JP2019207381A - Anti-glare laminate and manufacturing method and application for the same - Google Patents

Abstract

To provide an anti-glare laminate that can achieve both a high anti-glare property and prevention of screen glare even in a high-definition LCD and organic EL display.SOLUTION: A laminate including an internal haze layer, a base material layer, and an anti-glare layer is prepared, and the anti-glare layer is arranged on its surface. A surface of the anti-glare layer has an irregular shape in which the arithmetic average roughness Ra is 0.05 to 0.3 μm, the average length RSm of a roughness curve element is 5 to 35 μm, and the maximum sectional height Rt of a roughness curve is 0.1 to 2 μm. The haze of the laminate may be 10 to 80%. In the laminate, the coefficient of dynamic friction of the surface of the anti-glare layer may be 0.1 to 3, which is measured by using a surface contactor attached with an artificial skin under a condition of a load of 0.2 N, a travel speed of 50 mm/sec., and an effective measurement distance of 50 mm.SELECTED DRAWING: None

Description

  The present invention relates to an antiglare laminate capable of suppressing glare on the display surface of various display devices such as a liquid crystal display device (LCD) with a touch panel and an organic electroluminescence (EL) display, and a method for producing the same and its use.

  The antiglare film is widely used as a film for suppressing glare and improving visibility while preventing reflection of an outside scene on a display surface in an image display device such as an LCD or an organic EL display. Anti-glare films exhibit anti-glare properties by forming irregularities on the surface and scattering and reflecting external light, but depending on the application, hard coat properties and sliding properties with fingers are also required. In the antiglare film, as a method of forming the antiglare layer having hard coat properties, a method of roughening the surface of the antiglare layer by a physical method, or by adding particles to a binder resin, the surface of the antiglare layer is added. A method for forming irregularities, a method for forming irregularities on the surface of an antiglare layer by phase separation of resin components, and the like are known.

However, the antiglare layer obtained by these methods cannot simultaneously satisfy various properties required for the antiglare film. For example, among these methods, various films that suppress glare by a method of forming irregularities on the surface of the antiglare layer by phase separation of the resin component have been proposed. Japanese Patent No. 6190581 (Patent Document 1) , An antiglare film comprising an antiglare layer on the surface having elongated protrusions formed in accordance with phase separation of a plurality of resin components, having a haze of 10 to 40%, wherein the elongated protrusions The portion has a branched structure, and the total length is 100 μm or more, and the surface of the antiglare layer has one or more elongated protrusions per 1 mm ² and has a branched structure. An antiglare film is disclosed in which the length ratio of the convex portions to other convex portions is the former / the latter = 100/0 to 70/30.

  However, even with this antiglare film, it is difficult to balance the various characteristics by controlling the uneven shape, and in particular, there is still room for improving the glare. In particular, in recent years, image display devices (devices) such as LCDs and organic EL displays have been improved in definition, and the surface unevenness size is close to the order of the pixel size of the high-definition display. It is easy to occur.

  JP 2001-91707 A (Patent Document 2) discloses an antiglare film having an antiglare layer having a haze of 4 to 50% on a transparent support. An internal scattering layer formed of a UV crosslinkable hard coat material containing titanium dioxide particles having an average particle diameter of 50 nm is laminated on a transparent support formed of a cellulose film, and a multi-layer is further formed on the internal scattering layer. An antiglare film in which an antiglare layer formed of a cured product of a UV curable composition containing a functional acrylate, bis (methacryloylthiophenyl) sulfide, and crosslinked polystyrene particles having an average particle diameter of 2 μm is laminated has been produced.

  However, even with this anti-glare film, it has been difficult to achieve both high anti-glare properties and suppression of glare in high-definition LCDs and organic EL displays.

Japanese Patent No. 6190581 (Claims 1 and 3) JP 2001-91707 A (Claim 1 and Example 3)

  Accordingly, an object of the present invention is to provide an antiglare laminate (such as a film-like antiglare laminate) that can achieve both high antiglare properties and suppression of glare in high-definition LCDs and organic EL displays, and the production thereof. It is to provide a method.

  Another object of the present invention is to provide an antiglare laminate that can improve surface slipperiness and scratch resistance with a finger, and a method for producing the same.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have combined an internal haze layer with an antiglare layer having a specific uneven shape on the surface, thereby enabling high-definition LCDs and organic EL displays. The present inventors have found that high antiglare properties and suppression of glare can be achieved at the same time.

  That is, the laminate of the present invention is a laminate (film-like laminate) including an internal haze layer, a base material layer, and an antiglare layer, and having the antiglare layer on the surface thereof. The surface has an uneven shape having an arithmetic average roughness Ra of 0.05 to 0.3 μm, an average length of roughness curve elements RSm of 5 to 35 μm, and a roughness curve having a maximum cross-sectional height Rt of 0.1 to 2 μm. The haze of this laminate may be 10 to 80%. The laminate has a dynamic friction coefficient of 0.1 to 0.1 on the surface of the antiglare layer measured under the conditions of a load of 0.2 N, a moving speed of 50 mm / sec, and an effective measurement distance of 50 mm using a surface contactor with artificial skin attached. 3 may be sufficient. The antiglare layer may be a cured product of a curable composition containing one or more polymer components and one or more cured resin precursor components. The polymer component may contain cellulose esters and / or a (meth) acrylic polymer which may have a polymerizable group. The cured resin precursor component may contain urethane (meth) acrylate. The cured resin precursor component may further contain a fluorine-based compound having a polymerizable group. The curable composition may further contain a filler. The 60 ° gloss on the surface of the antiglare layer may be 0.1 to 70%. The internal haze layer may have a haze of 1 to 60%.

  The manufacturing method of the said laminated body including the glare-proof layer formation process which phase-separates by wet spinodal decomposition | disassembly and forms an uneven | corrugated shape is also contained in this invention.

  The display device provided with the said laminated body is also contained in this invention. This display device may be a liquid crystal display device with a touch panel or an organic EL display.

  In the present invention, since the internal haze layer and the antiglare layer having a specific uneven shape on the surface are combined, high antiglare properties and suppression of glare can be achieved even in high-definition LCDs and organic EL displays. Can be compatible. Furthermore, by adjusting the uneven shape on the surface of the antiglare layer, it is possible to improve surface slipperiness and scratch resistance with a finger.

[Anti-glare layer]
The laminated body of this invention contains an internal haze layer, a base material layer, and an anti-glare layer, and has the said anti-glare layer on the surface. The antiglare layer only needs to have an irregular surface with a specific shape from the point that it is possible to achieve both high antiglare properties and suppression of glare by combining with the internal haze layer. Conventional methods other than the forming method (for example, a method of forming a convex portion by following the shape of the particles) can be used.

  As a conventional method for forming the uneven shape, for example, a method of curing after phase-separating the resin component of a curable composition containing a phase-separable resin component, a mold having an uneven structure on the surface is used. Transfer method, method of forming a concavo-convex structure by cutting (for example, cutting using a laser or the like), method of forming a concavo-convex structure by polishing (for example, a sand blast method or a bead shot method), or uneven by etching Examples include a method of forming a structure. Among these methods, from the viewpoint of productivity and the like, a method in which the resin component of the curable composition containing a phase-separable resin component is cured after phase separation is preferable, and a method of phase separation by wet spinodal decomposition is preferable. Particularly preferred.

  The antiglare layer having an uneven shape formed by wet spinodal decomposition may be a cured product of a curable composition containing one or more polymer components and one or more cured resin precursor components. Specifically, the antiglare layer uses a composition (mixed liquid) containing one or more polymer components, one or more cured resin precursor components, and a solvent, and the solvent is dried from the liquid phase of the composition. In the process of evaporation or removal, phase separation by spinodal decomposition occurs with concentration, and a phase separation structure having a relatively regular interphase distance can be formed. More specifically, the wet spinodal decomposition is usually performed by coating the composition (uniform solution) on a support such as a base material layer or an internal haze layer, and evaporating the solvent from the coating layer. Can do.

(Polymer component)
As the polymer component, a thermoplastic resin is usually used. The thermoplastic resin is not particularly limited as long as it has high transparency and can form the above-described surface irregularities by spinodal decomposition. For example, styrene resin, (meth) acrylic polymer, organic acid vinyl ester polymer, vinyl ether Polymer, halogen-containing resin, polyolefin (including alicyclic polyolefin), polycarbonate, polyester, polyamide, thermoplastic polyurethane, polysulfone resin (polyethersulfone, polysulfone, etc.), polyphenylene ether resin (2,6-xylenol) Polymers), cellulose derivatives (cellulose esters, cellulose carbamates, cellulose ethers, etc.), silicone resins (polydimethylsiloxane, polymethylphenylsiloxane, etc.), rubber or elastomers ( Li butadiene, diene rubbers such as polyisoprene, styrene - butadiene copolymer, acrylonitrile - butadiene copolymer, acrylic rubber, urethane rubber, silicone rubber, etc.), and others. These thermoplastic resins can be used alone or in combination of two or more.

  Among these polymer components, styrene resin, (meth) acrylic polymer, vinyl acetate polymer, vinyl ether polymer, halogen-containing resin, alicyclic polyolefin, polycarbonate, polyester, polyamide, cellulose derivative, silicone type Resin, rubber or elastomer is generally used. Further, as the polymer component, a polymer component that is usually non-crystalline and soluble in an organic solvent (particularly a common solvent capable of dissolving a plurality of polymer components and a cured resin precursor component) is used. In particular, polymer components having high moldability or film formability, transparency and weather resistance, such as styrene resins, (meth) acrylic polymers, alicyclic polyolefins, polyesters, cellulose derivatives (cellulose esters, etc.), etc. (Meth) acrylic polymers and cellulose esters are particularly preferable.

As the (meth) acrylic polymer, a (meth) acrylic monomer alone or a copolymer, a copolymer of a (meth) acrylic monomer and a copolymerizable monomer, or the like can be used. Examples of (meth) acrylic monomers include (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, t-butyl (meth) acrylate, ( (Meth) acrylic acid isobutyl, (meth) acrylic acid hexyl, (meth) acrylic acid octyl, (meth) acrylic acid 2-ethylhexyl (meth) acrylic acid C _1-10 alkyl; (meth) acrylic acid phenyl ( (Meth) acrylic acid aryl; hydroxyalkyl (meth) acrylate such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate; glycidyl (meth) acrylate; N, N-dialkylaminoalkyl (meth) acrylate; (meth) acrylonitrile The alicyclic hydrocarbon group such as tricyclodecane The (meth) acrylate etc. which have can be illustrated. Examples of the copolymerizable monomer include styrene monomers such as styrene, vinyl ester monomers, maleic anhydride, maleic acid, and fumaric acid. These monomers can be used alone or in combination of two or more.

Examples of (meth) acrylic polymers include poly (meth) acrylic acid esters such as polymethyl methacrylate, methyl methacrylate- (meth) acrylic acid copolymers, and methyl methacrylate- (meth) acrylic acid esters. Examples thereof include a polymer, a methyl methacrylate-acrylic acid ester- (meth) acrylic acid copolymer, and a (meth) acrylic acid ester-styrene copolymer (MS resin and the like). Among these, poly (meth) acrylic acid C _1-6 alkyl such as poly (meth) acrylic acid methyl, especially methyl methacrylate as a main component (about 50 to 100% by mass, preferably about 70 to 100% by mass). A methyl methacrylate polymer is preferred.

Examples of cellulose esters include aliphatic organic acid esters (cellulose acetate such as cellulose diacetate and cellulose triacetate; C _1-6 such as cellulose propionate, cellulose butyrate, cellulose acetate propionate, and cellulose acetate butyrate). Examples include aliphatic carboxylic acid esters, aromatic organic acid esters (C _7-12 aromatic carboxylic acid esters such as cellulose phthalate and cellulose benzoate), inorganic acid esters (eg, cellulose phosphate, cellulose sulfate, etc.), and the like. It may be a mixed acid ester such as acetic acid / cellulose nitrate ester. These cellulose esters can be used alone or in combination of two or more. Among these, cellulose C _2-4 acylates such as cellulose diacetate, cellulose triacetate, cellulose acetate propionate, and cellulose acetate butyrate are preferable, and cellulose acetate C _3-4 acylates such as cellulose acetate propionate are particularly preferable.

The polymer component [particularly the (meth) acrylic polymer] may be a polymer having a functional group involved in the curing reaction (or a functional group capable of reacting with the cured resin precursor component). The polymer may have a functional group in the main chain or a side chain. The functional group may be introduced into the main chain by copolymerization or cocondensation, but is usually introduced into the side chain. Examples of such functional groups include condensable groups and reactive groups (for example, hydroxyl groups, acid anhydride groups, carboxyl groups, amino groups or imino groups, epoxy groups, glycidyl groups, isocyanate groups, etc.), polymerizable groups [ For example, C _2-6 alkenyl groups such as vinyl, propenyl, isopropenyl, butenyl and allyl, C _2-6 alkynyl groups such as ethynyl, propynyl and butynyl, C _2-6 alkenylidene groups such as vinylidene, or their polymerizability Examples include groups having a group (such as (meth) acryloyl group). Of these functional groups, a polymerizable group is preferable.

  As a method for introducing a polymerizable group into a side chain, for example, a thermoplastic resin having a functional group such as a reactive group or a condensable group is reacted with a polymerizable compound having a reactive group with the functional group. A method etc. can be illustrated.

  In the thermoplastic resin having a functional group, examples of the functional group include a carboxyl group or an acid anhydride group, a hydroxyl group, an amino group, and an epoxy group.

When the thermoplastic resin having a functional group is a thermoplastic resin having a carboxyl group or its acid anhydride group, examples of the polymerizable compound having a reactive group with the functional group include an epoxy group, a hydroxyl group, and an amino group. Examples thereof include a polymerizable compound having a group or an isocyanate group. Among these, polymerizable compounds having an epoxy group, for example, epoxycyclo C _5-8 alkenyl (meth) acrylates such as epoxycyclohexenyl (meth) acrylate, glycidyl (meth) acrylate, allyl glycidyl ether, etc. are widely used.

  As a typical example, a thermoplastic resin having a carboxyl group or its acid anhydride group and an epoxy group-containing compound, particularly a (meth) acrylic polymer ((meth) acrylic acid- (meth) acrylic ester copolymer) Etc.) and an epoxy group-containing (meth) acrylate (such as epoxycycloalkenyl (meth) acrylate and glycidyl (meth) acrylate). Specifically, a polymer having a polymerizable unsaturated group introduced into a part of the carboxyl group of the (meth) acrylic polymer, for example, the carboxyl group of the (meth) acrylic acid- (meth) acrylic acid ester copolymer. A (meth) acrylic polymer (cyclomer P, cyclomer P, in which a polymerizable group (photopolymerizable unsaturated group) is introduced into a side chain by reacting an epoxy group of 3,4-epoxycyclohexenylmethyl acrylate in part. Daicel Corporation) can be used.

  The introduction amount of the functional group (particularly polymerizable group) involved in the curing reaction for the thermoplastic resin is 0.001 to 10 mol, preferably 0.01 to 5 mol, more preferably 0 with respect to 1 kg of the thermoplastic resin. About 0.02 to 3 mol.

These polymer components can be used in appropriate combination. That is, the polymer component may be composed of a plurality of polymers. The plurality of polymers may be phase separable by wet spinodal decomposition. The plurality of polymers may be incompatible with each other. When combining a plurality of polymers, the combination of the first polymer and the second polymer is not particularly limited, but suitable as a plurality of polymers that are incompatible with each other near the processing temperature, for example, two polymers that are incompatible with each other Can be used in combination. For example, when the first polymer is a (meth) acrylic polymer (for example, polymethyl methacrylate, (meth) acrylic polymer having a polymerizable group, etc.), the second polymer is a cellulose ester ( Cellulose acetate C _3-4 acylate such as cellulose acetate propionate) or polyester (urethane modified polyester or the like) may be used.

  Further, from the viewpoint of scratch resistance after curing, at least one of a plurality of polymers, for example, one of the incompatible polymers (when combining the first polymer and the second polymer) , At least one polymer) is preferably a polymer having a functional group (particularly a polymerizable group) capable of reacting with the cured resin precursor component in the side chain.

  The mass ratio between the first polymer and the second polymer can be selected, for example, from the range of the former / the latter = 1/99 to 99/1, preferably about 10/90 to 97/3. When it is a (meth) acrylic polymer and the second polymer is a cellulose ester, the mass ratio of both polymers is the former / the latter = 30/70 to 95/5, preferably 50/50 to 90/10. More preferably, it is about 60/40 to 85/15 (particularly 70/30 to 80/20).

  In addition, as a polymer for forming a phase-separated structure, the said thermoplastic resin and another polymer other than the said two incompatible polymers may be contained.

  The glass transition temperature of the polymer component can be selected from the range of, for example, −100 ° C. to 250 ° C., preferably −50 ° C. to 230 ° C., and more preferably about 0 to 200 ° C. (for example, about 50 to 180 ° C.). From the viewpoint of surface hardness, the glass transition temperature is advantageously 50 ° C. or higher (for example, about 70 to 200 ° C.), preferably 100 ° C. or higher (for example, about 100 to 170 ° C.). The weight average molecular weight of the polymer component can be selected, for example, from 1,000,000 or less, preferably from about 1,000 to 500,000.

(Curing resin precursor component)
The cured resin precursor component is a compound having a functional group that reacts with heat or active energy rays (such as ultraviolet rays or electron beams), and is cured or crosslinked with heat or active energy rays to give a resin (particularly cured or crosslinked). Various curable compounds capable of forming (resin) can be used. Examples of the cured resin precursor component include thermosetting compounds or resins [low molecular weight compounds having epoxy groups, polymerizable groups, isocyanate groups, alkoxysilyl groups, silanol groups, etc. (for example, epoxy resins, unsaturated polyesters). Resin, urethane resin, silicone resin, etc.)], photocurable compounds curable by actinic rays (such as ultraviolet rays) (photocurable monomers, ultraviolet curable compounds such as oligomers), etc. The curable compound may be an EB (electron beam) curable compound. Note that a photocurable compound such as a photocurable monomer, an oligomer, or a photocurable resin that may have a low molecular weight may be simply referred to as a “photocurable resin”.

  Examples of the photocurable compound include monomers and oligomers (or resins, particularly low molecular weight resins).

  Examples of the monomers include monofunctional monomers [(meth) acrylic monomers such as (meth) acrylic acid esters, vinyl monomers such as vinylpyrrolidone, isobornyl (meth) acrylate, adamantyl ( (Meth) acrylates having a bridged cyclic hydrocarbon group such as (meth) acrylate], polyfunctional monomers having at least two polymerizable unsaturated bonds [ethylene glycol di (meth) acrylate, propylene glycol di (meth) ) Acrylate, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, alkylene glycol di (meth) acrylate such as hexanediol di (meth) acrylate; diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) ) Acrylate, (Poly) oxyalkylene glycol di (meth) acrylate such as reoxytetramethylene glycol di (meth) acrylate; bridged cyclic hydrocarbon groups such as tricyclodecane dimethanol di (meth) acrylate and adamantane di (meth) acrylate Di (meth) acrylate having: glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, penta Polymerizable unsaturation of about 3 to 6 such as erythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate Polyfunctional monomer having a focus, etc.], and others. Of these, polyfunctional (meth) acrylates having at least two (meth) acryloyl groups are widely used.

  Examples of the oligomer or resin include (meth) acrylates, epoxy (meth) acrylates, polyester (meth) acrylates, urethane (meth) acrylates, and silicone (meth) acrylates of bisphenol A-alkylene oxide adducts.

  These photocurable compounds can be used alone or in combination of two or more. Among these, a photocurable compound that can be cured in a short time, for example, an ultraviolet curable compound (such as a monomer, an oligomer, or a resin that may have a low molecular weight) or an EB curable compound is preferable. In particular, a practically advantageous resin precursor is an ultraviolet curable resin. In particular, in the present invention, the photocurable compound preferably contains urethane (meth) acrylate from the viewpoint that both high antiglare properties and suppression of glare can be achieved.

  The urethane (meth) acrylate may be a urethane (meth) acrylate obtained by reacting a polyisocyanate with a (meth) acrylate having an active hydrogen atom.

  Polyisocyanates may be urethane prepolymers produced by reaction of polyisocyanates and polyols (for example, polyester polyesters, polyether polyesters, etc.) and having free isocyanate groups, but from the point of scratch resistance, Polyisocyanates are preferred.

  Examples of the polyisocyanate include aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, aromatic polyisocyanates, and polyisocyanate derivatives.

Examples of the aliphatic polyisocyanate include C _2-16 alkane diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), and trimethylhexamethylene diisocyanate. Examples of the alicyclic polyisocyanate include 1,4-cyclohexane diisocyanate, isophorone diisocyanate (IPDI), 4,4′-methylenebis (cyclohexyl isocyanate), hydrogenated xylylene diisocyanate, norbornane diisocyanate, and the like. Examples of the araliphatic polyisocyanate include xylylene diisocyanate (XDI) and tetramethyl xylylene diisocyanate. Examples of aromatic polyisocyanates include phenylene diisocyanate, 1,5-naphthalene diisocyanate (NDI), diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), 4,4′-toluidine diisocyanate, and 4,4′-diphenyl ether diisocyanate. Etc. Examples of polyisocyanate derivatives include multimers such as dimers and trimers, biurets, allophanates, carbodiimides, and uretdiones. These polyisocyanates can be used alone or in combination of two or more.

Of these polyisocyanates, non-yellowing type diisocyanates or derivatives thereof, for example, aliphatic diisocyanates such as HDI, alicyclic diisocyanates such as IPDI, hydrogenated XDI, etc., because both scratch resistance and optical properties can be achieved. A non-yellowing diisocyanate or a derivative thereof such as _C4-12 alkane diisocyanate such as HDI (particularly C _5-8 alkane diisocyanate) is particularly preferable.

Examples of the (meth) acrylate having an active hydrogen atom include hydroxy C _2-6 alkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, and 2-hydroxy-3- Hydroxyalkoxy C _2-6 alkyl (meth) acrylates such as methoxypropyl (meth) acrylate; ditrimethylolethane tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri ( And (meth) acrylic acid partial esters of polyhydric alcohols such as (meth) acrylate and dipentaerythritol penta (meth) acrylate. These (meth) acrylates can be used alone or in combination of two or more. Of these, (meth) acrylic acid partial esters of polyhydric alcohols such as pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate are preferred from the viewpoint of scratch resistance.

  The number of (meth) acryloyl groups in one molecule of urethane (meth) acrylate (the number of functional groups) may be 2 or more (bifunctional or more), for example, 2 to 30, preferably 3 to 25 ( For example, 4 to 20), more preferably 5 to 15 (especially 8 to 12). If the number of (meth) acryloyl groups is too small, scratch resistance may be reduced.

  The weight average molecular weight of the urethane (meth) acrylate is not particularly limited, but may be 5000 or less (for example, 500 to 5000) in terms of polystyrene in gel permeation chromatography (GPC), for example, 550 to 4000, preferably It may be about 600 to 3000, more preferably about 800 to 2000 (particularly 1000 to 1500). If the molecular weight is too large, the scratch resistance may decrease.

  In addition to the urethane (meth) acrylate, the photocurable compound contains a fluorine-containing curable compound (a precursor component containing a fluorine atom or a fluorine-based compound having a polymerizable group) from the viewpoint that the surface can be modified. Is preferred.

  Examples of the fluorine-containing curable compound include fluorides of the above monomers and oligomers, such as fluorinated alkyl (meth) acrylates [for example, perfluorooctylethyl (meth) acrylate and trifluoroethyl (meth) acrylate], fluorine (Poly) oxyalkylene glycol di (meth) acrylate [eg, fluoroethylene glycol di (meth) acrylate, fluoropolyethylene glycol di (meth) acrylate, fluoropropylene glycol di (meth) acrylate, etc.], fluorine-containing epoxy resin, fluorine Examples thereof include urethane-based resins. Of these, fluoropolyether compounds having a (meth) acryloyl group are preferred. The fluorine-containing curable compound may be a commercially available fluorine-based polymerizable leveling agent.

  The ratio of a fluorine-containing curable compound is 0.1-5 mass parts with respect to 100 mass parts of curable compositions (total solid content), Preferably it is 0.2-4 mass parts, More preferably, it is 0.3. To 3 parts by mass (particularly 0.5 to 2 parts by mass). If the ratio of the fluorine-containing curable compound is too small, the effect of promoting phase separation may be reduced, and if it is too high, the scratch resistance may be reduced.

  The cured resin precursor component may further contain a filler in order to improve the antiglare property and the scratch resistance depending on the type.

  Examples of the filler may include inorganic particles such as silica particles, titania particles, zirconia particles, and alumina particles, and organic particles such as crosslinked (meth) acrylic polymer particles and crosslinked styrene resin particles. These fillers can be used alone or in combination of two or more.

  Of these fillers, silica particles are preferable because they are excellent in optical properties and can easily form an uneven shape that can achieve both transparency and antiglare properties by spinodal decomposition. The silica particles are preferably solid silica particles because the transparency of the laminate can be improved.

  The shape of the filler may be an anisotropic shape, but isotropic shape is preferable, and spherical shape is particularly preferable. The average particle diameter of the filler is, for example, about 0.1 to 10 μm, preferably about 0.5 to 5 μm, and more preferably about 0.8 to 3 μm.

  The ratio of a filler is 1-50 mass parts with respect to 100 mass parts of curable compositions (total solid content), Preferably it is 2-40 mass parts, More preferably, it is about 3-30 mass parts.

  The cured resin precursor component may further contain a curing agent depending on the type. For example, the thermosetting resin may contain a curing agent such as amines and polyvalent carboxylic acids, and the photocurable resin may contain a photopolymerization initiator. Examples of the photopolymerization initiator include conventional components such as acetophenones or propiophenones, benzyls, benzoins, benzophenones, thioxanthones, and acylphosphine oxides. The ratio of the curing agent such as the photopolymerization initiator is 0.1 to 20% by mass, preferably 0.5 to 10% by mass, and more preferably about 1 to 8% by mass with respect to the entire cured resin precursor component. .

  The cured resin precursor component may further contain a curing accelerator. For example, the photocurable resin may contain a photocuring accelerator, for example, a tertiary amine (such as a dialkylaminobenzoic acid ester), a phosphine photopolymerization accelerator, and the like.

(Combination of polymer component and cured resin precursor component)
In the present invention, among the polymer component and the cured resin precursor component, at least two components are used in a combination in which phase separation occurs near the processing temperature. Examples of combinations for phase separation include (a) a combination in which a plurality of polymer components are incompatible with each other, (b) a combination in which the polymer component and the cured resin precursor component are incompatible with each other, (C) A combination in which a plurality of cured resin precursor components are incompatible with each other and phase separated is exemplified. Among these combinations, usually, (a) a combination of a plurality of polymer components, or (b) a combination of a polymer component and a cured resin precursor component, and particularly (a) a combination of a plurality of polymer components is preferable. . When the compatibility of both of the phases to be separated is high, both do not effectively separate in the drying process for evaporating the solvent, and the function as an antiglare layer is reduced.

  Note that the polymer component and the cured resin precursor component are generally incompatible with each other. When the polymer component and the cured resin precursor component are incompatible and phase-separated, a plurality of polymer components may be used as the polymer component. When a plurality of polymer components are used, it is sufficient that at least one polymer component is incompatible with the cured resin precursor component, and other polymer components may be compatible with the cured resin precursor component. Further, it may be a combination of two polymer components that are incompatible with each other and a cured resin precursor component (in particular, a monomer or oligomer having a plurality of curable functional groups).

  When the polymer component is composed of a plurality of incompatible polymer components and phase-separated, the cured resin precursor component is compatible with at least one of the incompatible polymers at a processing temperature. Used in melting combinations. That is, when a plurality of polymer components that are incompatible with each other are constituted by, for example, a first polymer and a second polymer, the cured resin precursor component is in phase with either the first polymer or the second polymer. It may be dissolved, and may be compatible with both polymer components, but preferably it is compatible with only one polymer component. When compatible with both polymer components, at least two phases of a mixture based on the first polymer and the cured resin precursor component and a mixture based on the second polymer and the cured resin precursor component Phase separate.

  When the compatibility of the plurality of selected polymer components is high, the polymer components are not effectively separated from each other in the drying process for evaporating the solvent, and the function as an antiglare layer is reduced. The phase separation of multiple polymer components should be confirmed visually by checking whether residual solids become cloudy in the process of preparing a homogeneous solution using good solvents for both components and gradually evaporating the solvent. Can be easily determined.

  Furthermore, the refractive index of the polymer component and the cured or crosslinked resin produced by curing the cured resin precursor component are usually different from each other. In addition, the refractive indexes of the plurality of polymer components (first polymer and second polymer) are also different from each other. The difference in refractive index between the polymer component and the cured or cross-linked resin and the difference in refractive index between the plurality of polymer components (the first polymer and the second polymer) are, for example, 0.01 to 0.2, preferably 0. It may be about 05 to 0.15.

  The ratio (mass ratio) between the polymer component and the cured resin precursor component is not particularly limited, and can be selected, for example, from the range of the former / the latter = 1/99 to 95/5, for example, 2/98 to 90/10. (For example, 3/97 to 50/50), preferably 5/95 to 40/60, more preferably about 10/90 to 30/70 (especially 15/85 to 25/75). If the ratio of the polymer component is too small, the antiglare property may be lowered, and if it is too large, the scratch resistance may be lowered.

(Other ingredients)
The antiglare layer formed from the cured product of the curable composition is made of various additives such as leveling agents, stabilizers (antioxidants, UV absorbers, etc.), surfactants, water-soluble polymers, fillers. , Crosslinking agents, coupling agents, colorants, flame retardants, lubricants, waxes, preservatives, viscosity modifiers, thickeners, antifoaming agents, and the like. The ratio of an additive is about 0.01-10 mass% (especially 0.1-5 mass%) with respect to the whole glare-proof layer, for example.

(Thickness of anti-glare layer)
The thickness (average thickness) of the antiglare layer is, for example, about 1 to 20 μm, preferably 2 to 10 μm, more preferably about 3 to 8 μm (particularly 4 to 6 μm). In addition, in this specification and a claim, the average thickness of each layer can be calculated | required by measuring arbitrary 10 places using an optical film thickness meter, and calculating an average value.

[Internal haze layer]
The laminate of the present invention further includes an internal haze layer in addition to the antiglare layer. By combining this internal haze layer with the antiglare layer, glare can be suppressed while maintaining the antiglare property of the antiglare layer.

  The internal haze layer only needs to have a predetermined light scattering property, and the haze of the internal haze layer is, for example, 1 to 60% (for example, 3 to 58%), preferably 5 to 55%, more preferably 8 to. It is about 50% (especially 10 to 45%). If the haze of the internal haze layer is too small, glare may not be suppressed. Conversely, if it is too large, the visibility may be reduced.

  In addition, in this specification and a claim, a haze can be measured using a haze meter (Nippon Denshoku Industries Co., Ltd. "NDH-5000W") based on JISK7163.

  The internal haze layer only needs to have the haze, and may be a phase separation scattering layer formed by phase separation from a liquid phase, or a particle scattering layer in which particles are mixed in a resin component. May be.

(Phase separation scattering layer)
The phase-separated scattering layer may be a cured product of a curable composition (particularly a photocurable composition) containing one or more polymer components and one or more cured resin precursor components.

  As a polymer component, the polymer component illustrated by the term of the said glare-proof layer is mentioned. The said polymer component can be used individually or in combination of 2 or more types. Of the polymer components, polyester is preferable, and amorphous polyester is particularly preferable.

  The amorphous polyester may be any of a copolymer of dicarboxylic acid and diol, a copolymer of dicarboxylic acid, diol and hydroxycarboxylic acid, a copolymer of hydroxycarboxylic acid, and a copolymer of lactone. .

Examples of the dicarboxylic acid include _C8-20 aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid, 2,7-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,5-naphthalenedicarboxylic acid, adipic acid, C _4-12 alkanedicarboxylic acid such as azelaic acid and sebacic acid, C _4-12 cycloalkanedicarboxylic acid such as 1,4-cyclohexanedicarboxylic acid, and the like.

Examples of the diol include C _2-10 alkane diols such as ethylene glycol, propylene glycol, butane diol and neopentyl glycol, poly C _2-4 alkylene glycols such as diethylene glycol and polyethylene glycol, 1,4-cyclohexane dimethanol and the like. Aromatic diols such as C _4-12 cycloalkanediol, bisphenol A, bisphenol A-alkylene oxide adducts and the like can be mentioned.

  Examples of the hydroxycarboxylic acid include p-hydroxybenzoic acid and p-hydroxyethoxybenzoic acid.

Examples of the lactone include C _4-8 lactone such as β-butyrolactone, δ-valerolactone, and ε-caprolactone.

  The amorphous polyester may be further combined with a polyol (such as glycerin, trimethylolpropane, trimethylolethane, or pentaerythritol) and / or a polyvalent carboxylic acid (such as trimellitic acid or pyromellitic acid).

The specific amorphous polyester may be a copolymer having a poly C _2-4 alkylene-C _6-10 arylate skeleton as a main skeleton, for example, a poly C _2-4 alkylene-C _6-10 arylate. Among the structural units, a part of C _2-4 alkylene glycol is substituted with polyoxy C _2-4 alkylene glycol, C _5-10 alkylene glycol, alicyclic diol (cyclohexanedimethanol, hydrogenated bisphenol A, etc.), aromatic. Copolyesters substituted with other diols such as diols (such as bisphenol A and bisphenol A-alkylene oxide adducts), symmetric aromatic dicarboxylic acids such as terephthalic acid, and other asymmetric aromatic dicarboxylic acids such as phthalic acid and isophthalic acid acid, other radical such as aliphatic C _6-12 dicarboxylic acid such as adipic acid It may be substituted copolyester phosphate. The molar ratio of C _2-4 alkylene glycol to other diol can be selected from the range of the former / the latter = 99/1 to 10/90, for example, 95/5 to 20/80, preferably 90/10 to 30. / 70, more preferably about 80/20 to 50/50. The molar ratio of the symmetric aromatic dicarboxylic acid and the other dicarboxylic acid can be selected from the range of the former / the latter = 99/1 to 10/90, for example, 95/5 to 20/80, preferably 90/10 to 30. / 70, more preferably about 80/20 to 50/50.

  The number average molecular weight (Mn) of the amorphous polyester is, for example, 5000 to 50000, preferably 6000 to 40000, more preferably about 10,000 to 30000 in terms of polystyrene using GPC.

  Examples of the cured resin precursor component (particularly a photocurable compound) include the cured resin precursor components exemplified in the section of the antiglare layer. The said cured resin precursor component can be used individually or in combination of 2 or more types. Of the cured resin precursor components, it is preferable to include urethane (meth) acrylate.

  The urethane (meth) acrylate may be a urethane (meth) acrylate obtained by reacting a polyisocyanate with a (meth) acrylate having an active hydrogen atom.

Examples of the polyisocyanates include the polyisocyanates exemplified in the section of the antiglare layer. The polyisocyanates can be used alone or in combination of two or more. Of the polyisocyanates, non-yellowing type diisocyanates or derivatives thereof, for example, non-yellowing diisocyanates or derivatives thereof such as aliphatic diisocyanates such as HDI, alicyclic diisocyanates such as IPDI and hydrogenated XDI, and the like are preferable. Particularly preferred are C _4-12 alkane diisocyanates such as C _5-8 alkane diisocyanate.

Examples of the (meth) acrylate having an active hydrogen atom include (meth) acrylates having an active hydrogen atom exemplified in the section of the antiglare layer. Among the (meth) acrylates having active hydrogen atoms, hydroxyalkoxy such as hydroxy C _2-6 alkyl (meth) acrylate such as 2-hydroxyethyl (meth) acrylate and 2-hydroxy-3-methoxypropyl (meth) acrylate C _2-6 alkyl (meth) acrylate is preferred.

  The number of (meth) acryloyl groups in one molecule of urethane (meth) acrylate (the number of functional groups) may be 2 or more (bifunctional or more), for example, 2 to 10, preferably 2 to 5, More preferably, it is about 2 to 3 (especially 2).

  The weight average molecular weight of the urethane (meth) acrylate is not particularly limited, but may be 3000 or less (for example, 400 to 3000) in terms of polystyrene in gel permeation chromatography (GPC), for example, 450 to 2500, preferably It may be about 500 to 2000, more preferably about 600 to 1500 (particularly 800 to 1200).

  It is preferable that a photocurable compound contains a fluorine-containing curable compound from the point which can improve phase-separation property in addition to the said urethane (meth) acrylate. As a fluorine-containing curable compound, the fluorine-containing curable compound illustrated by the term of the glare-proof layer is mentioned. Of the fluorine-containing curable compounds, a fluoropolyether compound having a (meth) acryloyl group is preferred. The fluorine-containing curable compound may be a commercially available fluorine-based polymerizable leveling agent.

  In the phase-separated scattering layer, the combination in which the phases are separated from each other near the processing temperature may be a combination in which the polymer component and the cured resin precursor component are incompatible and phase separated. The difference in refractive index between the polymer component and the cured product of the cured resin precursor component may be, for example, about 0.01 to 0.2, preferably about 0.05 to 0.15.

  The cured resin precursor component may further contain a curing agent and a curing accelerator depending on the type. Preferred embodiments and ratios of the curing agent and the curing accelerator are the same as those in the antiglare layer.

  The ratio (mass ratio) between the polymer component and the cured resin precursor component is not particularly limited, and can be selected, for example, from the range of the former / the latter = 1/99 to 95/5, for example, 2/98 to 90/10. (For example, 3/97 to 50/50), preferably 5/95 to 40/60, more preferably about 10/90 to 30/70 (especially 15/85 to 25/75).

(Particle scattering layer)
In the particle-based scattering layer, it suffices if particles are blended in the resin component, and the resin component is not particularly limited as long as it is a transparent resin component having a refractive index different from that of the particles, but usually a cured resin precursor component Is used.

  Examples of the cured resin precursor component (particularly a photocurable compound) include the cured resin precursor components exemplified in the section of the antiglare layer. The said cured resin precursor component can be used individually or in combination of 2 or more types. Of the cured resin precursor components, it is preferable to include urethane (meth) acrylate.

  The urethane (meth) acrylate may be a urethane (meth) acrylate obtained by reacting a polyisocyanate with a (meth) acrylate having an active hydrogen atom.

Examples of the polyisocyanates include the polyisocyanates exemplified in the section of the antiglare layer. The polyisocyanates can be used alone or in combination of two or more. Of the polyisocyanates, non-yellowing type diisocyanates or derivatives thereof, for example, non-yellowing diisocyanates or derivatives thereof such as aliphatic diisocyanates such as HDI, alicyclic diisocyanates such as IPDI and hydrogenated XDI, and the like are preferable. Particularly preferred are C _4-12 alkane diisocyanates such as C _5-8 alkane diisocyanate.

  Examples of the (meth) acrylate having an active hydrogen atom include (meth) acrylates having an active hydrogen atom exemplified in the section of the antiglare layer. Of the (meth) acrylates having active hydrogen atoms, (meth) acrylic acid partial esters of polyhydric alcohols such as pentaerythritol tri (meth) acrylate are preferred.

  The number of (meth) acryloyl groups in one molecule of urethane (meth) acrylate (the number of functional groups) may be 2 or more (bifunctional or more), for example, 2 to 20, preferably 3 to 15 ( For example, 4 to 10), more preferably 4 to 8 (especially 5 to 7).

  The weight average molecular weight of the urethane (meth) acrylate is not particularly limited, but may be 3000 or less (for example, 500 to 3000) in terms of polystyrene in gel permeation chromatography (GPC), for example, 550 to 2000, preferably It may be about 600 to 1500, more preferably about 650 to 1000 (particularly 700 to 800).

  The cured resin precursor component may further contain a curing agent and a curing accelerator depending on the type. Preferred embodiments and ratios of the curing agent and the curing accelerator are the same as those in the antiglare layer.

  Examples of the particles include the filler exemplified in the item of the antiglare layer. The fillers (particles) can be used alone or in combination of two or more. Of the particles, silica particles are preferred. The silica particles are preferably solid silica particles because the transparency of the laminate can be suppressed.

  The shape of the particles may be anisotropic, but isotropic is preferable and spherical is particularly preferable. The average particle diameter of the particles is, for example, about 0.05 to 10 μm (for example, 0.1 to 5 μm), preferably 0.2 to 3 μm, and more preferably about 0.3 to 2 μm (particularly 0.5 to 1.5 μm). is there.

  The ratio of the particles is, for example, about 1 to 50 parts by mass, preferably 5 to 40 parts by mass, and more preferably 10 to 30 parts by mass (particularly 15 to 25 parts by mass) with respect to 100 parts by mass of the cured resin precursor. .

(Other ingredients)
The internal haze layer may also contain other components (various additives) exemplified in the item of the antiglare layer. The ratio of the additive is the same as that of the antiglare layer.

(Internal haze layer thickness)
The thickness (average thickness) of the internal haze layer is, for example, about 3 to 30 μm, preferably about 5 to 20 μm, and more preferably about 8 to 18 μm (particularly 10 to 15 μm). The average thickness of the internal haze layer is, for example, 1.2 to 5 times, preferably 1.3 to 3 times, more preferably 1.5 to 2.5 times (particularly 1) with respect to the average thickness of the antiglare layer. .8 to 2.2 times).

[Base material layer]
The laminate of the present invention includes a base material layer in addition to the antiglare layer and the internal haze layer. In the present invention, the antiglare layer only needs to be formed on the surface, and the lamination form is not particularly limited, and the internal haze layer and / or the antiglare layer is formed on at least one surface (one surface or both surfaces) of the base material layer. The internal haze layer and the antiglare layer may be directly laminated, or may be laminated via the base material layer, but from the viewpoint of productivity, etc., on one surface of the base material layer A laminated form in which an antiglare layer is laminated and an internal haze layer is laminated on the other surface is preferable.

  The base material layer only needs to be formed of a transparent material, and can be selected according to the use, and may be an inorganic material such as glass, but an organic material is generally used from the viewpoint of strength and moldability. Examples of the organic material include cellulose derivatives, polyesters, polyamides, polyimides, polycarbonates, (meth) acrylic polymers, and the like. Among these, cellulose esters, polyesters, polycarbonates and the like are widely used, and polyesters and polycarbonates are preferable.

  Examples of the polyester include polyalkylene arylates such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN). Examples of the polycarbonate include bisphenol type polycarbonate.

Of these, poly C _2-4 alkylene arylates such as PET and PEN, and bisphenol A type polycarbonates are preferred from the viewpoint of excellent balance of mechanical properties and transparency.

  The base material layer may also contain a conventional additive exemplified in the item of the antiglare layer. The ratio of the additive is the same as that of the antiglare layer.

  The base material layer may be a uniaxial or biaxially stretched film, but may be an unstretched film because it has a low birefringence and is optically isotropic.

  The base material layer may be subjected to surface treatment (for example, corona discharge treatment, flame treatment, plasma treatment, ozone or ultraviolet irradiation treatment), and may have an easy adhesion layer.

  The thickness (average thickness) of a base material layer is 5-2000 micrometers, for example, Preferably it is 15-1000 micrometers, More preferably, it is about 20-500 micrometers.

[Characteristics of laminate]
The laminate of the present invention has a relatively high haze despite high transparency and excellent visibility. The haze of the laminate is, for example, about 10 to 80%, preferably 30 to 75%, and more preferably 50 to 70% (particularly 60 to 65%). If the haze is too low, the antiglare property may be reduced. If the haze is too high, the visibility may be reduced.

  The total light transmittance of the laminate is, for example, about 70% or more (for example, 70 to 100%), preferably 80 to 99%, and more preferably about 85 to 98% (particularly 90 to 95%). If the total light transmittance is too low, the transparency may decrease.

  In the present specification and claims, the total light transmittance can be measured using a haze meter (“NDH-5000W” manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K7361.

  The 60 ° gloss on the surface of the antiglare layer is, for example, about 1 to 60% (for example, 5 to 55%), preferably about 10 to 40%, and more preferably about 15 to 30% (particularly 20 to 25%). If the 60 ° gloss is too small, the visibility may be reduced, whereas if it is too large, the antiglare property may be reduced.

  In the present specification and claims, 60 ° gloss can be measured using a gloss meter (“Poly-Gloss KT-GL0030” manufactured by TQC Co.) in accordance with JIS K8741.

  The arithmetic average roughness Ra of the antiglare layer surface may be 0.05 to 0.3 μm, preferably 0.06 to 0.25 μm, more preferably 0.07 to 0.25 μm (particularly 0.08 to About 0.2 μm). If Ra is too small, the antiglare property may be lowered, and if it is too large, the scratch resistance may be lowered.

  The average length RSm of the roughness curve element on the surface of the antiglare layer may be 5 to 35 μm, preferably 5 to 25 μm, and more preferably 8 to 20 μm (particularly 10 to 15 μm). If the RSm is too small, the antiglare property may be reduced. If the RSm is too large, the scratch resistance and the slipperiness with a finger may be reduced.

  The maximum sectional height Rt of the roughness curve on the surface of the antiglare layer may be 0.1 to 2 μm, preferably 0.1 to 1.5 μm (for example, 0.1 to 1 μm), more preferably 0.5. It is about -0.9 micrometer (especially 0.6-0.8 micrometer). If Rt is too small, the antiglare property may be lowered, and if it is too large, the scratch resistance may be lowered.

  In the present specification and claims, the arithmetic average roughness Ra, the average length RSm of the roughness curve element, and the maximum section height Rt of the roughness curve are in accordance with JIS B0601, and are non-contact surface / layer sections. Using a shape measurement system [“VertScan 2.0” manufactured by Ryoka System Co., Ltd.], it can be obtained based on a curve obtained by measuring the uneven shape of the surface of the antiglare layer.

  The surface of the antiglare layer is excellent in slipperiness with a finger, and was measured under the conditions of a load of 0.2 N, a moving speed of 50 mm / second, and an effective measurement distance of 50 mm using a surface contactor attached with artificial skin. The dynamic friction coefficient of the antiglare layer surface may be 3 or less, for example, 0.1 to 3, preferably 0.2 to 2, and more preferably about 0.3 to 1.5 (particularly 0.5 to 1). It is. If the dynamic friction coefficient is too high, the slipperiness with a finger may be reduced.

  In the present specification and claims, the dynamic friction coefficient can be measured using a dynamic friction measuring machine, and can be measured in detail by the method described in the examples described later. Various artificial rubber or urethane elastomer materials have been developed mainly in the medical field as artificial skins for surface contacts. In the present specification and claims, “Bio Skin” manufactured by Beaulux can be used as a commercial product of artificial skin.

  In addition to the antiglare layer, the internal haze layer, and the base material layer, the laminate of the present invention may be combined with an adhesive layer, a low refractive index layer, an antireflection layer, or the like as a conventional functional layer.

[Manufacturing method of laminate]
The manufacturing method of the laminated body of this invention should just include the glare-proof layer formation process which is phase-separated by wet spinodal decomposition | disassembly and forms an uneven | corrugated shape.

  In the antiglare layer forming step, when a curable composition containing one or more polymer components and one or more cured resin precursor components is used as a liquid composition for forming an antiglare layer in a wet manner, the curing is performed. The composition is coated on a support and dried to cause phase separation of at least two components selected from a polymer component and a cured resin precursor component by wet spinodal decomposition, and then phase separated curable properties. The composition may be cured by heat or active energy rays.

  The support may be an internal haze layer or the like laminated on the base material layer, but the base material layer is preferable from the viewpoint of productivity.

  The curable composition may contain a solvent. The solvent can be selected according to the kind and solubility of the polymer component and the cured resin precursor component, and at least solid content (for example, a plurality of polymer components and cured resin precursor components, reaction initiators, other additives) is uniform. Any solvent can be used as long as it can be dissolved in the solvent. In particular, the phase separation structure may be controlled by adjusting the solubility of the solvent in the polymer component and the cured resin precursor. Examples of such a solvent include ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), ethers (dioxane, tetrahydrofuran, etc.), aliphatic hydrocarbons (hexane, etc.), alicyclic hydrocarbons ( Cyclohexane), aromatic hydrocarbons (toluene, xylene, etc.), halogenated carbons (dichloromethane, dichloroethane, etc.), esters (methyl acetate, ethyl acetate, butyl acetate, etc.), water, alcohols (ethanol, isopropanol, Butanol, cyclohexanol, etc.), cellosolves [methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether (1-methoxy-2-propanol), etc.], cellosolve acetates, sulfoxides (dimethylsulfate) Kishido etc.), amides (dimethylformamide, dimethylacetamide, etc.), and others. The solvent may be a mixed solvent.

Of these solvents, it is preferable to include ketones such as methyl ethyl ketone, and a mixture of ketones and alcohols (aliphatic alcohols such as butanol) and / or esters (aliphatic carboxylic acid esters such as butyl acetate). A solvent is more preferable, and a mixed solvent of ketones (particularly di-C _1-4 alkyl ketone) and alcohols (particularly C _1-6 alkanol) is most preferable. In the mixed solvent, the ratio of alcohols and / or esters (total amount when both are mixed) is, for example, 1 to 150 parts by mass (for example, 3 to 100 parts by mass), preferably 100 parts by mass of ketones, It is about 5-100 mass parts, More preferably, it is about 10-30 mass parts (especially 15-20 mass parts). In the present invention, by appropriately combining solvents, phase separation by spinodal decomposition can be adjusted, and an uneven shape that can achieve both visibility, transparency, and antiglare properties can be formed.

  The concentration of the solute (polymer component, cured resin precursor component, reaction initiator, other additives) in the mixed solution can be selected within a range where phase separation occurs and a range where casting properties and coating properties are not impaired. It is 80 mass%, Preferably it is 10-70 mass%, More preferably, it is about 20-50 mass% (especially 30-40 mass%) grade.

  As a coating method, conventional methods such as roll coater, air knife coater, blade coater, rod coater, reverse coater, bar coater, comma coater, dip squeeze coater, die coater, gravure coater, micro gravure coater, silk screen coater. Method, dip method, spray method, spinner method and the like. Of these methods, the bar coater method and the gravure coater method are widely used. If necessary, the coating solution may be applied a plurality of times.

  After casting or coating the mixed solution, the temperature is near or lower than the boiling point of the solvent (for example, 1 to 120 ° C., preferably 5 to 50 ° C., particularly about 10 to 50 ° C. lower than the boiling point of the solvent). By evaporating the solvent, the phase separation by spinodal decomposition can be induced. The evaporation of the solvent is usually drying, for example, depending on the boiling point of the solvent, 30 to 200 ° C. (eg 30 to 100 ° C.), preferably 40 to 120 ° C., more preferably 50 to 90 ° C. (especially 60 to 85 ° C.). ) By drying at about a temperature.

  By such spinodal decomposition accompanied by evaporation of the solvent, regularity or periodicity can be imparted to the average distance between the domains of the phase separation structure.

  When the dried curable composition is finally cured by actinic rays (ultraviolet rays, electron beams, etc.) or heat, the phase separation structure formed by spinodal decomposition can be immediately immobilized. The curing of the curable composition may be combined with heating, light irradiation, or the like depending on the type of the cured resin precursor component.

  The heating temperature can be selected from an appropriate range, for example, about 50 to 150 ° C. The light irradiation can be selected according to the type of the photocuring component or the like, and usually ultraviolet rays, electron beams, etc. can be used. A general-purpose light 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 (light source such as helium-cadmium laser or excimer laser) can be used. Irradiation light amount (irradiation energy) differs by the thickness of the coating film, for example, 10 to 10000 mJ / cm ^2, preferably 20~5000mJ / cm ^2, more preferably 30~3000mJ / cm ² approximately. If necessary, the light irradiation may be performed in an inert gas atmosphere.

  The production method of the present invention includes an internal haze layer forming step in addition to the antiglare layer forming step. From the viewpoint of productivity and the like, in the internal haze forming step, of the front and back surfaces of the base material layer, It is preferable to laminate an internal haze layer on the surface on which the glare layer is not laminated.

  When the internal haze layer is a phase separation type scattering layer, the internal haze layer forming step applies a curable composition containing at least one polymer component and at least one cured resin precursor component onto the base material layer. And drying, at least two components selected from a polymer component and a cured resin precursor component are phase-separated by wet spinodal decomposition, and then the phase-separated curable composition is cured with heat or active energy rays. It is also possible to use a method.

  The curable composition may contain a solvent. As a solvent, the solvent illustrated by the said glare-proof layer formation process can be utilized. The said solvent can be used individually or in combination of 2 or more types. Of the solvents, ketones such as methyl ethyl ketone are preferred.

  The concentration of the solute (polymer component, cured resin precursor component, reaction initiator, other additives) in the mixed solution is, for example, 1 to 80% by mass, preferably 10 to 70% by mass, and more preferably 20 to 50% by mass. (Especially 35 to 45% by mass).

  As a coating method, a drying method, and a curing method of such a curable composition, the method exemplified in the antiglare layer forming step can be used, and preferred embodiments are also the same.

  When the internal haze layer is a particle-based scattering layer, the internal haze layer forming step is performed by applying a curable composition containing a cured resin precursor component and particles onto the base material layer and drying, and then heat or active energy. It may be a method of curing with a wire.

  The curable composition may contain a solvent. As a solvent, the solvent illustrated by the said glare-proof layer formation process can be utilized. The said solvent can be used individually or in combination of 2 or more types. Of the solvents, ketones such as methyl ethyl ketone are preferred.

  The concentration of the solute (cured resin precursor component, particles, reaction initiator, other additives) in the mixed solution is, for example, 1 to 80% by mass, preferably 10 to 70% by mass, and more preferably 30 to 60% by mass ( In particular, it is about 45 to 50% by mass).

  As a coating method, a drying method, and a curing method of such a curable composition, the method exemplified in the antiglare layer forming step can be used, and preferred embodiments are also the same.

[Display device]
Since the laminate of the present invention can achieve both high antiglare properties and suppression of glare, it can be used for various display devices, such as liquid crystal display devices (LCD), organic EL displays, and the like. Therefore, it is useful as a display device with a touch panel, particularly as a high-definition LCD with touch panel or an organic EL display.

  Specifically, the LCD may be a reflective LCD that uses external light to illuminate a display unit that includes a liquid crystal cell, or a transmissive LCD that includes a backlight unit that illuminates the display unit. May be. In the reflective LCD, incident light from the outside can be taken in via the display unit, and the display unit can be illuminated by reflecting the transmitted light that has passed through the display unit by the reflecting member. In the reflective LCD, the laminate of the present invention can be disposed in the optical path ahead of the reflective member. For example, the laminate of the present invention can be disposed or laminated on the front surface (viewing side front surface) of the display unit, and in particular, disposed on the front surface of an LCD having a collimated backlight unit and not having a prism sheet. May be.

  In a transmissive LCD, a backlight unit allows light from a light source (a tubular light source such as a cold cathode tube or a point light source such as a light-emitting diode) to enter from one side and exit from the front exit surface. A light guide plate (for example, a light guide plate having a wedge-shaped cross section) may be provided. If necessary, a prism sheet may be provided on the front side of the light guide plate. In general, a reflection member for reflecting light from the light source toward the emission surface is disposed on the back surface of the light guide plate. In such a transmissive LCD, usually, the laminate of the present invention can be disposed in the optical path ahead of the light source. For example, the laminate can be disposed or laminated on the front surface of the display unit.

  In the organic EL display, the organic EL has a light emitting element for each pixel, and this light emitting element is usually a negative electrode such as a metal / electron injection layer / electron transport layer / light emitting layer / hole transport layer / It is formed of a positive electrode such as a hole injection layer / ITO / a substrate such as a glass plate or a transparent plastic plate. Also in the organic EL display, the laminate of the present invention may be disposed in the optical path.

  Moreover, you may utilize the laminated body of this invention as an aftermarket protection or protection film for preventing the damage | wound of LCD with a touch panel, and an organic EL display.

  EXAMPLES Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. The raw materials used in Examples and Comparative Examples are as follows, and the obtained laminates were evaluated by the following methods.

[material]
Acrylic resin having a polymerizable group: a compound obtained by adding 3,4-epoxycyclohexenylmethyl acrylate to a part of the carboxyl group of a (meth) acrylic acid- (meth) acrylic acid ester copolymer, manufactured by Daicel Corporation "Cyclomer P (ACA) 320M", solid content 40% by mass
Cellulose acetate propionate: “CAP-482-20” manufactured by Eastman, acetylation degree = 2.5%, propionyl degree = 46%, polystyrene-equivalent number average molecular weight 75000
Amorphous polyester: “Byron 20SS” manufactured by Toyobo Co., Ltd., solid content: 30% by mass
Urethane acrylate A: 15 functional urethane acrylate, theoretical molecular weight 2300, “N-15HA” manufactured by Shin-Nakamura Chemical Co., Ltd.
Urethane acrylate B: 10-functional aliphatic urethane acrylate, average molecular weight 1200, “KRM8452” manufactured by Daicel Ornex Co., Ltd.
Urethane acrylate C: bifunctional aliphatic urethane acrylate, average molecular weight 1000, “Ebecryl 8402” manufactured by Daicel Ornex Co., Ltd.
Urethane acrylate D: Hexafunctional urethane acrylate, theoretical molecular weight 700-800, Shin-Nakamura Chemical Co., Ltd. “UA-1100H”
Fluorine group-containing UV-reactive surface modifier: DIC Corporation's “Megafac RS-75”
Silica-containing acrylic coating liquid: Silica fine particle-containing acrylic ultraviolet curable compound, “Z-757-4RL” manufactured by Aika Industry Co., Ltd., solid content: 43% by mass
Silica spherical fine particles: “Seahoster KE-P100” manufactured by Nippon Shokubai Co., Ltd.
Photoinitiator A: “Irgacure 907” manufactured by BASF Japan
Photoinitiator B: “Irgacure 184” manufactured by BASF Japan
PET film: polyethylene terephthalate film, “O321” manufactured by Mitsubishi Plastics, Inc., thickness 125 μm
PC film: polycarbonate film, “Iupilon FS-2000” manufactured by Mitsubishi Gas Chemical Co., Inc., thickness 400 μm.

[Thickness of antiglare layer and internal haze layer]
Using an optical film thickness meter, 10 arbitrary positions were measured, and an average value was calculated.

[Haze]
Based on JIS K7163, using a haze meter (trade name “NDH-5000W” manufactured by Nippon Denshoku Co., Ltd.), the surface of the antiglare layer was placed on the light receiver side and measured.

[Total light transmittance]
Based on JIS K7361, it measured using the haze meter (Nippon Denshoku Co., Ltd. make, brand name "NDH-5000W").

[60 ° gloss]
Measurement was performed at an angle of 60 ° using a gloss meter (“Polygloss KT-GL0030” manufactured by TQC Co.) according to JIS Z8741.

[Arithmetic average roughness Ra, average length RSm of roughness curve elements, maximum cross section height Rt of roughness curve]
In accordance with JIS B0601, using a non-contact surface / layer cross-sectional shape measurement system [“VertScan 2.0” manufactured by Ryoka System Co., Ltd.], the curve obtained by measuring the uneven shape of the anti-glare layer surface Based on this, the arithmetic average roughness Ra, the average length RSm of the roughness curve elements, and the maximum section height Rt of the roughness curve were determined.

[Steel wool (SW) resistance]
Using a steel wool durability tester equipped with a 1 cm diameter stick covered with steel wool # 0000, the load was changed at room temperature (20-25 ° C.) at a speed of 50 mm / sec and a distance of 5 cm. After the surface of the glare layer was rubbed back and forth 10 times, it was visually checked to determine the maximum load without any scratches.

[Anti-glare]
Fluorescent lamps with no louvers were projected on the laminate, and the glare of the specularly reflected light was visually confirmed and evaluated according to the following criteria. ◎: Feel no glare ○: Feel the glare slightly × : I feel dazzling.

[Glittering]
The laminate was pasted on a smartphone with a resolution of 441 ppi, and the standard deviation σ of the brightness of the display was measured using a glare measuring device (manufactured by Komatsu NTC Co., Ltd.) as an index of glare. The glare measurement device uses a camera with a resolution of 48 to 1.3 million pixels, displays the smartphone display in green, adjusts the camera focus, adjusts the brightness to 170, and then pastes the laminate to the display to obtain the standard deviation in brightness. It was measured.

[Dynamic friction coefficient]
Using a dynamic friction coefficient measuring device ("Handy Tribomaster TL201Ts" manufactured by Trinity Labs Co., Ltd.), the frictional force at a load of 0.2 N, a speed of 50 mm / second, and an effective measurement distance of 50 mm was measured. Artificial skin (“Bio Skin” manufactured by Beaulux Co., Ltd.) was attached to the surface contact, and the surface of the antiglare layer was slid to determine the dynamic friction coefficient.

(Preparation of coating solution for antiglare layer)
Preparation of Coating Solution 1 58 parts by mass of an acrylic resin having a polymerizable group, 7 parts by mass of cellulose acetate propionate, 106 parts by mass of urethane acrylate A, 1 part by mass of a fluorine group-containing UV-reactive surface modifier, 3 parts by mass of photoinitiator A Part was dissolved in a mixed solvent of 250 parts by mass of methyl ethyl ketone (MEK) and 39 parts by mass of 1-butanol to prepare a coating solution 1.

Preparation of Coating Liquid 2 A coating liquid 2 was prepared in the same manner as the coating liquid 1 except that urethane acrylate B was used instead of urethane acrylate A.

Preparation of coating solution 3 A coating solution 3 was prepared in the same manner as the coating solution 2 except that the mixed solvent was changed to a mixed solvent of 186 parts by mass of MEK, 80 parts by mass of butyl acetate and 39 parts by mass of 1-butanol.

Preparation of coating liquid 4 The ratio of the acrylic resin having a polymerizable group is changed to 7 parts by mass, the ratio of cellulose acetate propionate is changed to 6 parts by mass, and the ratio of urethane acrylate A is changed to 108 parts by mass. Prepared a coating solution 4 in the same manner as the coating solution 1.

Preparation of Coating Liquid 5 67 parts by mass of an acrylic resin having a polymerizable group, 5 parts by mass of cellulose acetate propionate, 119 parts by mass of urethane acrylate A, an appropriate amount of a fluorine group-containing UV-reactive surface modifying agent, and 3 parts by mass of a photoinitiator A The coating liquid 5 was prepared by dissolving in a mixed solvent of 166 parts by mass of MEK, 39 parts by mass of 1-butanol and 107 parts by mass of butyl acetate.

Preparation of Coating Solution 6 Coating solution 6 was prepared by mixing coating solution 1 and silica-containing acrylic coating solution so that the former / the latter = 40/60 in terms of the solid mass ratio.

(Preparation of coating solution for internal haze layer)
Preparation of Coating Liquid 7 100 parts by mass of urethane acrylate C, 83.5 parts by mass of amorphous polyester, an appropriate amount of reactive surface modifier, and 1.3 parts by mass of photoinitiator B are dissolved in 130 parts by mass of MEK, and coating liquid 7 ( A phase separation system) was prepared.

Preparation of Coating Liquid 8 100 parts by mass of urethane acrylate D, 20 parts by mass of silica spherical fine particles, and 2 parts by mass of photoinitiator B were mixed with 133 parts by mass of MEK to prepare a coating liquid 8 (particle system).

(Production of laminate)
Comparative Examples 1-5
Using a wire bar, each coating solution is coated on a PET film as a base material layer, dried in an oven at 80 ° C. for 1 minute, and the coating layer is formed so as to have each coating thickness shown in Table 1. Formed. Subsequently, the coating layer was irradiated with ultraviolet rays from a high-pressure mercury lamp (made by Eye Graphics Co., Ltd.) for about 10 seconds to cure the coating layer (ultraviolet ray irradiation amount: 400 mJ / cm ² ) to form an antiglare layer. A layered laminate was obtained.

Comparative Example 6
A laminate was obtained in the same manner as in Comparative Examples 1 to 5 except that a PC film was used instead of the PET film and the coating liquid 6 was coated.

Examples 1, 4 and 6
The surface of the laminate obtained in Comparative Examples 1, 4 and 6 is coated on the surface opposite to the antiglare layer using a wire bar, and the coating liquid 7 is coated in an oven at 80 ° C. for 1 minute. It dried and formed the coating film with a thickness of 12 micrometers. Subsequently, the coating film was cured by irradiating ultraviolet rays from a high pressure mercury lamp (manufactured by Eye Graphics Co., Ltd.) for about 10 seconds (ultraviolet ray irradiation amount: 400 mJ / cm ² ) to form a phase separation internal haze layer.

Examples 2, 3 and 5
The surface of the laminate obtained in Comparative Examples 2, 3 and 5 is coated with the coating liquid 8 using a wire bar on the side opposite to the antiglare layer, and is placed in an oven at 80 ° C. for 1 minute. It dried and formed the coating film of thickness 11 micrometers. Subsequently, the coating film was cured by irradiating ultraviolet rays from a high-pressure mercury lamp (manufactured by Eye Graphics Co., Ltd.) for about 10 seconds (ultraviolet ray irradiation amount: 400 mJ / cm ² ) to produce a particle-based internal haze layer.

  Table 1 shows the evaluation results of the laminates obtained in the comparative examples and the examples.

  As is clear from the results in Table 1, the laminates of the examples can achieve both antiglare properties and glare properties, have a low dynamic friction coefficient, good slipperiness with fingers, and excellent scratch resistance. ing. On the other hand, the laminated body of a comparative example cannot improve glare property.

  The laminate of the present invention is a display device such as various display devices such as LCD, cathode ray tube display device, organic or inorganic EL display, field emission display (FED), surface electric field display (SED), rear projection television display, etc. It can be used as an anti-glare film for use in automobiles. In particular, it has excellent slipperiness and scratch resistance with fingers, so that it can be used for car navigation displays, game machines, smartphones, personal computers (PCs) (tablet PCs, notebooks or laptops). It is suitable for a display device with a touch panel such as a top type PC, a desktop type PC, or the like.

Claims (12)

  The laminate includes an internal haze layer, a base material layer, and an antiglare layer, and has the antiglare layer on the surface, and the surface of the antiglare layer has an arithmetic average roughness Ra of 0.05 to 0.3 μm, The laminated body which has uneven | corrugated shape of average length RSm5-35micrometer of roughness curve element, and maximum cross-section height Rt0.1-2micrometer of a roughness curve.   The laminate according to claim 1, wherein the haze is 10 to 80%.   The dynamic friction coefficient of the antiglare layer surface is 0.1 to 3 measured using a surface contact with an artificial skin attached under the conditions of a load of 0.2 N, a moving speed of 50 mm / second, and an effective measurement distance of 50 mm. The laminate according to 1 or 2.   The laminate according to any one of claims 1 to 3, wherein the antiglare layer is a cured product of a curable composition containing at least one polymer component and at least one cured resin precursor component.   The laminate according to claim 4, wherein the polymer component includes cellulose esters and / or a (meth) acrylic polymer that may have a polymerizable group, and the cured resin precursor component includes urethane (meth) acrylate. body.   The laminate according to claim 5, wherein the cured resin precursor component further comprises a fluorine-based compound having a polymerizable group.   The laminated body in any one of Claims 4-6 in which a curable composition further contains a filler.   The laminate according to any one of claims 1 to 7, wherein the 60 ° gloss on the surface of the antiglare layer is 0.1 to 70%.   The laminate according to any one of claims 1 to 8, wherein the internal haze layer has a haze of 1 to 60%.   The manufacturing method of the laminated body in any one of Claims 1-9 including the glare-proof layer formation process which is phase-separated by wet spinodal decomposition | disassembly and forms uneven | corrugated shape.   The display apparatus provided with the laminated body in any one of Claims 1-9.   The display device according to claim 11, which is a liquid crystal display device with a touch panel or an organic EL display.