of the matting agent 10 ⁇ m or less, induction of sparkle can be easily prevented, and by making the average particle size 0.1 ⁇ m or more, antiglare property and Newton ring prevention property can be easily developed.
- the matting agent of this example is preferably composed of a combination of a plurality of matting agents having different average particle diameters.
- the average particle size is preferably 0.1 ⁇ m or more, more preferably 0.5 ⁇ m or more, further preferably 2.5 ⁇ m or more, preferably 4.0 ⁇ m or less, more preferably 3.5 ⁇ m or less.
- the average particle diameter of the first matting agent is preferably 3.0 ⁇ m or more, more preferably 4.0 ⁇ m or more, preferably 10.0 ⁇ m or less, more preferably 7.0 ⁇ m or less, and even more preferably 6 It is more preferable to include at least a second matting agent of 0.0 ⁇ m or less.
- a matting agent of this example when only two types (the first matting agent and the second matting agent) described above are used in combination (not containing the third and subsequent matting agents other than these two types), in addition, it is preferable to use particles having a variation coefficient of particle size distribution of 15% or less, preferably 10% or less (so-called monodisperse particles).
- a particle having a particle diameter distribution coefficient of variation of 15% or less is used, causing a large local convex portion. Easy to prevent sparkle.
- the coefficient of variation (CV value: coefficient of variation) is a value indicating the dispersion state of the particle size distribution, and the standard deviation of the particle size distribution (the square root of unbiased dispersion) is the arithmetic average value of the particle size (average particle size) It is the percentage of the value divided by (diameter). That is, it shows how much the spread of particle size distribution (variation of particle size) is relative to the average value (arithmetic average diameter).
- CV value (no unit) (standard deviation / average) Value). The smaller the CV value, the narrower the particle size distribution (sharp), and the larger the CV value, the wider the particle size distribution (broad).
- the content of the matting agent is preferably 0.05 parts by weight or more, more preferably 0.1 parts by weight or more, preferably 5 parts by weight or less, more preferably 3 parts by weight with respect to 100 parts by weight of the resin content. Part or less, more preferably 1 part by weight or less.
- first mat these two types are also included, including the case where a third or subsequent mat agent other than the above-described two types (first mat agent, second mat agent) is contained.
- the weight ratio of the first matting agent to the second matting agent in all matting agents is preferably 8: 2 to 6: 4.
- the “average particle size” and “coefficient of variation in particle size distribution” of the matting agent in this example are values measured by a Coulter counter method.
- the Coulter counter method is a method of electrically measuring the number and size of matting agent particles dispersed in a solution, in which particles are dispersed in an electrolyte and electricity flows using suction force. This is a method of measuring a voltage pulse proportional to the volume of a particle by replacing the electrolyte by the volume of the particle when passing the particle through the pores, increasing the resistance. Therefore, by measuring the height and number of the voltage pulses electrically, the number of particles and the individual particle volume are measured, and the particle size and particle size distribution are obtained.
- additives such as a leveling agent, an ultraviolet absorber and an antioxidant may be added.
- the optical functional layer 12 can be formed by applying the above-described curable composition of the present example to the transparent substrate 11 by curing it by applying, drying and irradiating with ionizing radiation.
- the optical functional layer 12 has a surface hardness that does not cause damage even when steel wool # 0000 with a load of 200 g / 2 cm 2 is reciprocated five times (preferably 10 times) or more.
- the number of reciprocations by the steel wool # 0000 on the surface of the optical functional layer 12 is 10 times. It can be more than once.
- the thickness of the optical function layer 12 is preferably 0.5 ⁇ m or more, more preferably 1 ⁇ m or more, preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and particularly preferably 3 ⁇ m or less.
- the display element front film 1 of this example has a total light transmittance (JIS K7361-1: 1997) of 85% or more and a haze (JIS K7136: 2000) of 10% or less. preferable.
- the usage application of the hard coat film of the present invention is not limited to the above-described front surface of the display element.
- it can be used for other applications such as a transparent electrode film, an anti-scattering film (for example, a configuration in which an adhesive layer is provided on the surface opposite to the optical functional layer 12 of the transparent base material 11), and a printing film.
- the display element 4 (4a, 4b, 4c) with the surface member of this example is configured by disposing the surface member 2 (2a, 2b, 2c) on the display element 3. ing.
- the display element 3 include a liquid crystal display element, a CRT display element, a plasma display element, and an EL display element.
- the surface member 2 include a protective plate 2a, a touch panel 2b, and a polarizing plate 2c.
- the display element front film 1 of this example is included in at least a part of these surface members 2 (2a, 2b, 2c).
- the protective plate 2a as an example can be constituted by, for example, a transparent resin plate represented by an acrylic resin plate.
- the thickness of the protective plate 2a is usually about 0.1 to 2.0 mm.
- the method of the touch panel 2b as an example is not particularly limited, and can be configured by, for example, a resistive touch panel, a capacitive touch panel, or the like.
- the display element-attached film 1 is laminated on the surface side of the protective plate 2a as a glare-proof film.
- the element 4a may be configured.
- the display element 4a with a surface member can also be configured by laminating the display element front film 1 of this example as a Newton ring prevention film on the back side of the protective plate 2a.
- the display element front film 1 itself of this example may be provided on the display element 3 as a protective plate 2 a having antiglare properties and / or Newton ring preventing properties.
- the display element 4b with a surface member is laminated
- the display element-attached display element 4b can be configured by laminating the display element front film 1 of this example as a Newton ring prevention film on the back side of the touch panel 2b.
- the display element-attached display element 4b can be configured by using the display element front film 1 itself of this example as a Newton ring prevention film as a member on the outermost surface, middle, or rearmost surface of the touch panel 2b. .
- the surface member 2 is the polarizing film 2c, as shown in FIG. 3, a display with a surface member is provided by bonding the film 1 for a display element front surface of this example as an antiglare film on the surface side of the polarizing film 2c.
- the element 4c can be configured.
- the predetermined function (prevention) Sparkling can be prevented and coating film hardness is increased while providing dazzling properties, Newton's ring prevention properties, and the like.
- Example 1 On one side of a 125 ⁇ m thick transparent polyester film (Cosmo Shine A4350: Toyobo Co., Ltd.), a coating liquid a having the following formulation was applied, dried and irradiated with ultraviolet rays to form an optical functional layer having a thickness of 3 ⁇ m. A hard coat film was obtained. In addition, the weight conversion amount of solid content is shown in parentheses.
- Example 2 A hard coat film of this example was obtained in the same manner as in Example 1 except that the addition amount of the resin A in the coating liquid a was changed to 65 parts (solid content 26 parts).
- Example 3 A hard coat film of this example was obtained in the same manner as in Example 1 except that the addition amount of the resin A in the coating liquid a was changed to 250 parts (solid content: 100 parts).
- Example 4 A hard coat film of this example was obtained in the same manner as in Example 1 except that the resin A of the coating liquid a was changed to the resin B and the addition amount was changed to 95 parts (solid content 42.75 parts). .
- Example 5 A hard coat film of this example was obtained in the same manner as in Example 1 except that the matting agent A of the coating liquid a was changed to the matting agent B.
- Example 6 A hard coat film of this example was obtained in the same manner as in Example 1 except that the resin A of the coating liquid a was changed to the resin C.
- Example 7 A hard coat film of this example was obtained in the same manner as in Example 1 except that the matting agent A of the coating liquid a was changed to the matting agent C.
- Example 8 The amount of resin A added to coating solution a was changed to 97.2 parts (solid content 38.9 parts). Further, a hard coat film of this example was obtained in the same manner as in Example 1 except that the matting agent A of the coating liquid a was changed to the matting agent E and the addition amount thereof was changed to 0.14 part.
- Example 9 The addition amount of the resin A in the coating solution a was changed to 250 parts (solid content 100 parts), and the addition amount of the ionizing radiation curable resin was changed to 48.75 parts (solid content 39 parts). Further, a hard coat film of this example was obtained in the same manner as in Example 1 except that the matting agent A of the coating liquid a was changed to the matting agent E and the addition amount thereof was changed to 0.14 part.
- Example 10 The addition amount of the resin A in the coating liquid a was changed to 47.6 parts (solid content 19.0 parts), and the addition amount of the ionizing radiation curable resin was changed to 256 parts (solid content 204.75 parts). Further, a hard coat film of this example was obtained in the same manner as in Example 1 except that the matting agent A of the coating liquid a was changed to the matting agent D and the addition amount thereof was changed to 0.14 part.
- Example 11 The amount of resin A added to coating solution a was changed to 97.2 parts (solid content 38.9 parts). Further, a hard coat film of this example was obtained in the same manner as in Example 1 except that the matting agent A of the coating liquid a was changed to the matting agent D and the addition amount thereof was changed to 0.14 part.
- Example 12 The addition amount of the resin A in the coating liquid a was changed to 196.4 parts (solid content 78.6 parts), and the addition amount of the ionizing radiation curable resin was changed to 62 parts (solid content 50 parts). Further, a hard coat film of this example was obtained in the same manner as in Example 1 except that the matting agent A of the coating liquid a was changed to the matting agent D and the addition amount thereof was changed to 0.14 part.
- Example 13 The addition amount of the resin A in the coating solution a was changed to 250 parts (solid content 100 parts), and the addition amount of the ionizing radiation curable resin was changed to 48.75 parts (solid content 39 parts). Further, a hard coat film of this example was obtained in the same manner as in Example 1 except that the matting agent A of the coating liquid a was changed to the matting agent D and the addition amount thereof was changed to 0.14 part.
- Example 14 Example 1 was repeated except that the amount of resin A added to coating solution a was changed to 97.2 parts (solid content 38.9 parts) and the amount of matting agent A was changed to 0.14 parts. Thus, a hard coat film of this example was obtained.
- Example 15 The addition amount of the resin A in the coating solution a was changed to 250 parts (solid content 100 parts), and the addition amount of the ionizing radiation curable resin was changed to 48.75 parts (solid content 39 parts). Further, a hard coat film of this example was obtained in the same manner as in Example 1 except that the addition amount of the matting agent A in the coating liquid a was changed to 0.14 part.
- Example 16 A part (0.07 part) of the matting agent D (average particle size 3 ⁇ m, variation coefficient 9%) of the coating liquid a was replaced with the matting agent E (average particle size 1.8 ⁇ m, variation coefficient 9%). That is, except that the matting agent D (addition amount is 0.14 part) of the coating liquid a is changed to two kinds of matting agent D and matting agent E (addition amount is 0.07 part each) having different average particle diameters. Produced the hard coat film of this example in the same manner as in Example 11 (resin A content: 28%).
- Example 17 A part (0.07 part) of the matting agent D (average particle diameter 3 ⁇ m, variation coefficient 9%) of the coating liquid a was replaced with the matting agent A (average particle diameter 5 ⁇ m, variation coefficient 9%). That is, except that the matting agent D (addition amount is 0.14 part) of the coating liquid a is changed to two types of matting agent A and matting agent D (addition amount is 0.07 part each) having different average particle diameters.
- the hard coat film of this example in the same manner as in Example 11 (resin A content: 28%).
- Example 1 A hard coat film of this example was obtained in the same manner as in Example 1 except that the resin A of the coating liquid a was changed to the resin D and the addition amount was changed to 95 parts (solid content 42.5 parts). .
- Example 2 A hard coat film of this example was obtained in the same manner as in Example 1 except that the resin A of the coating liquid a was changed to the resin E and the addition amount was changed to 95 parts (solid content 42.75 parts). .
- Example 3 A hard coat film of this example was obtained in the same manner as in Example 1 except that the amount of the resin A added to the coating solution a was changed to 40 parts (solid content 16 parts).
- Example 4 A hard coat film of this example was obtained in the same manner as in Example 1 except that the amount of the resin A added to the coating liquid a was changed to 300 parts (120 parts solids).
- Table 1 summarizes information such as the types (A to E) and content ratios of resins used in each example, and the types (A to E) and addition amounts of matting agents used in each example.
- Example 7 the ratio of the ionizing radiation curable resin and the resin A or C corresponding to the compound A2 in the coating solution is in the optimum range, and in Example 4, it is also in the optimum range.
- the blended resin A or C has a higher glass transition temperature.
- sparkle prevention properties ⁇
- Example 7 the same resin content as in Examples 1, 5, and 6 was used in the same amount.
- a matting agent having a coefficient of variation of particle distribution exceeding 15% was used. Used alone. Therefore, although slightly inferior in anti-sparkle properties as compared with other Examples 1 to 6, the anti-sparkle property level was sufficiently excellent.
- Examples 10 to 13 as compared with Examples 1 to 7, a matting agent having a small average particle diameter was used alone, and the addition amount was reduced to 20%.
- Examples 8 and 9 as compared with Examples 1 to 7, a matting agent having a smaller average particle diameter than that of Examples 10 to 13 was used alone, and the addition amount was reduced to 20%.
- the addition amount of the matting agent was reduced to 20% as compared with Examples 1 to 7.
- Examples 16 and 17 unlike Examples 1 to 15, two matting agents having different average particle diameters are used in combination, and compared to Examples 1 to 7, mats are similar to Examples 8 to 15. The amount of agent added was reduced to 20%.
- the content ratio of Resin A, B, or C was appropriate as in Examples 1 to 7. Therefore, it was confirmed that excellent results were obtained in the same manner as in Examples 1, 5, and 6, that is, the obtained hard coat films were extremely excellent in sparkle prevention ( ⁇ ).
- Comparative Example 1 the weight ratio of the ionizing radiation curable resin and the resin D in the coating solution is within the range of the present invention, but the glass transition temperature of the used resin D is low and the weight average molecular weight is also low. Is small. Therefore, the obtained hard coat film could not prevent sparkle.
- Comparative Example 1 no reactive functional group is introduced into the resin D used. Therefore, the obtained hard coat film was inferior in surface hardness.
- Comparative Example 2 the weight ratio of the ionizing radiation curable resin to the resin E in the coating solution, the glass transition temperature of the resin E used, and the weight average molecular weight are all within the scope of the present invention. A reactive functional group is not introduced into E. Therefore, although the obtained hard coat film could prevent sparkle, the surface hardness was inferior.
- Comparative Example 7 the resin A was included in the coating solution, but the weight ratio between the resin A and the ionizing radiation curable resin was outside the scope of the present invention. Therefore, the obtained hard coat film could not prevent sparkle as in Comparative Examples 3 and 4.
- Comparative Example 7 compared with Comparative Example 3, a matting agent having a small average particle diameter was used, and the amount added was reduced to 20%. Therefore, the obtained hard coat film had an increased surface hardness as compared with Comparative Example 3.
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Abstract
Description
本発明の第1の観点に係るハードコートフィルムは、マット剤と、樹脂分としての電離放射線硬化型樹脂を含む硬化性組成物の硬化物で構成してあり、前記マット剤に起因した凸部を表面に複数備えてなる光学機能層を有し、
前記硬化性組成物は、樹脂分として、さらに、下記(a)及び(b)の1つ以上を含み、
全樹脂分中での含有割合が、電離放射線硬化型樹脂:50重量%以上85重量%未満、下記(a)及び(b):15重量%を超え50重量%以下であることを特徴とする。
前記硬化性組成物は、樹脂分として、さらに、下記(a)及び(b)の1つ以上を含み、
前記凸部のアスペクト比が、0.043以上に調整されていることを特徴とする。
本発明の第2の観点に係る表面部材付き表示素子は、表示素子上に表面部材を配置され、前記表面部材を、光学機能層を防眩層およびニュートンリング防止層の少なくともいずれかとして利用した本発明のハードコートフィルムで構成したことを特徴とする。
樹脂分とマット剤を含み、
前記樹脂分は、電離放射線硬化型樹脂と、下記(a)及び(b)の1つ以上とを含み、
全樹脂分中での含有割合が、電離放射線硬化型樹脂:50重量%以上85重量%未満、下記(a)及び(b):15重量%を超え50重量%以下であることを特徴とする。
(b)熱硬化型樹脂に反応性官能基が導入されており、重量平均分子量が7万以上で、かつガラス転移温度が45℃以上の化合物。
化合物に導入される反応性官能基は、光硬化性不飽和基であることが望ましい。
(1)ハードコートフィルム及び硬化性組成物において、マット剤を、平均粒子径が0.1~10μmのもので構成することができる。マット剤は、所定の平均粒子径を持つ単一のマット剤で構成してもよいが、平均粒子径が異なる複数のマット剤を組み合わせて用いることが好ましい。この場合、少なくとも、平均粒子径が0.1~4.0μmの第1のマット剤と、平均粒子径が3.0~10.0μmの第2のマット剤を含むようにすることができる。マット剤は、第1のマット剤と第2のマット剤のみを組み合わせて用いることもできる。この場合、それぞれの、粒子径分布の変動係数が15%以下のものを用いることができる。含有させるすべてのマット剤中での、第1のマット剤と第2のマット剤の重量比率は、第3以降のマット剤の含有、非含有を問わず、8:2~6:4とすることができる。マット剤は、その使用が単一であるか複数であるかを問わず、マット剤全体で、100重量部の樹脂分に対して0.05~5重量部の範囲で含有させることができる。
(3)ハードコートフィルム及び硬化性組成物において、(a)の熱可塑性樹脂及び(b)の熱硬化型樹脂の少なくともいずれかの反応性官能基として、(メタ)アクリロイル基を用いることができる。
第1の観点に係るハードコートフィルムは、マット剤に起因して光学機能層の表面に配置される複数の凸部のアスペクト比が、0.043以上に調整されることが好ましい。
(5)第1の観点に係る表面部材付き表示素子において、表面部材の表面側に、光学機能層を防眩層として利用した本発明のハードコートフィルムを含むことができる。また表面部材の背面側に、光学機能層をニュートンリング防止層として利用した本発明のハードコートフィルムを含むことができる。また表面部材を、保護板、タッチパネルまたは偏光フィルムで構成することができる。
(7)本発明の表面部材付き表示素子は、表示素子上に表面部材を配置され、前記表面部材がタッチパネルであり、該タッチパネルの最表面部材を、光学機能層を防眩層として利用した本発明のハードコートフィルムで構成することができる。
また、特定の樹脂分中に反応性官能基を導入させたので、電離放射線硬化型樹脂との結合が強固になる。その結果、該反応性官能基を導入していないものを配合した場合と比較して、塗膜硬度がより高められる。
本発明のハードコートフィルム及び表面部材付き表示素子は、本発明の硬化性組成物の硬化物で構成した光学機能層を有するので、防眩性やニュートンリング防止性と、スパークル防止性の両特性を同時に満足するとともに、塗膜硬度が高められている。
図1に示すように、本例の表示素子前面用フィルム1は、透明基材11上に光学機能層12が積層してある。
光重合開始剤としては、アセトフェノン類、ベンゾフェノン類、ミヒラーケトン、ベンゾイン、ベンジルメチルケタール、ベンゾイルベンゾエート、α-アシルオキシムエステル、チオキサンソン類などの光ラジカル重合開始剤や、オニウム塩類、スルホン酸エステル、有機金属錯体などの光カチオン重合開始剤が挙げられる。紫外線増感剤としては、n-ブチルアミン、トリエチルアミン、トリ-n-ブチルホスフィンなどが挙げられる。
熱可塑性樹脂としては、例えば、ポリエステル系樹脂、アクリル系樹脂、ポリカーボネート系樹脂、セルロース系樹脂、アセタール系樹脂、ビニル系樹脂、ポリエチレン系樹脂、ポリスチレン系樹脂、ポリプロピレン系樹脂、ポリアミド系樹脂、ポリイミド系樹脂、フッ素系樹脂などが挙げられる。
熱硬化型樹脂としては、例えば、ポリエステルアクリレート系樹脂、ポリウレタンアクリレート系樹脂、エポキシアクリレート系樹脂、エポキシ系樹脂、メラミン系樹脂、フェノール系樹脂、シリコーン系樹脂などが挙げられる。
熱可塑性樹脂と熱硬化型樹脂とを比較すると、表面形状を調整しやすく、取扱い性に優れるという点で熱可塑性樹脂が好適である。
なお、本例での化合物A2のTgは、硬化前のものである。
(a)熱可塑性樹脂に反応性官能基として光硬化性不飽和基が導入されており、重量平均分子量が7万以上で、かつガラス転移温度が45℃以上の化合物A1、
(b)熱硬化型樹脂に反応性官能基として光硬化性不飽和基が導入されており、重量平均分子量が7万以上で、かつガラス転移温度が45℃以上の化合物A2。
なお、本例のマット剤として、上述した2種(第1のマット剤、第2のマット剤)以外の、第3以降のマット剤を含有する場合も含め、これら2種(第1のマット剤、第2のマット剤)を組み合わせて用いる場合、全マット剤中での、第1のマット剤と第2のマット剤の重量比率は、8:2~6:4であることが好ましい。
コールターカウンター法とは、溶液中に分散しているマット剤粒子の数及び大きさを、電気的に測定する方法であって、粒子を電解液中に分散させ、吸引力を使って電気が流れている細孔に粒子を通過させる際に、粒子の体積分だけ電解液が置換され、抵抗が増加し、粒子の体積に比例した電圧パルスを測定する方法である。従って、この電圧パルスの高さと数とを電気的に測定することにより、粒子数と個々の粒子体積を測定して、粒子径及び粒子径分布を求めるものである。
光学機能層12の厚みは、好ましくは0.5μm以上、より好ましくは1μm以上であって、好ましくは10μm以下、より好ましくは5μm以下、特に好ましくは3μm以下とされる。
表示素子3としては、例えば、液晶表示素子、CRT表示素子、プラズマ表示素子、EL表示素子などが挙げられる。表面部材2としては、例えば、保護板2a、タッチパネル2b、偏光板2cなどが挙げられる。本例では、これら表面部材2(2a,2b,2c)の少なくとも一部に、本例の表示素子前面用フィルム1を含む。
なお、本例において、樹脂A~E、マット剤A~Eは次のものを用いた。
[樹脂B] 下記合成例2で得られた熱硬化性アクリル樹脂(固形分45%、ガラス転移温度:77℃、重量平均分子量:80,000、反応性官能基:アクリロイル基)、
[樹脂C] 下記合成例3で得られた熱硬化性アクリル樹脂(固形分40%、ガラス転移温度:86℃、重量平均分子量:100,000、反応性官能基:アクリロイル基)、
[樹脂D] 熱可塑性アクリル樹脂(アクリディック49-394-IM:DIC社、固形分50%、ガラス転移温度:16℃、重量平均分子量:65,000、反応性官能基:なし)、
[樹脂E] 熱可塑性アクリル樹脂(アクリディックA195:DIC社、固形分40%、ガラス転移温度:94℃、重量平均分子量:85,000、反応性官能基:なし)。
反応容器中に、溶媒としてメチルイソブチルケトン(MIBK)150重量部を供給して90℃まで加熱し維持した。メチルメタクリレート(MMA)61重量部、グリシジルメタクリレート(GMA)26重量部に、ラジカル重合開始剤としてアゾビス-2-メチルブチロニトリル(ABN-E)1.5重量部を混合したものを、2時間に亘って徐々に反応容器中に滴下した後、4時間に亘って放置した。その後、モノマー組成物を120℃で1時間に亘って加熱し重合体を得た。
次に、重合体を60℃まで冷却した後、重合体に、アクリル酸(AA)13重量部、重合禁止剤としてパラメトキシフェノール(MQ)0.05重量部、触媒としてトリフェニルホスフィン(TPP)0.5重量部を混合し、混合物を得た。その後、混合物を110℃で8時間に亘って加熱して、重合体にアクリル酸(AA)を付加させ、これにより熱硬化性樹脂に反応性官能基(アクリロイル基)が導入された化合物A2に相当する樹脂A(不揮発分40%、ガラス転移点86℃、重量平均分子量80,000)を製造した。
反応容器中に、溶媒としてメチルイソブチルケトン(MIBK)122重量部を供給して90℃まで加熱し維持した。メチルメタクリレート(MMA)40重量部、グリシジルメタクリレート(GMA)40重量部に、ラジカル重合開始剤としてアゾビス-2-メチルブチロニトリル(ABN-E)1.5重量部を混合したものを、2時間に亘って徐々に反応容器中に滴下した後、4時間に亘って放置した。その後、モノマー組成物を120℃で1時間に亘って加熱し重合体を得た。
次に、重合体を60℃まで冷却した後、重合体に、アクリル酸(AA)20重量部、重合禁止剤としてパラメトキシフェノール(MQ)0.05重量部、触媒としてトリフェニルホスフィン(TPP)0.5重量部を混合し、混合物を得た。その後、混合物を110℃で8時間に亘って加熱して、重合体にアクリル酸(AA)を付加させ、これにより熱硬化性樹脂に反応性官能基(アクリロイル基)が導入された化合物A2に相当する樹脂B(不揮発分45%、ガラス転移点60℃、重量平均分子量80,000)を製造した。
反応容器中に、溶媒としてメチルイソブチルケトン(MIBK)150重量部を供給して90℃まで加熱し維持した。メチルメタクリレート(MMA)61重量部、グリシジルメタクリレート(GMA)26重量部に、ラジカル重合開始剤としてアゾビス-2-メチルブチロニトリル(ABN-E)1.0重量部を混合したものを、2時間に亘って徐々に反応容器中に滴下した後、4時間に亘って放置した。その後、モノマー組成物を120℃で1時間に亘って加熱し重合体を得た。
次に、重合体を60℃まで冷却した後、重合体に、アクリル酸(AA)13重量部、重合禁止剤としてパラメトキシフェノール(MQ)0.05重量部、触媒としてトリフェニルホスフィン(TPP)0.5重量部を混合し、混合物を得た。その後、混合物を110℃で8時間に亘って加熱して、重合体にアクリル酸(AA)を付加させ、これにより熱硬化性樹脂に反応性官能基(アクリロイル基)が導入された化合物A2に相当する樹脂C(不揮発分40%、ガラス転移点86℃、重量平均分子量100,000)を製造した。
[マット剤B] アクリル樹脂粒子(テクポリマーSSX-105:積水化成品工業社、平均粒子径5.3μm、変動係数8.5%)
[マット剤C] アクリル樹脂粒子(テクポリマーMB20X-5:積水化成品工業社、平均粒子径5μm、変動係数:約20%)。
[マット剤D] アクリル樹脂粒子(MX-300:綜研化学工業社、平均粒子径3μm、変動係数9%)
[マット剤E] アクリル樹脂粒子(MX-180TA:綜研化学工業社、平均粒子径1.8μm、変動係数9%)。
厚み125μmの透明ポリエステルフィルム(コスモシャインA4350:東洋紡績社)の一方の面に、下記処方の塗布液aを塗布、乾燥、紫外線照射し、厚み3μmの光学機能層を形成し、実施例1のハードコートフィルムを得た。なお、括弧内に固形分の重量換算量を示した。
・電離放射線硬化型樹脂(固形分80%) 125部(100部)
(ユニディック17-813:DIC社)、
・樹脂A 107部(42.8部)
・光重合開始剤 3部
(イルガキュア184:チバ・ジャパン社)
・マット剤A 0.7部
・希釈溶剤 200部
塗布液aの樹脂Aの添加量を65部(固形分26部)に変更した以外は、実施例1と同様にして本例のハードコートフィルムを得た。
塗布液aの樹脂Aの添加量を250部(固形分100部)に変更した以外は、実施例1と同様にして本例のハードコートフィルムを得た。
塗布液aの樹脂Aを樹脂Bに変更し、かつその添加量を95部(固形分42.75部)に変更した以外は、実施例1と同様にして本例のハードコートフィルムを得た。
塗布液aのマット剤Aをマット剤Bに変更した以外は、実施例1と同様にして本例のハードコートフィルムを得た。
塗布液aの樹脂Aを樹脂Cに変更した以外は、実施例1と同様にして本例のハードコートフィルムを得た。
塗布液aのマット剤Aをマット剤Cに変更した以外は、実施例1と同様にして本例のハードコートフィルムを得た。
塗布液aの樹脂Aの添加量を97.2部(固形分38.9部)に変更した。また、塗布液aのマット剤Aをマット剤Eに変更し、かつその添加量を0.14部に変更した以外は、実施例1と同様にして本例のハードコートフィルムを得た。
塗布液aの樹脂Aの添加量を250部(固形分100部)に変更し、かつ電離放射線硬化型樹脂の添加量を48.75部(固形分39部)に変更した。また、塗布液aのマット剤Aをマット剤Eに変更し、かつその添加量を0.14部に変更した以外は、実施例1と同様にして本例のハードコートフィルムを得た。
塗布液aの樹脂Aの添加量を47.6部(固形分19.0部)に変更し、かつ電離放射線硬化型樹脂の添加量を256部(固形分204.75部)に変更した。また、塗布液aのマット剤Aをマット剤Dに変更し、かつその添加量を0.14部に変更した以外は、実施例1と同様にして本例のハードコートフィルムを得た。
塗布液aの樹脂Aの添加量を97.2部(固形分38.9部)に変更した。また、塗布液aのマット剤Aをマット剤Dに変更し、かつその添加量を0.14部に変更した以外は、実施例1と同様にして本例のハードコートフィルムを得た。
塗布液aの樹脂Aの添加量を196.4部(固形分78.6部)に変更し、かつ電離放射線硬化型樹脂の添加量を62部(固形分50部)に変更した。また、塗布液aのマット剤Aをマット剤Dに変更し、かつその添加量を0.14部に変更した以外は、実施例1と同様にして本例のハードコートフィルムを得た。
塗布液aの樹脂Aの添加量を250部(固形分100部)に変更し、かつ電離放射線硬化型樹脂の添加量を48.75部(固形分39部)に変更した。また、塗布液aのマット剤Aをマット剤Dに変更し、かつその添加量を0.14部に変更した以外は、実施例1と同様にして本例のハードコートフィルムを得た。
塗布液aの樹脂Aの添加量を97.2部(固形分38.9部)に変更し、かつマット剤Aの添加量を0.14部に変更した以外は、実施例1と同様にして本例のハードコートフィルムを得た。
塗布液aの樹脂Aの添加量を250部(固形分100部)に変更し、かつ電離放射線硬化型樹脂の添加量を48.75部(固形分39部)に変更した。また、塗布液aのマット剤Aの添加量を0.14部に変更した以外は、実施例1と同様にして本例のハードコートフィルムを得た。
塗布液aのマット剤D(平均粒子径3μm、変動係数9%)の一部(0.07部)をマット剤E(平均粒子径1.8μm、変動係数9%)に置き換えた。すなわち、塗布液aのマット剤D(添加量は0.14部)を平均粒子径が異なる2種類のマット剤D及びマット剤E(添加量はそれぞれ0.07部とした)に変更した以外は、実施例11(樹脂Aの含有割合が28%)と同様にして本例のハードコートフィルムを得た。
塗布液aのマット剤D(平均粒子径3μm、変動係数9%)の一部(0.07部)をマット剤A(平均粒子径5μm、変動係数9%)に置き換えた。すなわち、塗布液aのマット剤D(添加量は0.14部)を平均粒子径が異なる2種類のマット剤A及びマット剤D(添加量はそれぞれ0.07部とした)に変更した以外は、実施例11(樹脂Aの含有割合が28%)と同様にして本例のハードコートフィルムを得た。
塗布液aの樹脂Aを樹脂Dに変更し、かつその添加量を95部(固形分42.5部)に変更した以外は、実施例1と同様にして本例のハードコートフィルムを得た。
塗布液aの樹脂Aを樹脂Eに変更し、かつその添加量を95部(固形分42.75部)に変更した以外は、実施例1と同様にして本例のハードコートフィルムを得た。
塗布液aの樹脂Aの添加量を40部(固形分16部)に変更した以外は、実施例1と同様にして本例のハードコートフィルムを得た。
塗布液aの樹脂Aの添加量を300部(固形分120部)に変更した以外は、実施例1と同様にして本例のハードコートフィルムを得た。
塗布液aの樹脂Aを添加せず(添加量はゼロ)、また、塗布液aのマット剤Aをマット剤Eに変更し、かつその添加量を0.14部に変更した以外は、実施例1と同様にして本例のハードコートフィルムを得た。
塗布液aの樹脂Aを添加せず(添加量はゼロ)、また、塗布液aのマット剤Aをマット剤Dに変更し、かつその添加量を0.14部に変更した以外は、実施例1と同様にして本例のハードコートフィルムを得た。
塗布液aの樹脂Aの添加量を27.8部(固形分11.1部)に変更した。また、塗布液aのマット剤Aをマット剤Dに変更し、かつその添加量を0.14部に変更した以外は、実施例1と同様にして本例のハードコートフィルムを得た。
各例により得られたハードコートフィルムについて、以下の評価を行った。結果を表2に示す。
サイズ:3インチ、解像度:480×854dpiのワイドVGA液晶(表示素子)の液晶表示画面の全面をグリーン表示にした上で、該液晶表示画面上に各ハードコートフィルムを載置し、目視で液晶表示画面の観察を行った。その結果、スパークルが全く視認できなかったものを「◎」、スパークルが僅かに視認できるが支障がなかったものを「〇」、該「〇」評価よりも若干劣るが支障がなかったものを「△」、スパークルをはっきりと視認できたものを「×」とした。
各ハードコートフィルムを、表面が平滑なガラス板の上に光学機能層が密着するように乗せて指で押しつけ、ニュートンリングの発生状態を目視で観察した。その結果、ニュートンリングが見えなかったものを「○」、ニュートンリングが見えたものを「×」とした。
三波長蛍光灯ランプ下で黒い下地の上に各ハードコートフィルムを光学機能層が上面になるように置き、蛍光灯の映り込みを目視で評価した。その結果、蛍光灯のランプの輪郭が映り込まなかったものを「○」、僅かではあるが映り込んだものを「△」とした。
三波長蛍光灯ランプ下で黒い下地の上に各ハードコートフィルムを光学機能層が上面になるように置き、♯0000のスチールウールを200g/約2cm2の荷重で5回擦り(5回往復)、表面の傷を目視で観察した。その結果、傷が全く見えなかったものを「◎」、傷がほとんど見えなかったものを「○」、傷が僅かに見えるが支障がなかったものを「△」、傷がはっきり見えたものを「×」とした。
一部のハードコートフィルムの光学機能層の、それぞれ任意の凸部部分の5箇所について、共焦点レーザー顕微鏡(VK-9710、キーエンス社製)を使用し、対物レンズ:150倍、高さ測定ピッチ:0.01μmの条件で撮影した。そして得られた、凹凸形状の一方向(Y方向)に沿って切断した断面の凹凸プロファイルから、5箇所の凸部について、それぞれ凸部の高さHと裾野長さLを求め、その後、それぞれのアスペクト比(HのLに対する比H/L)を算出して表面性状を評価した。最終的には算出値5点の平均(Ave.)を各ハードコートフィルムのアスペクト比とした。
表1及び表2に示すように、実施例1~17では、塗布液中に、樹脂分として、電離放射線硬化型樹脂と、化合物A2に相当する樹脂A~Cのいずれかとを本発明の範囲で含む。その結果、得られた各ハードコートフィルムは、すべて、スパークル防止性に優れていた。これとともに、表面硬度が非常に高められていた。
なお、実施例7では、実施例1,5,6と同様の樹脂分を同量で使用したが、実施例1,5,6と異なり、粒子分布の変動係数が15%を超えるマット剤を単独で使用した。そのため、他の実施例1~6と比較して、スパークル防止性につき若干の劣りが認められたものの、十分に優れたスパークル防止性レベルにあった。
しかしながら、実施例8~17ではいずれも、実施例1~7と同様に樹脂A、B又はCの含有割合を適切とした。そのため、実施例1,5,6と同様に優れた結果、すなわち得られた各ハードコートフィルムは、スパークル防止性に極めて優れていること(◎)が確認できた。
比較例2では、塗布液中での電離放射線硬化型樹脂と樹脂Eとの重量比、使用した樹脂Eのガラス転移温度と重量平均分子量のいずれも本発明の範囲内であるが、使用した樹脂Eに反応性官能基が導入されていない。そのため、得られたハードコートフィルムは、スパークルは防止できていたが、表面硬度が劣っていた。
Claims (21)
- マット剤と、樹脂分としての電離放射線硬化型樹脂を含む硬化性組成物の硬化物で構成してあり、前記マット剤に起因した凸部を表面に複数備えてなる光学機能層を有するハードコートフィルムであって、
前記硬化性組成物は、樹脂分として、さらに、下記(a)及び(b)の1つ以上を含み、
全樹脂分中での含有割合が、電離放射線硬化型樹脂:50重量%以上85重量%未満、下記(a)及び(b):15重量%を超え50重量%以下であることを特徴とするハードコートフィルム。
(a)熱可塑性樹脂に光硬化性不飽和基が導入されており、重量平均分子量が7万以上で、かつガラス転移温度が45℃以上の化合物、
(b)熱硬化型樹脂に光硬化性不飽和基が導入されており、重量平均分子量が7万以上で、かつガラス転移温度が45℃以上の化合物。 - 請求項1記載のフィルムにおいて、前記凸部のアスペクト比が0.043以上であることを特徴とするハードコートフィルム。
- マット剤と、樹脂分としての電離放射線硬化型樹脂を含む硬化性組成物の硬化物で構成してあり、前記マット剤に起因した凸部を表面に複数備えてなる光学機能層を有するハードコートフィルムであって、
前記硬化性組成物は、樹脂分として、さらに、下記(a)及び(b)の1つ以上を含み、
前記凸部のアスペクト比が0.043以上であることを特徴とするハードコートフィルム。
(a)熱可塑性樹脂に光硬化性不飽和基が導入されており、重量平均分子量が7万以上で、かつガラス転移温度が45℃以上の化合物、
(b)熱硬化型樹脂に光硬化性不飽和基が導入されており、重量平均分子量が7万以上で、かつガラス転移温度が45℃以上の化合物。 - 請求項1~3のいずれかに記載のフィルムにおいて、前記マット剤は、平均粒子径が0.1~10μmであることを特徴とするハードコートフィルム。
- 請求項1~4のいずれかに記載のシートにおいて、前記マット剤は、平均粒子径が異なる複数のマット剤を組み合わせてなり、少なくとも、平均粒子径が0.1~4.0μmの第1のマット剤と、平均粒子径が3.0~10.0μmの第2のマット剤を含むことを特徴とするハードコートフィルム。
- 請求項5記載のシートにおいて、前記マット剤が、前記第1のマット剤と前記第2のマット剤のみを組み合わせてなり、それぞれの、粒子径分布の変動係数が15%以下のものを用いたことを特徴とするハードコートフィルム。
- 請求項5又は6記載のシートにおいて、すべての前記マット剤中での、前記第1のマット剤と前記第2のマット剤の重量比率が、8:2~6:4であることを特徴とするハードコートフィルム。
- 請求項1~7のいずれかに記載のフィルムにおいて、前記マット剤は、100重量部の樹脂分に対して0.05~5重量部の範囲で含有されていることを特徴とするハードコートフィルム。
- 請求項1~8のいずれかに記載のフィルムにおいて、前記光学機能層は、防眩効果を発現させる防眩層、または干渉縞の発生を抑制するニュートンリング防止層であることを特徴とするハードコートフィルム。
- 請求項1~8のいずれかに記載のフィルムにおいて、前記(a)の化合物及び前記(b)の化合物の少なくともいずれかの光硬化性不飽和基として、(メタ)アクリロイル基を用いたことを特徴とするハードコートフィルム。
- 表示素子上に表面部材を配置した表面部材付き表示素子において、前記表面部材は、その少なくとも一部に、請求項1~8のいずれかに記載のハードコートフィルムを含むことを特徴とする表面部材付き表示素子。
- 表示素子上に表面部材を配置した表面部材付き表示素子において、前記表面部材を、前記光学機能層を防眩層およびニュートンリング防止層の少なくともいずれかとして利用した請求項1~8のいずれかに記載のハードコートフィルムで構成したことを特徴とする表面部材付き表示素子。
- 請求項12記載の表示素子において、前記表面部材が保護板、タッチパネルまたは偏光フィルムであることを特徴とする表面部材付き表示素子。
- 防眩効果と干渉縞の発生抑制との少なくとも1つの光学機能を発現させる光学機能層を形成するための硬化性組成物において、
樹脂分とマット剤を含み、
前記樹脂分は、電離放射線硬化型樹脂と、下記(a)及び(b)の1つ以上とを含み、
全樹脂分中での含有割合が、電離放射線硬化型樹脂:50重量%以上85重量%未満、下記(a)及び(b):15重量%を超え50重量%以下であることを特徴とする硬化性組成物。
(a)熱可塑性樹脂に光硬化性不飽和基が導入されており、重量平均分子量が7万以上で、かつガラス転移温度が45℃以上の化合物、
(b)熱硬化型樹脂に光硬化性不飽和基が導入されており、重量平均分子量が7万以上で、かつガラス転移温度が45℃以上の化合物。 - 請求項9記載のフィルムにおいて、前記(a)の化合物及び前記(b)の化合物の少なくともいずれかの光硬化性不飽和基として、(メタ)アクリロイル基を用いたことを特徴とするハードコートフィルム。
- 表示素子上に表面部材を配置した表面部材付き表示素子において、前記表面部材は、その少なくとも一部に、請求項9記載のハードコートフィルムを含むことを特徴とする表面部材付き表示素子。
- 表示素子上に表面部材を配置した表面部材付き表示素子において、前記表面部材は、その少なくとも一部に、請求項10記載のハードコートフィルムを含むことを特徴とする表面部材付き表示素子。
- 表示素子上に表面部材を配置した表面部材付き表示素子において、前記表面部材を、前記光学機能層を防眩層およびニュートンリング防止層の少なくともいずれかとして利用した請求項9記載のハードコートフィルムで構成したことを特徴とする表面部材付き表示素子。
- 表示素子上に表面部材を配置した表面部材付き表示素子において、前記表面部材を、前記光学機能層を防眩層およびニュートンリング防止層の少なくともいずれかとして利用した請求項10記載のハードコートフィルムで構成したことを特徴とする表面部材付き表示素子。
- 請求項18記載の表示素子において、前記表面部材が保護板、タッチパネルまたは偏光フィルムであることを特徴とする表面部材付き表示素子。
- 請求項19記載の表示素子において、前記表面部材が保護板、タッチパネルまたは偏光フィルムであることを特徴とする表面部材付き表示素子。
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- 2014-09-19 JP JP2015539161A patent/JP6521524B2/ja active Active
- 2014-09-19 CN CN201480050495.7A patent/CN105531606B/zh active Active
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WO2021200884A1 (ja) * | 2020-03-31 | 2021-10-07 | 大日本印刷株式会社 | 光学積層体、並びに、これを備える偏光板、表面板及び画像表示装置 |
Also Published As
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JP6521524B2 (ja) | 2019-05-29 |
TW201514622A (zh) | 2015-04-16 |
TWI635358B (zh) | 2018-09-11 |
JPWO2015046047A1 (ja) | 2017-03-09 |
KR102225360B1 (ko) | 2021-03-09 |
CN105531606B (zh) | 2019-03-22 |
KR20160061359A (ko) | 2016-05-31 |
CN105531606A (zh) | 2016-04-27 |
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