TWI672519B - Watermark resistant film and touch panel display - Google Patents

Abstract

In a capacitance type touch panel display having a void layer inside, a watermark-resistant film is laminated on at least one of the surfaces facing through the void layer, which is transparent and has a measurement area of 10 μm × 10 μm on the surface. The calculated arithmetic average roughness Ra1 is a concavo-convex structure having an average roughness Ra1 of 0.7 nm or more and less than 5 nm and an arithmetic average roughness Ra2 of 500 μm × 500 μm in the measurement area of 10 to 50 nm. In particular, a watermark-resistant film may be laminated on the surface on the front side of the touch panel among the surfaces facing through the gap layer. This film is used in a capacitive touch panel display having a void layer inside to prevent the occurrence of watermarks, and can suppress glare even in a high-definition display device.

Description

Watermark-resistant film and touch panel display

The invention relates to a water-resistant film laminated on at least one of the surfaces facing through the gap layer in a capacitance-type touch panel display with a gap layer inside, and a capacitance-type touch panel provided with the film. monitor.

With the advancement of electronic displays with human-machine interfaces, dialog-type input systems have become popular. Among them, touch panel (coordinate input device) and display integrated devices are in ATMs (automatic teller machines), product management, and external work. (Diplomatic, sales), guidance display, entertainment equipment, etc. are widely used. In a lightweight and thin display such as a liquid crystal display, the keyboard can be used without using its features, and the use of touch panels in mobile devices has also increased. The touch panel is a device such as a finger or a pen that presses a specified position, and inputs specified information, etc. to a computer or other device. According to the method of position detection, it can be classified into optical, ultrasonic, electrostatic, and capacitive methods. Resistive film method, etc.

Among these methods, the capacitance method is a method of detecting a position by utilizing a change in the capacitance, but in recent years, from the viewpoint of excellent performance, a projection type capacitance type touch panel system using an ITO grid method is used. In smartphone, mobile phone, electronic paper, tablet type Personal computers (PCs), tablet PCs, gaming machines, and other mobile devices are being used and attracting attention. Especially in smart phones and tablet PCs, high-definition display devices have also begun to spread, and in these devices, optical characteristics such as high transparency and anti-glare properties are also required. In addition, a TV equipped with a touch panel on the display of a high-resolution TV (4K TV) that has four times the number of pixels of a display panel as a Full HD TV, or a high-resolution TV used in the construction or medical fields. Handwriting input devices have also been developed. As a display surface (upper transparent electrode) of a touch panel display of such a device, a transparent material is used, and as the transparent material, a glass material is widely used in terms of excellent transparency or heat resistance. However, since glass materials are easily broken, they are likely to be broken due to dropping, etc., and fragments are scattered. Therefore, it is necessary to take measures to prevent fragments from scattering even if they are broken. Therefore, as a method for preventing the scattering of fragments due to the breakage of the upper electrode (cover glass) formed of a glass material, it is known to attach a hard-to-break plastic to the inside (back or inner layer) of the cover glass. A method for a thin film (a film for preventing the scattering of glass fragments).

The scattering prevention film is usually a transparent resin layer such as a polyethylene terephthalate (PET) film, and an adhesive layer which is laminated on one side of the transparent resin layer and integrated with the cover glass [ OCA (optical transparent adhesive) film, etc.], and a transparent hard coat (CHC) layer laminated on the other side of the transparent resin layer and used to prevent damage during the production or distribution steps form. For example, in a capacitive touch panel using the ITO gate method, an ITO (indium oxide-tin oxide-based composite oxide) film is laminated on the inner side (inner side or inner layer) of the cover glass disposed on the outermost surface. This ITO film is attached with the scattering prevention film The CHC layer side is arranged on a display element (display unit) such as a liquid crystal display (LCD) or an organic electroluminescence (EL) display (OLED). The CHC layer and the display element may be integrated through a transparent adhesive layer or the like. From the viewpoint of productivity, etc., an adhesive layer (spacer) is provided between the CHC layer and the end portion (peripheral portion or outer frame portion) of the display element. ) Exists and integrates, and a method of forming a void (space layer) between the hard coat layer and the liquid crystal layer is widespread. Furthermore, in recent years, in PC flat panels and the like, there is a large demand for weight reduction and thinning. As a cover glass (glass substrate) for an upper electrode, only one glass type using only one glass substrate is also popular. However, in an ITO grid type capacitive touch panel (particularly a glass type) provided with such a space layer (space part), if the display surface is touched with a finger or a pen, the upper electrode is easily bent, and CHC The layer and the surface of the display element (polarizing layer in the LCD, etc.) are closely adhered without separation, and a phenomenon of blackening (black spots) occurs. This phenomenon is called watermark (WM). For this phenomenon, in the conventional touch panel, micron-sized particles are mixed in the hard coating layer to form a micron-sized uneven structure on the surface, which becomes a watermark-resistant ( AWM) layer, suppresses the adhesion between the AWM layer and the surface of the display element, and prevents the occurrence of WM. However, in recent years, with the high definition of touch panel displays, glare occurs in the scattering prevention film having an AWM layer containing particles, and visibility is reduced. In particular, if the height of the convex portion is increased, the AWM characteristics are improved, but on the other hand, dazzling is likely to occur, and the AWM characteristics and the optical characteristics are in a difficult trade-off relationship.

Japanese Patent Publication No. 5440747 (Patent Document 1) discloses a display device with a capacitance type touch panel including a display device and a capacitance type touch panel arranged with a gap between the display device and the capacitance type touch panel. , The aforementioned display which is opposed to each other across the aforementioned gap The surface roughness of the surface of the device or the touch panel of the aforementioned electrostatic capacity method is adjusted to 1.5 nm to 400 nm. In the examples of this document, a protective sheet is formed by using a hard-coat layer-forming composition containing a polyfunctional (meth) acrylate and colloidal silica with a particle diameter of 100 nm to form a protective sheet with a surface roughness of 50 ~ 300nm uneven structure. Further, in the comparative example of this document, a protective sheet having an uneven structure with a surface roughness of 1 nm was produced, and a Newton ring system was clearly generated, and it was also attached to a polarizing plate.

However, even in a display device with a touch panel with an electrostatic capacity method, in a tablet PC or the like that has been advanced in high definition in recent years, dazzling has occurred, and optical characteristics are insufficient.

[Prior technical literature] [Patent Literature]

Patent Document 1: Japanese Patent No. 5440747 (Scope of Patent Application, Examples)

Therefore, an object of the present invention is to provide a watermark-resistant film and a capacitive touch panel display having the same. The watermark-resistant film is a capacitive touch panel display with a gap layer inside to prevent watermarks from occurring, and Even in a high-definition display device, glare can be suppressed.

Another object of the present invention is to provide a watermark-resistant film and an electrostatic capacity type touch panel display having the same. The watermark-resistant film can suppress glass breakage due to a touch panel display including a cover glass. The resulting glass fragments were scattered.

Still another object of the present invention is to provide a watermark-resistant film and a capacitive touch panel display having the same. The watermark-resistant film is low in haze, excellent in transparency, and also has scratch resistance.

The present inventors made an intensive review in order to achieve the aforementioned problems. As a result, they found that the inner surface of the void-forming layer contained in the capacitive touch panel display was laminated with an anti-watermark film, which was transparent and on the surface. It has a small uneven structure with an arithmetic average roughness Ra1 calculated in the measurement area of 10 μm × 10 μm of 0.7 nm or more and less than 5 nm and an arithmetic average roughness Ra2 calculated in the measurement area of 500 μm × 500 μm between 10 and 50 nm. Low Ra, which was not considered to exhibit watermark resistance in the conventional technical knowledge, also has a concave-convex structure equivalent to large undulations in addition to the minute uneven structure, which can prevent the occurrence of watermarks, and can make the watermark-resistant characteristics and high definition The dazzling suppression in the display device coexists, and the present invention has been completed.

That is, the watermark-resistant film of the present invention is a watermark-resistant film laminated on at least one surface of a surface facing through the gap layer in a capacitive touch panel display having a gap layer inside, which is transparent. The surface has a concave-convex structure having an arithmetic average roughness Ra1 calculated in a measurement region of 10 μm × 10 μm of 0.7 nm or more and less than 5 nm and an arithmetic average roughness Ra2 calculated in a measurement region of 500 μm × 500 μm of 10 to 50 nm. The watermark resistant film may also be a transparent laminated film including a transparent resin layer and a watermark resistant layer. The watermark resistant layer is laminated on one side of the transparent resin layer, and contains a hardening resin, a thermoplastic It is formed by the hardened material of the hardening composition of the resin and metal oxide particles having an average primary particle diameter of 1 to 50 nm, and the surface has an arithmetic average roughness Ra1 of 0.8 nm or more and less than 1.5 nm in the measurement area of 10 μm × 10 μm. The uneven structure. The curable resin includes a curable resin having a polymerizable group having 4 or less functions and a curable resin having a polymerizable group of 5 or more functions. The thermoplastic resin is a cellulose derivative. The metal oxide fine particles may be selected from antimony-containing compounds. At least one of the group consisting of tin oxide, antimony oxide, tin oxide, and zinc oxide.

The watermark-resistant film of the present invention may be further laminated with a low refractive index layer on the surface of the side having the uneven structure, or may be further laminated with an adhesive layer on the surface of the side opposite to the side having the uneven structure. The watermark-resistant film of the present invention has a water contact angle on the surface of the side having a concave-convex structure, which can be 65 to 80 °.

In the present invention, a capacitive touch panel display is also included, which has a void layer inside, and the aforementioned watermark-resistant film is laminated on at least one of the surfaces facing through the void layer. The touch panel display of the present invention may also have a watermark-resistant film laminated on the surface of the front side of the touch panel among the surfaces facing through the gap layer. The touch panel of the present invention may include only one transparent substrate between the gap layer and the display surface. The transparent substrate may also be a glass plate having a thickness of 50 to 3000 μm.

In the present invention, on the inner surface of the void-forming layer included in the electrostatic capacity type touch panel display (especially a glass-type display), the laminated layer is transparent and has a measurement area on the surface. An anti-watermarking film having a concave-convex structure with an arithmetic average roughness Ra1 of 10 μm × 10 μm in a domain of 0.7 nm or more and less than 5 nm and an arithmetic average roughness Ra2 of 500 μm × 500 μm in a measurement area of 10 nm or more and less than 50 nm. This can suppress glare even in a high-definition display device. In addition, if a water-resistant film is laminated on the front surface of the touch panel among the surfaces facing through the gap layer, glass fragments caused by cracking of the glass of the touch panel display including the cover glass can be suppressed. Flying away. Furthermore, if it is formed by the hardened | cured material of a specific hardenable composition, it will be low haze, it will be excellent in transparency, and it can improve abrasion resistance.

[Form of Implementing Invention]

[Characteristics of anti-watermark film]

The anti-watermark (AWM) film of the present invention is a capacitive touch panel display having a void layer inside, which is laminated on at least one of the surfaces facing through the aforementioned void layer, and can also be laminated on the touch panel. The front surface can also be laminated on the rear surface. If it is laminated on the front surface of the touch panel, it can also be used as a scattering prevention film for glass fragments of a touch panel including a cover glass.

The AWM film of the present invention has a relatively small uneven structure on the surface, and the arithmetic average roughness Ra1 calculated in the measurement area of 10 μm × 10 μm is 0.7 nm to 5 nm (for example, 0.75 nm to 2 nm), especially even if it is less than 1.5 Micro-convex structure in nm can also be displayed The AWM property is preferably 0.8 nm to 1.5 nm, and more preferably 0.9 to 1.48 nm (especially 0.95 to 1.45 nm). If Ra1 is too small, the AWM performance is reduced, and if it is too large, dazzling is likely to occur on high-definition displays. The concave-convex structure may be formed on the outermost surface of the AWM thin film. For example, when a low-refractive index layer is formed on the outermost surface, the low-refractive index layer only needs to have such Ra1.

The AWM film of the present invention has a larger uneven structure (undulation) in addition to the fine uneven structure described above. The arithmetic average roughness Ra2 calculated in the measurement area of 500 μm × 500 μm is 10 to 50 nm (for example, 11 to 45 nm), especially AWM properties can be exhibited even with a minute uneven structure of 40 nm or less, preferably 12 to 44 nm, and more preferably about 13 to 40 nm. If Ra2 is too small, the AWM performance is reduced, and if it is too large, dazzling is likely to occur on high-definition displays. The concave-convex structure may be formed on the outermost surface of the AWM film. For example, when a low-refractive index layer is formed on the outermost surface, the low-refractive index layer only needs to have such Ra2. In the present invention, in addition to the aforementioned Ra1 having a fine uneven structure, Ra2 having an undulating structure in such a range can coexist AWM properties and suppression of glare.

In the present invention, Ra1 and Ra2 can be measured by a method according to JIS B0601.

The AWM film of the present invention is transparent. When the thickness is 100 μm, the total light transmittance according to JIS K7361 is, for example, 70 to 100%, preferably 80 to 100% (for example, 85 to 99%), and more preferably 90 to 98. % (Especially 92 ~ 96%).

The haze of the AWM thin film system of the present invention is also small. At 100 μm, the haze rate according to JIS K7136 is, for example, 0.2 to 1.5%, more preferably 0.25 to 1%, and even more preferably 0.3 to 0.6% (especially 0.4 to 0.5%). In the present invention, by having such a low haze value, even in a high-definition display, dazzling can be suppressed and visibility can be improved.

The sharpness of the penetrating image of the AWM film of the present invention is, for example, 80 to 100%, preferably 85 to 99%, and more preferably 88 to 98% (especially 90 to 97%) when using an optical comb with a width of 0.5 mm. )about. If the transparency of the transmitted image is within the aforementioned range, there will be less scattering of the penetrating light in a straight direction, and even when a transparent laminated film is provided on a high-definition display device, the scattering from each pixel will be reduced to prevent glare.

The sharpness of the transmitted image refers to the quantification of the blur or distortion of the light after passing through the film. The transmitted image sharpness is measured by an optical comb that moves transmitted light from the film, and the value is calculated from the amount of light in the light and dark portions of the optical comb. That is, when the film obscures the penetrating light, as the image of the slit imaged on the optical comb becomes thicker, the amount of light in the penetrating portion becomes 100% or less. On the other hand, the non-penetrating portion becomes due to light leakage. Above 0%. The value C of the clarity of the transmitted image is the maximum transmitted light M from the transparent portion of the optical comb and the minimum transmitted light m from the opaque portion, which is defined by the following formula.

C (%) = [(M-m) / (M + m)] × 100

That is, the closer the value of C is to 100%, the smaller the blur of the image due to the transparent laminated film [Reference; Suga, Sanda Village, Painting Technology, July 1985].

The reflectance of the AWM thin film system of the present invention is also low, which may be 10% Hereinafter, it is, for example, 0.1 to 8%, preferably 0.5 to 6%, and more preferably about 1 to 5%.

The surface of the AWM film system of the present invention is also excellent in wettability, and the water contact angle of the surface on the side having the uneven structure is 80 ° or less (for example, 65 to 80 °), such as 69 to 80 °, and more preferably 70 to 75 ° , Especially preferably around 71 ~ 74 °. If the water contact angle is too low, slippage may be reduced and scratch resistance may be reduced. This water contact angle only needs to be provided on the outermost surface of the AWM film. For example, when the low refractive index layer is formed on the outermost surface, the low refractive index layer only needs to have such a water contact angle. In the present invention, the water contact angle can be measured using an automatic-dynamic contact angle meter, and in detail, it can be measured by a method described in Examples described later.

[Material and structure of AWM film]

As long as the AWM film has the aforementioned characteristics, the material system is not particularly limited, and it may be an inorganic material or an organic material. However, from the viewpoint of excellent mechanical properties such as flexibility, organic materials such as resin are preferred. From the viewpoint of mechanical properties and productivity, particularly preferred is a transparent laminated film, which includes a transparent resin layer and a surface laminated on one side of the transparent resin layer and has a surface that satisfies the aforementioned arithmetic average roughness Ra1 and Ra2. Watermark (AWM) layer with a concave-convex structure.

(AWM layer)

The AWM layer is formed of a hardened product of a hardenable composition containing a hardenable resin, a thermoplastic resin, and metal oxide particles having an average primary particle diameter of 1 to 100 nm.

(A) Hardening resin

Hardening resin (hardening monomer or hardening resin precursor) Compounds that have functional groups that react by heat or active energy rays (such as ultraviolet rays or electron rays) can be hardened or crosslinked by heat or active energy rays, etc., and can form resins (especially hardened or crosslinked resins). Various hardening compounds. Examples of the curable resin include a thermosetting compound or a resin [a low molecular weight compound having an epoxy group, a polymerizable group, an isocyanate group, an alkoxysilyl group, or a silanol group (for example, an epoxy resin, Unsaturated polyester resins, urethane resins, silicone resins, etc.), photocurable compounds (photocurable monomers, oligomers) that can be hardened by active light (ultraviolet rays, etc.) UV-curable compounds, etc.) and the like, and the photo-curable compounds may be EB (electron beam) -curable compounds. In the present invention, a photocurable compound such as a photocurable monomer, oligomer, or a photocurable resin having a low molecular weight may be referred to simply as a "photocurable resin".

The photocurable compound includes, for example, a monomer, an oligomer (or a resin, and particularly a low molecular weight resin). The monomer can be classified into, for example, a monofunctional monomer having one polymerizable group and a polyfunctional monomer having at least two polymerizable groups.

Examples of the monofunctional monomer include (meth) acrylic monomers such as (meth) acrylates, vinyl monomers such as vinylpyrrolidone, and (meth) acrylic acid isomers. (Meth) acrylate and the like having a bridged cyclic hydrocarbon group such as esters, adamantane (meth) acrylate and the like.

The polyfunctional monomer includes a polyfunctional monomer having about 2 to 8 polymerizable groups. Examples of the bifunctional monomer include ethylene glycol di (meth) acrylate and propylene glycol di (methyl). ) Acrylate, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hexanediol Alkanediol di (meth) acrylate such as di (meth) acrylate; diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyoxytetramethylene glycol (Poly) oxyalkylene glycol di (meth) acrylate such as di (meth) acrylate; tricyclodecanedimethanol di (meth) acrylate, adamantane di (meth) acrylate, etc. Di (meth) acrylates and the like that bridge cyclic hydrocarbon groups.

Examples of 3 to 8 functional monomers include glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

Examples of the oligomer or resin include (meth) acrylates and epoxy (meth) acrylates of bisphenol A-alkylene oxide adducts (bisphenol A-type epoxy (meth) acrylates and phenolic resins) Varnish-type epoxy (meth) acrylate, etc.), polyester (meth) acrylate (e.g., aliphatic polyester-type (meth) acrylate, aromatic polyester-type (meth) acrylate, etc.), (Poly) urethane (meth) acrylate (polyester urethane (meth) acrylate, polyether urethane (meth) acrylate, etc.), polysiloxane (Meth) acrylates and the like. These (meth) acrylate oligomers or resins may also include the copolymerizable monomers exemplified under the item of (meth) acrylic resin in the aforementioned polymer component. These photocurable compounds are used alone or in combination of two or more kinds.

Furthermore, from the viewpoint of improving the strength of the AWM layer, the curable resin may contain fluorine atoms or inorganic particles. Examples of the fluorine-containing curable compound include fluorides of the monomers and oligomers described above, such as ( Fluoroalkyl (meth) acrylate [e.g., perfluorooctyl ethyl (meth) acrylate or trifluoroethyl (meth) acrylate, etc.], fluorinated (poly) oxyalkylene glycol di (meth) acrylic acid Esters [for example, fluoroethylene glycol di (meth) acrylate, fluoropropylene glycol di (meth) acrylate, etc.], fluorine-containing epoxy resins, urethane-based resins, and the like. Examples of the curable compound containing inorganic particles include inorganic particles having a polymerizable group on the surface (for example, silica particles whose surface is modified with a silane coupling agent having a polymerizable group). The nano-sized silica particles having a polymerizable group on the surface are, for example, a polyfunctional hybrid UV curing agent (Z7501) commercially available from JSR (KK).

Preferred curable resins are light-curable compounds that can be cured in a short time, such as ultraviolet curable compounds (which may be monomers, oligomers, or low-molecular-weight resins), and EB curable compounds. The curable resin which is practically advantageous is an ultraviolet curable resin.

In addition, in the present invention, in order to improve the scratch resistance of the AWM layer, the curable resin preferably contains a resin having two or more functions (for example, about 2 to 10 functions), and more preferably three or more functions (for example, about 3 to 8 functions). The polymerizable group-curable resin is, in particular, a polyfunctional (meth) acrylate, such as a (meth) acrylate having 3 or more functions (especially 4 to 8 functions) (for example, dipentaerythritol hexa (meth) acrylate).

Furthermore, in the present invention, in order to form a specific surface uneven structure on the surface of the AWM layer, it is preferable to combine polymerization having 4 or less functions (preferably 2 to 4 functions, and more preferably 3 to 4 functions) in combination. A curable resin having a flexible group and a curable resin having a polymerizable group having 5 or more functions (for example, 5 to 10 functions, preferably 5 to 8 functions, and more preferably about 5 to 7 functions). In particular, it is also possible to combine 2 to 4 functional (meth) acrylates [especially pentaerythritol three 3 to 4-functional (meth) acrylates such as (meth) acrylates and 5 to 8-functional (meth) acrylates [especially 5- to 7-functional (meth) such as dipentaerythritol hexa (meth) acrylate )Acrylate].

A curable resin having a polymerizable group of 4 or less (for example, 2 to 4-functional (meth) acrylate) and a curable resin having a polymerizable group of 5 or more (for example, 5 to 10 functional (meth) acrylate) ) The weight ratio is the former / the latter = 99/1 ~ 1/99, preferably 90/10 ~ 10/90, more preferably 70/30 ~ 30/70 (especially 60/40 ~ 40/60) . In the present invention, a specific uneven structure can be formed on the surface of the AWM layer by combining the curable resin having the functional group number in such a ratio without impairing the mechanical characteristics.

Considering compatibility with the thermoplastic resin described later, the molecular weight of the curable resin is 5,000 or less (for example, 100 to 5,000), preferably 2000 or less (for example, 200 to 2000), and more preferably 1,000 or less (for example, 300 to 1,000). The molecular weight is the weight-average molecular weight measured by gel permeation chromatography (GPC) in terms of polystyrene, and the low molecular weight can be calculated from the molecular formula.

The curable composition may include a curing agent depending on the type of the curable resin. For example, the thermosetting resin may include a curing agent such as an amine or a polycarboxylic acid, and the photocurable resin may include a photopolymerization initiator. As the photopolymerization initiator, conventional components such as acetophenones or phenylacetones, benzoin, benzoin, diphenylketone, thioxanthone, and fluorenylphosphine oxide can be exemplified. Wait. The content of the hardener such as a light hardener is 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, and more preferably 1 to 8 parts by weight based on 100 parts by weight of the curable resin. (Especially about 1 to 5 parts by weight), or about 3 to 8 parts by weight.

The curable resin may contain a curing accelerator. For example, the photocurable resin may contain a photohardening accelerator such as a tertiary amine (such as a dialkylaminobenzoate), a phosphine-based photopolymerization accelerator, and the like.

(B) Thermoplastic resin

The thermoplastic resin is blended to improve mechanical properties such as flexibility for the AWM layer, and is preferably a resin that does not have a reactive group (particularly, a polymerizable group such as an ethylenically unsaturated bond) that does not participate in the curing reaction of the curable resin.

Examples of such thermoplastic resins include styrene resins [polystyrene, copolymers of styrene and (meth) acrylic monomers, AS resins, styrene-butadiene copolymers, and the like], (methyl ) Acrylic resin [Poly (meth) acrylate such as polymethyl methacrylate, methyl methacrylate- (meth) acrylic copolymer, methyl methacrylate- (meth) acrylate copolymer, Methyl methacrylate-acrylate- (meth) acrylic acid copolymer, (meth) acrylate-styrene copolymer (MS resin, etc.), (meth) acrylic acid- (meth) acrylate- (methyl) Base) acrylic iso Esters, etc.], organic acid vinyl ester resins [ethylene-vinyl acetate copolymer, vinyl acetate-vinyl chloride copolymer, vinyl acetate- (meth) acrylate copolymer, polyvinyl alcohol, ethylene-vinyl alcohol copolymerization Materials, polyvinyl acetal resin, etc.], vinyl ether resins (polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl propyl ether, polyvinyl third butyl ether, etc.), halogen-containing Resin [polyvinyl chloride, polyvinylidene fluoride, vinyl chloride-vinyl acetate copolymer, vinyl chloride- (meth) acrylate copolymer, vinylidene chloride- (meth) acrylate copolymer, etc.], Olefin resins [Homopolymers of olefins such as polyethylene and polypropylene, ethylene-vinyl acetate copolymers, ethylene-vinyl alcohol copolymers, ethylene- (meth) acrylic copolymers, ethylene- (meth) acrylates Copolymer, alicyclic olefin resin, etc.], polycarbonate resin (bisphenol A polycarbonate, etc.), polyester resin (polyethylene terephthalate, polybutylene terephthalate) , polyethylene naphthalate, polyethylene terephthalate, etc. C _2-4 alkylene aryl ester, C _2-4 alkylene arylate copolyesters non etc. (Polyester, etc.), polyamide resins (polyamide 46, polyamide 6, polyamide 66, polyamide 610, polyamide 612, polyamide 11, polyamide 12, etc.) Polyamines, etc.), thermoplastic polyurethane resins (polyester urethane-based resins, etc.), polyfluorene-based resins (polyether fluorene, polyfluorene, etc.), polyphenylene ether-based resins ( Polymers of 2,6-xylenol, etc.), cellulose derivatives (cellulose esters, etc.), polysiloxane resins (polydimethylsiloxane, polymethylphenylsiloxane, etc.), rubber or Elastomers (dibutene rubber such as polybutadiene, polyisoprene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, acrylic rubber, urethane rubber, polysilicon Oxygen rubber, etc.). These thermoplastic resins may be used alone or in a combination of two or more.

Among these thermoplastic resins, styrene resins, (meth) acrylic resins, alicyclic olefin resins, polyester resins, cellulose derivatives, etc. are widely used, but they are excellent in transparency and heat resistance. From the viewpoint that mechanical properties such as flexibility can also be improved, cellulose derivatives are preferred.

The cellulose derivatives include cellulose esters, cellulose ethers, and cellulose carbamates.

Examples of cellulose esters include aliphatic organic acid esters (cellulose acetates such as cellulose diacetate and cellulose triacetate; cellulose propionate, cellulose butyrate, and cellulose). C _2-6 halogenates such as acetate propionate, cellulose acetate butyrate, etc.), aromatic organic acid esters (C _7-12 aromatics such as cellulose phthalate, cellulose benzoate, etc.) Carboxylic acid esters), inorganic acid esters (for example, cellulose phosphate, cellulose sulfate, etc.) and the like. Cellulose esters may also be mixed acid esters such as acetic acid and nitrocellulose.

Examples of cellulose ethers include cyanoethyl cellulose; hydroxy C _2-4 alkyl cellulose such as hydroxyethyl cellulose and hydroxypropyl cellulose; and C such as methyl cellulose and ethyl cellulose. _1-6 alkyl cellulose; carboxymethyl cellulose or a salt thereof, benzyl cellulose, ethynyl alkyl cellulose, and the like. Examples of the cellulose carbamates include cellulose phenyl carbamate and the like.

These cellulose derivatives may be used alone or in combination of two or more. Among these cellulose derivatives, cellulose esters are preferred, especially cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, and cellulose acetate. Cellulose C _2-6 compounds such as esters, cellulose acetate butyrate and the like. Among them, in order to have high solubility in the solvent, the preparation of the coating liquid is easy, and the viscosity of the coating liquid can be easily adjusted by a small amount of addition, and at the same time, the excessive aggregation of the fine particles in the coating liquid is suppressed, and the storage stability is improved. Cellulose C _2-4 compounds such as cellulose diacetate, cellulose acetate propionate, cellulose acetate butyrate (especially cellulose acetate C _3-4 , such as cellulose acetate propionate) Halide).

The ratio of the thermoplastic resin to 100 parts by weight of the curable resin is, for example, 0.1 to 30 parts by weight, and preferably 0.1 to 10 parts by weight (for example, 0.3 to 5 parts by weight), more preferably about 0.5 to 3 parts by weight (especially 0.8 to 2 parts by weight). The ratio of the thermoplastic resin to 100 parts by weight of the metal oxide fine particles is, for example, 100 to 1,000 parts by weight, preferably 150 to 500 parts by weight, and more preferably about 200 to 400 parts by weight. In the present invention, by adjusting the ratio of the thermoplastic resin, the balance between mechanical properties such as scratch resistance and impact absorption or cushioning properties can be adjusted. If it is within this range, the balance between the two is excellent.

(C) Metal oxide fine particles

In the present invention, by mixing metal oxide fine particles in the AWM layer, the distribution of the metal oxide in the resin component becomes uneven due to the occurrence of convection, and the resin component bulges. On the surface of the AWM layer, it can be formed. A small uneven structure that suppresses the occurrence of watermarks and the occurrence of dazzling. The metal oxide fine particles are excellent in transparency and scratch resistance, and when a low refractive index layer is formed thereon, the adhesion with the low refractive index layer can also be improved.

Examples of the metal oxide constituting the metal oxide fine particles include a Group 4A metal oxide (such as titanium oxide and zirconia), a Group 5A metal oxide (such as vanadium oxide), and a Group 6A metal oxide of the periodic table. (Molybdenum oxide, tungsten oxide, etc.), Group 7A metal oxide (manganese oxide, etc.), Group 8 metal oxide (nickel oxide, iron oxide, etc.), Group 1B metal oxide (copper oxide, etc.), Group 2B metal oxides (zinc oxide, etc.), Group 3B metal oxides (alumina, indium oxide, etc.), Group 4B metal oxides (tin oxide, etc.), Group 5B metal oxides (antimony oxide, etc.), etc. .

These metal oxide fine particles may be used alone or in combination of two or more. Among these metal oxide fine particles, preferably Metal oxides containing antimony, tin, and zinc, such as antimony trioxide, antimony tetraoxide, antimony pentoxide, antimony-containing tin oxide (antimony-doped tin oxide), tin oxide, zinc oxide, and the like are particularly preferred. Fine particles (especially antimony-containing tin oxide particles (ATO particles)) of at least one selected from the group consisting of antimony-containing tin oxide, antimony oxide, tin oxide, and zinc oxide.

The metal oxide fine particles may be in the form of a dispersion liquid dispersed in a solvent. Examples of the solvent include water, alcohols (lower alcohols such as methanol, ethanol, isopropanol, butanol, and cyclohexanol), and ketones (acetone, methyl ethyl ketone, and methyl isobutyl ketone). , Cyclohexanone, etc.), esters (methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl formate, ethyl formate, etc.), ethers (diethyl ether, diethyl ether Alkanes, tetrahydrofuran, etc.), aliphatic hydrocarbons (hexane, etc.), alicyclic hydrocarbons (cyclohexane, etc.), aromatic hydrocarbons (benzene, etc.), halogenated hydrocarbons (dichloromethane, dichloroethane, etc.) ), Cellosolvents (methyl cellosolve, ethyl cellosolve, etc.), cellosolve acetates, amidoamines (dimethylformamide, dimethylacetamide, etc.), etc. These solvents may be used alone or in a combination of two or more. Among these solvents, a mixture of lower alcohols such as ethanol or isopropanol (for example, a weight ratio of ethanol / isopropanol = 90/10 to 50/50 (especially 80/20 to 60/40) is widely used. Solvent). The concentration of the metal oxide fine particles in the dispersion is, for example, 0.1 to 50% by weight, preferably 1 to 40% by weight, and more preferably about 5 to 30% by weight. In order to disperse in these solvents, the surface of the metal oxide fine particles may be subjected to a conventional surface treatment.

The shape of the metal oxide fine particles is not particularly limited, and examples thereof include a spherical shape, an ellipsoidal shape, a polygonal shape (a polygonal hammer shape, a cube shape, a rectangular parallelepiped shape, etc.), a plate shape, a rod shape, and an irregular shape. Form table From the viewpoint of a uniform uneven structure, an isotropic shape such as a spherical shape is preferable.

The number-average primary particle size of the metal oxide fine particles is, for example, 1 to 50 nm, preferably 1.5 to 40 nm (for example, 2 to 30 nm), and more preferably 3 to 15 nm (especially 5 to 10 nm). If the primary particle diameter is too small, it is difficult to form a concave-convex structure system on the surface of the AWM layer. If it is too large, it is difficult to form a minute concave-convex structure system, and it is larger than the wavelength of light, which may cause glare. Yu. In the present invention, instead of using particles having a large particle diameter, by using nano-sized particles, the particles are produced under specific conditions, and a minute uneven structure can be formed.

In the present invention, the number-average primary particle size is based on a particle size distribution meter such as a dynamic light scattering method, and a particle size measuring device ("PAR-III" manufactured by Otsuka Electronics Co., Ltd.) can be used. Determination.

Based on 100 parts by weight of the curable resin. The ratio of the metal oxide fine particles is, for example, 0.05 to 10 parts by weight, preferably 0.1 to 5 parts by weight, and particularly preferably about 0.15 to 3 parts by weight (especially 0.2 to 1 part by weight). If the proportion of the fine particles is too small, it is difficult to form the uneven structure system on the surface of the AWM layer, and if it is too large, it is difficult to form the minute uneven structure system. In the present invention, even if the proportion of the fine particles is small, an uneven structure capable of achieving AWM properties can be formed.

(D) Other additives

Various additives can be contained in the AWM layer, such as other fine particles (organic fine particles, inorganic fine particles, etc.), leveling agents, stabilizers (antioxidants, ultraviolet absorbers, etc.), surfactants, water-soluble polymers, Filler, crosslinker, coupling agent, colorant, flame retardant, lubricant , Wax, preservative, viscosity adjuster, tackifier, defoamer, etc. The ratio of the additive to the entire AWM layer is, for example, about 0.01 to 10% by weight (especially 0.1 to 5% by weight).

In the present invention, although the reason is not determined, a fine particle aggregating agent is not used (for example, the agglomerating agent described in Japanese Patent Application Laid-Open No. 2009-265143), and a small amount of metal oxide fine particles are appropriately agglomerated in the AWM layer and A nucleus is formed, and by the convection effect in the drying step, the metal oxide fine particles are aggregated on the surface of the AWM layer together with the resin component before hardening to form a convex portion. Perhaps because of this, it is possible to form a minute uneven structure having AWM properties and suppressing glare. Therefore, the AWM layer system is substantially free of an aggregating agent. In addition, in the action of the present invention, it is presumed that the types and blending ratios of the curable resin, the thermoplastic resin, and the solvent are also related.

The thickness (average thickness) of the AWM layer is, for example, 0.5 to 30 μm, preferably 0.8 to 20 μm, and more preferably 1 to 10 μm (especially 2 to 5 μm).

(Transparent resin layer)

As the transparent resin layer (or substrate layer), a plastic film or sheet (unstretched or stretched plastic film) formed of a transparent resin having high flexibility and excellent crack resistance can be used. As the transparent resin, the same resin as the thermoplastic resin exemplified for the AWM layer can be used. Preferred transparent resins include, for example, cellulose derivatives [cellulose triacetate (TAC), cellulose acetate such as cellulose diacetate, etc.], polyester resins [PET, poly Polybutylene terephthalate (PBT), polyarylate resin, etc.], polyfluorene resin [polyfluorene, polyether fluorene, etc.], polyetherketone resin [polyetherketone, polyetheretherketone, etc.], Polycarbonate resin (bisphenol A polycarbonate, etc.), polyolefin Hydrocarbon resins (polyethylene, polypropylene, etc.), cyclic polyolefin resins [TOPAS (registered trademark), ARTON (registered trademark), ZONEX (registered trademark) ), Etc.], halogen-containing resins (polyvinylidene chloride, etc.), (meth) acrylic resins (polymethyl methacrylate resins, etc.), styrene resins (polystyrene, etc.), vinyl acetate Or vinyl alcohol resin (polyvinyl alcohol, etc.). Plastic films formed from such transparent resins can also be uniaxially or biaxially stretched.

In optically isotropic transparent plastic films, for example, polyester and cellulose derivatives are included. Particularly, in terms of excellent balance of heat resistance and transparency, it is preferable to use a polymer such as PET or PEN. C2-4 Thin film formed by alkylene aryl ester. The transparent resin layer may be a biaxially stretched film.

The transparent resin layer may contain conventional additives (for example, an ultraviolet absorber, etc.) which are exemplified under the item of the aforementioned AWM layer. The ratio of the additive to the entire transparent resin layer is, for example, about 0.01 to 10% by weight (especially 0.1 to 5% by weight).

The thickness (average thickness) of the transparent resin layer can be selected from a range of, for example, 5 to 1000 μm, preferably 15 to 500 μm, and more preferably 20 to 300 μm (especially 30 to 100 μm).

(Low refractive index layer)

The AWM film of the present invention is on the surface of the uneven structure (the surface with the uneven structure) having the aforementioned arithmetic average roughness Ra, especially on the AWM layer of the transparent laminated film, in order to reduce the surface of the AWM film (especially the AWM layer). To increase the transmittance of outgoing light to the outside, and it is also possible to further laminate a low refractive index layer. Moreover, the detailed mechanism is unknown , But by laminating a low refractive index layer, AWM properties can also be improved.

As the low-refractive index layer, a conventional low-refractive index layer can be used, for example, the low-refractive index layer described in Japanese Patent Application Laid-Open No. 2001-100006 and Japanese Patent Application Laid-Open No. 2008-58723. The low-refractive index layer usually contains a combination of a curable resin exemplified under the item of a low-refractive index resin or an AWM layer and a fluorine-containing compound or a low-refractive index inorganic filler.

Examples of the low refractive index resin include fluororesins such as methylpentene resin, diethylene glycol bis (allyl carbonate) resin, polyvinylidene fluoride (PVDF), and polyvinyl fluoride (PVF).

In addition, the low refractive index layer is generally preferably a fluorine-containing compound or a low refractive index inorganic filler. If a fluorine-containing compound or a low refractive index inorganic filler is used, the refractive index of the low refractive index layer can be reduced as desired. rate.

Examples of the fluorine-containing compound include a functional group (a crosslinkable group or a hardenable group such as a polymerizable group) having a fluorine atom that reacts with heat or active energy rays (such as ultraviolet rays or electron rays), Hardened or crosslinked due to heat or active energy rays, etc., which can form a fluorine-containing resin precursor of a fluorine-containing resin (particularly a hardened or crosslinked resin).

Examples of such a fluorine-containing resin precursor include a fluorine atom-containing thermosetting compound or resin [having a fluorine atom together with a reactive group (epoxy group, isocyanate group, carboxyl group, hydroxyl group, etc.), and a polymerizable group (ethylene Low molecular weight compounds such as radicals, allyl, (meth) acryl, etc.), photo-curable compounds or resins (light-curable fluorine-containing UV curable compounds such as polymers, oligomers, etc.).

As the thermosetting compound or resin, for example, a low molecular weight resin obtained by using at least a fluorine-containing monomer may be exemplified. For example, instead of a part or all of the polyol component constituting the monomer, a fluorine-containing polyol (especially two Alcohol) is an epoxy-based fluorine-containing resin; similarly, instead of a part or all of the polyol and / or the polycarboxylic acid component, a fluorine atom-containing polyol and / or a fluorine atom-containing polycarboxylic acid component is used. The unsaturated polyester-based fluorine-containing resin obtained; instead of a part or all of the polyol and / or polyisocyanate component, a urethane-based fluorine-containing product obtained by using a fluorine atom-containing polyol and / or polyisocyanate component Resin. These thermosetting compounds or resins may be used alone or in combination of two or more kinds.

The photocurable compound includes, for example, a monomer and an oligomer (or a resin, particularly a low molecular weight resin). As the monomer, for example, the monofunctional monomer and polyfunctional exemplified under the item of the AWM layer can be exemplified. Fluorine atom-containing monomers corresponding to polymer monomers [Monomers of fluorine atom-containing (meth) acrylic monomers such as fluoroalkyl esters of (meth) acrylic acid, vinyl monomers such as fluoroolefins, etc. Functional monomers; di (meth) acrylates of fluorinated alkanediols such as 1-fluoro-1,2-di (meth) propenyloxyethane, etc.] and the like. As the oligomer or resin, a fluorine atom-containing oligomer or resin corresponding to the oligomer or resin exemplified under the item of the anti-glare layer can be used. These photocurable compounds may be used alone or in combination of two or more.

The proportion of the fluorine-containing compound in the low refractive index layer may be, for example, 1% by weight or more, for example, about 5 to 90% by weight with respect to the entire low refractive index layer.

Examples of the low-refractive index inorganic filler include the fillers described in Japanese Patent Application Laid-Open No. 2001-100006, but low-refractive index fillers such as silica or magnesium fluoride are preferred, and silica is particularly preferred. . The silica may be hollow silica described in Japanese Patent Laid-Open No. 2001-233611, Japanese Patent Laid-Open No. 2003-192994, and the like. Hollow silica not only has a large effect of improving the transmittance, but also has an excellent effect of improving the AWM properties.

The number average particle diameter of the inorganic filler is 100 nm or less, preferably 80 nm or less (for example, 10 to 80 nm), and more preferably about 20 to 70 nm.

The proportion of the low-refractive index inorganic filler in the low-refractive index layer may be, for example, 1% by weight or more, for example, about 5 to 90% by weight relative to the entire low-refractive index layer. Moreover, the inorganic filler with a low refractive index may be modified by the surface of a coupling agent (titanium coupling agent, silane coupling agent). Furthermore, in order to increase the strength of the coating film, the low refractive index layer also contains other inorganic fillers.

The refractive index of the low refractive index layer is, for example, 1.3 to 1.5, and preferably about 1.35 to 1.45. In the present invention, the refractive index can be measured at a wavelength of 633 nm using a Metricon (R) coupler.

The thickness of the low refractive index layer is, for example, 50 to 1000 nm, preferably 60 to 500 nm, and more preferably 70 to 300 nm (especially 80 to 200 nm).

(Adjacent layer)

The AWM film of the present invention is on the inside of the surface having the uneven structure having the aforementioned arithmetic average roughness Ra (the surface opposite to the side having the uneven structure), especially in the case of a transparent laminated film, where the transparent resin layer is not laminated The AWM layer may be further laminated on the surface on the side. The adhesive layer may be formed of a transparent adhesive resin that can be integrated with electrodes of a touch panel, a polarizing plate, or the like, as a transparent adhesive. Examples of the agent resin include conventional adhesive resins and adhesive resins.

Examples of the adhesive resin include thermoplastic resins (polyolefins, cyclic polyolefins, acrylic resins, styrene resins, vinyl acetate resins, polyesters, polyamides, and thermoplastic polyurethanes). , Thermosetting resin (epoxy resin, phenol resin, polyurethane, unsaturated polyester, vinyl ester resin, diallyl phthalate resin, polyfunctional (meth) acrylate, amine Methacrylate (meth) acrylate, polysiloxane (meth) acrylate, polysiloxane resin, amine resin, cellulose derivative, etc.). These adhesive resin systems may be used alone or in combination of two or more.

Examples of the adhesive resin include terpene resins, rosin resins, petroleum resins, rubber adhesives, modified polyolefins, acrylic adhesives, and silicone adhesives. These adhesive resins may have a crosslinkable group (isocyanate group, hydroxyl group, carboxyl group, amine group, epoxy group, methylol group, alkoxysilyl group, etc.). These adhesive resin systems may be used alone or in combination of two or more.

Among these transparent adhesive resins, acrylic adhesives and silicone adhesives (especially acrylic adhesives) are preferred from the viewpoint of excellent optical characteristics and operability.

As the acrylic pressure-sensitive adhesive, for example, a pressure-sensitive adhesive containing an acrylic copolymer containing a C _2-10 alkyl acrylate such as ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate as a main component can be used. Examples of the copolymerizable monomer of the acrylic copolymer include a (meth) acrylic monomer [for example, (meth) acrylic acid, methyl (meth) acrylate, hydroxyethyl (meth) acrylate, (Hydroxypropyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, N-hydroxymethacrylamine, etc.) , Polymerizable nitrile compounds [for example, (meth) acrylonitrile, etc.], unsaturated dicarboxylic acids or derivatives thereof (for example, maleic anhydride, iconic acid, etc.), vinyl esters (for example, vinyl acetate, acrylic acid, etc.) Acid vinyl esters, etc.), aromatic vinyls (for example, styrene, etc.), and the like.

As the polysiloxane adhesive, for example, a polysiloxane rubber component [made of monofunctional R ₃ SiO _1/2 (wherein R represents an alkyl group such as a methyl group, a phenyl group, etc.) dissolved in an organic solvent can be used. Aryl, etc. The same below) MQ resin made of tetrafunctional SiO ₂ etc.] and polysiloxane resin component (difunctional R ₂ SiO alone, or a combination of difunctional R ₂ SiO and monofunctional R ₃ SiO _1/2 oily or gelatinous components, etc.). The aforementioned silicone rubber component may also be crosslinked.

The adhesive layer may also include a conventional additive (for example, an ultraviolet absorber, etc.) exemplified under the item of the aforementioned AWM layer. The ratio of the additive to the entire adhesive layer is, for example, about 0.01 to 10% by weight (especially 0.1 to 5% by weight).

The thickness (average thickness) of the adhesive layer is, for example, 1 to 100 μm, preferably 2 to 80 μm, and particularly preferably 3 to 70 μm (especially 5 to 50 μm).

[Manufacturing method of AWM film]

The AWM film of the present invention is not particularly limited as long as it has a concave-convex structure having the above-mentioned arithmetic average roughness Ra on one surface, and a conventional film forming method or the like can be used. When forming an AWM film from a transparent laminated film, for example, a coating step of coating a hardening composition on one side of the transparent resin layer may be performed, and the applied hardening composition may be dried and then irradiated with active energy rays to be hardened. Hardening step To make.

In the coating step, the curable composition usually includes a mixed liquid (particularly, a liquid composition such as a uniform solution) containing the aforementioned curable resin, thermoplastic resin, metal oxide fine particles, and a solvent. In a preferable aspect, as the mixed solution, a composition containing a photocurable resin, a thermoplastic resin, fine metal oxide particles, a photopolymerization initiator, and a solvent capable of dissolving the photocurable resin and the thermoplastic resin is used.

The solvent may be selected in accordance with the type and solubility of the curable resin and the thermoplastic resin, and any solvent may be used as long as it can dissolve at least the solid components (curable resin, thermoplastic resin, reaction initiator, and other additives) uniformly. Examples of such a solvent include ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.) and ethers (dioxane Alkanes, tetrahydrofuran, etc.), aliphatic hydrocarbons (hexane, etc.), alicyclic hydrocarbons (cyclohexane, etc.), aromatic hydrocarbons (toluene, xylene, etc.), halogenated hydrocarbons (dichloromethane, dichloride, etc.) Ethane, etc.), esters (methyl acetate, ethyl acetate, butyl acetate, etc.), water, alcohols (ethanol, isopropanol, butanol, cyclohexanol, etc.), cellosolves (methyl solvent Cellulose, ethyl cellosolve, propylene glycol monomethyl ether (1-methoxy-2-propanol), etc.), cellosolve acetates, fluorenes (dimethyl fluorene, etc.), amidine Class (dimethylformamide, dimethylacetamide, etc.) and the like. These solvents may be used singly or in combination of two or more kinds, and may also be mixed solvents. Among these solvents, ketones such as methyl ethyl ketone or cyclohexanone, alcohols such as butanol or 1-methoxy-2-propanol, and the like may be mixed. For example, the ratio (weight ratio) of the former / the latter of the aforementioned ketones to the aforementioned alcohols = 90/10 to 10/90, preferably 80/20 to 40/60, and more preferably 70/30 to 50/50 mixing. In addition, the former / the latter of the ketones and the alkyl ketones such as methyl ethyl ketone and the cyclohexanone may be 95/5 to 50/50 (especially 90/10 to 70/30) The right-to-left ratio (weight ratio) is mixed. In addition, alkanols such as butanol and cellosolves such as 1-methoxy-2-propanol can be used. The former / the latter = 5/95 to 50/50 (especially 10/90 to 30/70). The ratio (weight ratio) is mixed. In the present invention, the degree of aggregation of the metal oxide fine particles can also be controlled by a suitable combination of solvents. In the present invention, in particular, by combining solvents in such a ratio, a surface structure having a fine uneven structure and an undulating structure can be formed.

The concentration of the solute (curable resin, thermoplastic resin, fine metal oxide particles, reaction initiator, and other additives) in the mixture can be selected within a range that does not impair the castability or coatability, for example, 1 ~ 80% by weight, preferably 5 to 60% by weight, and more preferably 15 to 40% by weight (especially 20 to 40% by weight).

Examples of the coating method include conventional methods such as a roll coater, an air knife coater, a blade coater, a rod coater, a reverse coater, a bar coater, a comma coater, and a dip-extrusion. Coater, die coater, gravure coater, micro gravure coater, screen coater method, dip method, spray method, spin method, etc. Among these methods, a bar coater method or a gravure coater method is widely used. Furthermore, if necessary, the coating liquid may be applied a plurality of times.

In the coating step, the solvent is evaporated after casting or coating the mixed solution. The evaporation of the solvent can be carried out generally at a temperature of about 40 to 150 ° C, preferably 50 to 120 ° C, and more preferably about 60 to 100 ° C, according to the boiling point of the solvent.

In the present invention, although the coating liquid does not contain an aggregating agent, However, nanometer-sized metal oxide fine particles are moderately aggregated in the coating solution to form a nucleus, and the metal oxide fine particles are aggregated on the surface together with the resin component system before hardening by the convection effect caused by the evaporation of the solvent. To form a convex portion.

In the curing step, the applied curable composition is finally cured by active light (ultraviolet rays, electron beams, etc.) or heat to form an AWM layer. The curing system of the curable resin can be combined with heating, light irradiation, etc. according to the type of the curable resin.

The heating temperature can be selected within an appropriate range, for example, about 50 to 150 ° C. The light irradiation system can be selected according to the type of the light-hardening component and the like, and generally, ultraviolet rays, electron beams, and the like can be used. A common exposure source is usually an ultraviolet irradiation device.

As the light source, for example, in the case of ultraviolet rays, a deep UV lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a halogen lamp, a laser light source (a light source such as a helium-cadmium laser, an excimer laser, etc.) can be used. The amount of irradiation light (irradiation energy) varies with the thickness of the coating film, and can be selected from a range of about 10 to 10,000 mJ / cm ² (for example, 50 to 8000 mJ / cm ² ). For example, it can be 10 to 5000 mJ / cm ² . It is preferably 30 to 3000 mJ / cm ² , and more preferably 50 to 1000 mJ / cm ² .

The light irradiation may be performed in an inert gas environment if necessary. In particular, when photocuring is used, not only can the curable resin be immediately fixed by curing the curable resin, but also low-molecular components such as oligomers can be suppressed from being precipitated by heat from the inside of the transparent resin layer. Furthermore, abrasion resistance can be imparted to the AWM layer.

When a low refractive index layer is further formed on the AWM layer, It can be formed by applying or casting the coating liquid using the same method as the aforementioned AWM layer, and then hardening it with active light or heat.

Furthermore, in the present invention, a surface structure having a fine uneven structure and an undulating structure can be formed by drying the low-refractive index layer at a relatively high temperature (temperature for evaporating the solvent) and drying. The drying temperature can be performed according to the boiling point of the solvent, for example, at a temperature of about 40 to 200 ° C, preferably at 60 to 180 ° C, and more preferably at about 80 to 150 ° C (especially 100 to 140 ° C).

In the present invention, in order to improve the adhesion of other layers (for example, a low refractive index layer or a transparent conductive layer) to the AWM layer, the AWM layer may be subjected to a surface treatment. Examples of the surface treatment include a conventional surface treatment such as a corona discharge treatment, a flame treatment, a plasma treatment, an ozone or an ultraviolet irradiation treatment, and the like.

[Capacitive touch panel display]

The electrostatic capacity type touch panel display of the present invention has a void layer inside, and the AWM film is laminated on at least one of the surfaces facing through the void layer.

The above-mentioned void layer is not particularly limited, but a transparent electrode including a transparent conductive layer, and a display device such as an LCD or an OLED are usually provided with an adhesive layer (spacer) at an end portion (peripheral portion or outer portion) of both. Frame part). The surface of the transparent electrode may be formed of, for example, a transparent conductive layer such as an ITO (indium oxide-tin oxide composite oxide) film. When the surface of the display device is an LCD or the like, it may be formed of a polarizing layer, for example. The AWM film of the present invention may be laminated on the surface facing through the gap layer, for example, it may be formed on the surface of the transparent conductive layer. It has a concave-convex structure, but the transparent conductive layer is usually covered with a protective layer such as a hard coat layer for its own protection. Therefore, it is effective to use an AWM film on this protective layer. Especially for a display in which a transparent substrate is formed of a glass plate, from the point of suppressing the scattering of glass fragments caused by glass breakage, among the surfaces facing through the gap layer, it is preferably on the touch panel. AWM film is laminated on the surface of the display body.

The thickness of the void layer is, for example, 0.05 to 1 mm, preferably 0.1 to 0.5 mm, and more preferably about 0.15 to 0.3 mm.

The electrostatic capacity type touch panel display of the present invention only needs to have a void layer inside, but the layer on the surface side of the void layer is easy to flex and watermarks are likely to occur. From the point of significantly showing the effect of the present invention, The transparent substrate contained between the Jia-series gap layer and the display surface is only one display (one glass-type display).

The transparent substrate may be formed of a transparent material, and examples thereof include a substrate formed of a transparent resin, glass, or the like exemplified under the item of a transparent resin layer. Among them, when the AWM film is laminated on the surface opposite to the touch panel through the gap layer, the AWM film also functions as a glass chip anti-scattering film. From a point of view, a glass plate is preferable.

As the glass plate, for example, soda lime glass, borosilicate glass, crown glass, barium-containing glass, strontium-containing glass, boron-containing glass, low-alkali glass, alkali-free glass, crystallized transparent glass, and silica can be used. Glass plate made of glass, quartz glass, heat-resistant glass, etc.

The thickness (average thickness) of the transparent substrate (especially the glass plate in a glass plate type display) is, for example, 50 to 3000 μm, and preferably 100 ~ 2000μm, more preferably about 200 ~ 1500μm.

In the electrostatic capacity type touch panel display of the present invention, a transparent substrate such as a glass plate is usually a transparent electrode that is laminated with a transparent conductive layer.

Examples of the transparent conductive layer include metal oxides such as indium oxide-tin oxide-based composite oxide (ITO), fluorine-doped tin oxide (FTO), InO ₂ , SnO ₂ , ZnO, or the like, or gold, silver, A layer made of a metal such as platinum or palladium (especially a metal oxide layer such as an ITO film). Such a transparent conductive layer can be formed by a conventional method, for example, sputtering, vapor deposition, chemical vapor deposition, or the like (usually sputtering). The thickness (average thickness) of the transparent conductive layer is, for example, 0.01 to 0.05 μm, preferably 0.015 to 0.03 μm, and more preferably about 0.015 to 0.025 μm.

The transparent conductive layer formed on the transparent substrate is based on the type of touch panel, and is usually formed in a planar manner by analogy, and is formed in a stripe manner in digital mode. As a method for forming the transparent conductive layer into a planar shape or a strip shape, for example, a method of forming a transparent conductive layer over the entire surface of a glass substrate and then patterning it into a planar shape or a strip shape by etching is used to form a pattern in advance. Methods, etc.

When the AWM film is laminated on the front surface of the touch panel, the transparent conductive layer of such a transparent electrode can also be laminated with an AWM film through an adhesive layer.

The electrostatic capacity type touch panel display of the present invention can also be combined with other optical elements (for example, various optical elements arranged in the optical path such as a polarizing plate, a phase difference plate, and a light guide plate). When a polarizing plate is laminated on a display device such as an LCD, the polarizing plate can also be thin through AWM The film was then laminated to laminate the AWM film.

[Example]

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited by these examples. The following items were used to evaluate the AWM films obtained in the examples and comparative examples.

[Full light transmittance and haze]

A haze meter (manufactured by Nippon Denshoku Corporation, trade name "NDH-5000W") was used to measure the total light transmittance in accordance with JIS K7361, and the haze was measured in accordance with JIS K7136.

[Penetration image (image) sharpness]

The sharpness of the image of the optical film is parallel to the direction of the comb teeth of the optical comb in accordance with JIS K7105 by using an image measuring device (manufactured by SUGA Tester Co., Ltd., trade name "ICM-1T"). Method, a thin film is installed and measurement is performed. The optical sharpness of the optical comb with a width of 0.5 mm was measured in the optical comb of the image measuring device.

[Reflectivity]

A black film was bonded to the transparent resin layer side of the transparent laminated film, and an integrating sphere reflection intensity measuring device (U-3300, manufactured by Hitachi High-Technologies Co., Ltd.) was used to measure the integrated reflectance (transparency conversion).

[Scratch resistance]

Wipe the # 0000 steel wool back and forth 10 times with a load of 2.45 N / cm ² on the surface on which the uneven structure is formed (the surface of the low refractive index layer or the AWM layer), and visually confirm the flaw. According to the number of the flaw, Evaluation was performed using the following criteria.

○: 0 ~ 5

△: 6 ~ 9

×: 10 or more.

[Pencil hardness]

Pencil hardness was measured in accordance with JIS K5400 under a load of 7.4N.

[Arithmetic average roughness Ra1]

According to JIS B0601, the arithmetic mean roughness of the surface (concave-convex surface) of the AWM film side of the AWM film was measured from the adhesive layer side of the AWM film obtained from the examples and comparative examples by the following procedure. That is, a scanning probe microscope (manufactured by SII Nano Technology Co., Ltd.) was used, and a silicon cantilever was used as a probe. The measurement mode was Tapping mode, and the measurement area was 10 μm × 10 μm, and images were input. For the obtained image, the analysis software attached to the scanning probe microscope was used as the image processing for removing the undulations. After performing the Flatatten process (0 times) and the Planefit process (XY) once, the arithmetic average roughness was calculated. Degree Ra1.

[Arithmetic average roughness Ra2]

According to JIS B0601, a non-contact surface shape measurement system ("VertScan 2.0" manufactured by Ritsubishi Systems Corporation) was used to set the measurement area to 500 μm × 500 μm, and the arithmetic average roughness Ra2 was measured.

[Water contact angle of AWM layer]

Using an automatic-dynamic contact angle meter ("Type DCA-UZ" manufactured by Kyowa Interface Science Co., Ltd.), five points of the contact angle of each liquid of about 3 μL were measured on the coating film and averaged.

[Dazzling Evaluation]

The dazzling judgment on the display surface is tied to a transparent glass with a thickness of 3mm On the board, the AWM films obtained in the examples and comparative examples were pasted through an adhesive layer of an AWM film, and the AWM film surface and the monitor were used on a 5-inch LCD monitor (1920 x 1080 pixels, resolution 440ppi). They were placed facing each other so that the monitor became a green display. The following criteria were used to evaluate the glare when visually observed from the front of the monitor.

◎: No dazzling feeling

○: Slightly dazzling

△: feel dazzling

×: Strongly dazzling.

[Watermark Resistance (AWM)]

A 0.7 mm transparent glass plate obtained through the adhesive layer of the AWM film obtained in the examples and comparative examples was bonded to the AWM film. Secondly, a 10-inch-sized polarizing plate having a gap of 0.2 mm in width on the outer periphery was superimposed so as to face the AWM layer of the aforementioned AWM film. Finally, the central part of the transparent glass plate was pressed under a load of 20 N / cm ² for 10 seconds, and the state after being released for 10 seconds was evaluated using the following criteria.

◎: AWM film is not in close contact with transparent glass plate

○: The AWM film and the transparent glass plate are in close contact with each other

×: Both of them are in close contact.

[Preparation of coating liquid]

(Watermark-resistant coating liquid: AWM-1)

50 parts by weight of dipentaerythritol hexaacrylate ("DPHA" manufactured by DAICEL-ALLNEX (stock)) and 50 parts by weight of pentaerythritol tripropylene Acid ester ("PETRA" manufactured by DAICEL-ALLNEX (stock)), 1.2 parts by weight of cellulose acetate propionate ("CAP" manufactured by Eastman Corporation), dissolved in 131 parts by weight of methyl ethyl ketone (MEK), 65 parts by weight Parts of a mixed solvent of 1-methoxy-2-propanol (MMPG), 22 parts by weight of 1-butanol (BuOH), and 24 parts by weight of cyclohexanone. To this solution, 2 parts by weight of a photopolymerization initiator ("Irgacure 184" by BASF Japan Co., Ltd.) and 1 part by weight of a photopolymerization initiator ("Irgacure 907" by BASF Japan Co., Ltd.) were added and Dissolve. Furthermore, to this solution, 1.5 parts by weight of ATO particles ("ELCOM SH-1212ATV" manufactured by Nippon Kasei Kasei Co., Ltd.) with a primary particle diameter of 8 nm and 20% by weight of alcohol (ethanol / isopropanol = 80 / 20 (weight ratio) mixed solvent) dispersion liquid), and stirred for 1 hour to prepare AWM layer coating liquid: AWM-1.

(Watermark-resistant coating liquid: AWM-2)

A watermark-resistant coating liquid: AWM-2 was prepared in the same manner as AWM-1, except that the amount of ATO particles was changed to 3.0 parts by weight.

(Watermark-resistant coating solution: AWM-3)

AWM-3 was prepared in the same manner as AWM-1 except that the amount of ATO particles was changed to 4.5 parts by weight.

(Watermark-resistant coating liquid: AWM-4)

AWM-4 was prepared in the same manner as AWM-1 except that the amount of ATO particles was changed to 7.5 parts by weight.

(Watermark-resistant coating solution: AWM-5)

AWM-5 was prepared in the same manner as AWM-1 except that the amount of ATO particles was changed to 20 parts by weight.

(Watermark-resistant coating solution: AWM-6)

Other than changing the amount of ATO particles added to 0.5 parts by weight, AWM-1 similarly prepared a watermark-resistant coating liquid: AWM-6.

(Watermark-resistant coating liquid: AWM-7)

A commercially available acrylic microparticle dispersion liquid ("K-001" manufactured by Sekisui Chemical Industries, Ltd., 20% by weight of solid content) was used.

(Water-resistant coating solution: AWM-8)

A watermark-resistant coating liquid: AWM-8 was prepared in the same manner as AWM-1, except that the amount of ATO particles was changed to 30 parts by weight.

(Low refractive index layer coating liquid: LC)

A commercially available hollow silica fine particle dispersion ("ELCOM P-5063" manufactured by Nippon Kasei Kasei Co., Ltd., with a solid content of 3% by weight) was diluted with isopropyl alcohol (IPA), and the solid content was adjusted to 2.4% by weight. LC.

Example 1

As a transparent resin layer, a PET film (PET made by Mitsubishi Resin Co., Ltd. with a thickness of 75 μm) was used. On this film, AWM layer coating liquid AWM-1 was applied using a bar coater # 8, and then dried at 80 ° C. for 1 minute. The coating film was passed through an ultraviolet irradiation device (high-pressure mercury lamp made by USHIO Electric Co., Ltd., ultraviolet irradiation amount: 100 mJ / cm ² ), and subjected to ultraviolet curing treatment to form an AWM layer having a minute surface uneven structure and hard coating property. The thickness of the AWM layer in the obtained transparent laminated film was about 3 μm.

On the AWM layer of the obtained transparent laminated film, a low refractive index layer coating liquid LC was applied using a bar coater # 4, and dried at 120 ° C. for 1 minute. Then, the coating film was passed through an ultraviolet irradiation device (high-pressure mercury lamp made by USHIO Electric Co., Ltd., ultraviolet irradiation amount: 100 mJ / cm ² ), and was subjected to ultraviolet curing treatment to form a low refractive index layer. The thickness of the low-refractive index layer in the obtained low-reflection transparent laminated film (AWM film) was about 100 nm. An adhesive layer having a thickness of 25 μm was formed on the surface of the PET film of the obtained AWM film.

Examples 2 to 5 and Comparative Example 1

An AWM film was produced in the same manner as in Example 1 except that AWM-2 to 6 were used instead of AWM-1 as the AWM layer coating liquid.

Comparative Example 2

As a transparent resin layer, a PET film (PET made by Mitsubishi Resin Co., Ltd. with a thickness of 75 μm) was used. On this film, AWM layer coating liquid AWM-7 was applied using a bar coater # 8, and then dried at 80 ° C. for 1 minute. The coating film was passed through an ultraviolet irradiation device (manufactured by USHIO Electric Co., Ltd., high-pressure mercury lamp, ultraviolet irradiation amount: 100 mJ / cm ² ), and subjected to ultraviolet curing treatment to form an AWM layer having a surface uneven structure and hard coatability. The thickness of the AWM layer in the obtained transparent laminated film (AWM film) was about 3 μm. An adhesive layer having a thickness of 25 μm was formed on the surface of the PET film of the obtained AWM film.

Comparative Example 3

On the AWM layer of the transparent laminated film (film before forming the adhesive layer) obtained in Comparative Example 2, a low refractive index layer coating liquid LC was applied using a bar coater # 4, and dried at 120 ° C for 1 minute. Then, the coating film was passed through an ultraviolet irradiation device (high-pressure mercury lamp made by USHIO Electric Co., Ltd., ultraviolet irradiation amount: 100 mJ / cm ² ), and was subjected to ultraviolet curing treatment to form a low refractive index layer. The thickness of the low-refractive index layer in the obtained low-reflection transparent laminated film (AWM film) was about 100 nm. An adhesive layer having a thickness of 25 μm was formed on the surface of the PET film of the obtained AWM film.

Comparative Example 4

As a transparent resin layer, a PET film (PET made by Mitsubishi Resin Co., Ltd. with a thickness of 75 μm) was used. AWM layer coating solution AWM-8 was applied on the film using a bar coater # 8, and then dried at 80 ° C. for 1 minute. The coating film was passed through an ultraviolet irradiation device (high-pressure mercury lamp made by USHIO Electric Co., Ltd., ultraviolet irradiation amount: 100 mJ / cm ² ), and subjected to ultraviolet curing treatment to form an AWM layer having a surface uneven structure and hard coatability. The thickness of the AWM layer in the obtained transparent laminated film (AWM film) was about 3 μm. An adhesive layer having a thickness of 25 μm was formed on the surface of the PET film of the obtained AWM film.

The AWM films obtained in Examples 1 to 5 and Comparative Examples 1 to 4 were evaluated, and the results are shown in Table 1.

As is clear from the results in Table 1, the AWM film of the example is excellent in abrasion resistance and optical characteristics, and can suppress the occurrence of dazzling even in a high-definition display, and has AWM properties. In contrast, the AWM film of the comparative example cannot coexist with the suppression of glare and AWM properties.

[Industrial availability]

The AWM film of the present invention can be used to have Capacitive touch panel display with gap layer. As a touch panel display, for example, it can be used in the display section of electrical, electronic, or precision equipment such as PCs, televisions, mobile phones (smart phones), electronic paper, gaming machines, mobile devices, clocks, and desktop computers. , Used in combination with display devices (LCD, plasma display devices, organic or inorganic EL display devices, etc.) electrostatic capacitance type touch panel displays. Especially from the viewpoint of excellent visibility, it is suitable as a projection type capacitive touch panel (such as LCD or OLED) using ITO grid method for PC, 4K TV, smart phone, tablet PC, tablet, game machine, etc. High-definition display touch panel).

Claims (10)

A watermark-resistant film is a watermark-resistant film laminated on at least one surface of a plurality of surfaces facing each other across the gap layer in a capacitive touch panel display having a gap layer inside. The surface has a concavo-convex structure having an arithmetic average roughness Ra1 calculated in a measurement area of 10 μm × 10 μm of 0.7 μm or more and less than 5 nm and an arithmetic average roughness Ra2 calculated in a measurement area of 500 μm × 500 μm of 10 to 50 nm. The watermark resistant film of claim 1, wherein the watermark resistant film is a transparent laminated film including a transparent resin layer and a watermark resistant layer, and the watermark resistant layer is laminated on one side of the transparent resin layer and includes a hardening property. It is formed of hardened material of resin, thermoplastic resin, and hardenable composition of metal oxide particles having an average primary particle diameter of 1 to 50 nm, and has an arithmetic average roughness Ra1 calculated on the surface of 10 μm × 10 μm in the measurement area of 0.8 nm or more. 1.5nm uneven structure. For example, the watermark-resistant film of claim 1 or 2, wherein the curable resin includes a curable resin having a polymerizable group of 4 or less functions and a curable resin having a polymerizable group of 5 or more functions, a thermoplastic resin-based cellulose derivative, The metal oxide fine particles are at least one selected from the group consisting of antimony-containing tin oxide, antimony oxide, tin oxide, and zinc oxide. The watermark-resistant film according to claim 1 or 2, wherein a low refractive index layer is further laminated on the surface of the side having the uneven structure. The watermark-resistant film according to claim 1 or 2, wherein an adhesive layer is further laminated on the surface opposite to the side having the uneven structure. For example, the watermark-resistant film of claim 1 or 2, wherein the water contact angle of the surface on the side with the uneven structure is 65 ~ 80 °. An electrostatic capacity type touch panel display is provided with a void layer inside, and a watermark-resistant film according to any one of claims 1 to 6 is laminated on at least one surface of a plurality of surfaces facing through the void layer. . For example, the touch panel display of claim 7, wherein a watermark-resistant film is laminated on the surface of the front side of the touch panel among the plurality of surfaces facing through the gap layer. The touch panel display of claim 7, wherein the transparent substrate contained between the gap layer and the display surface is only one piece. The touch panel display of claim 9, wherein the transparent substrate is a glass plate having a thickness of 50 to 3000 μm.