WO2014178365A1 - Functional glass - Google Patents

Abstract

The present invention relates to a functional glass, in which a resin film on which a functional layer has been layered and a thin film glass are laminated via an adhesive layer, is characterized in that the adhesive layer comprises a condensate of a reactive metal compound and a hydroxyl group-containing polymer compound.

Description

Functional glass

The present invention relates to a glass with a function provided with a function.

In recent years, the size of display devices has been increasing, and mobile devices have also been increasing. Thin and lightweight display devices are required. A glass substrate is generally used for the display device, and the display device can be made thin and light by thinning the glass substrate. However, when the glass substrate is thinned, the glass substrate is easily broken and the handling property is deteriorated.

Therefore, in Patent Document 1, in order to provide a glass with anti-scattering performance that is excellent in anti-scattering effect and further excellent in transparency, high surface hardness, weather resistance, chemical resistance, durability, and heat resistance, photocuring is performed. Has proposed a glass with anti-scattering performance characterized by curing a photocurable resin composition containing a cage-shaped silsesquioxane resin having a property and laminating it with a resin film.

In Patent Document 2, a thin film tempered glass excellent in impact resistance and penetration resistance can be obtained. A glass plate and an organic polymer film are made of an ethylene vinyl acetate copolymer, a polyvinyl acetal resin, and A film tempered glass laminated through a transparent adhesive layer made of at least one selected from vinyl chloride resins has been reported.

On the other hand, Patent Document 3 discloses a hard-hardened hardened adhesive sheet in which a hard coat adhesive film having a specific range of Martens hardness is combined with a protective film and a release film so as to have a specific total thickness. It describes that the crack of the hard coat layer at the time of punching can be made difficult to occur while having the coat layer.

As described above, several techniques for reinforcing a glass by providing a scattering prevention sheet and a hard coat layer in a base glass used in a display device have already been studied.

However, in recent years, demands for thinning, hardness, and smoothness of such base glass have further increased. In particular, touch panels that can be input by touching the display screen with a finger or pressing with a pen are widespread, but such touch panels particularly require toughness (flexibility), and conventional base glass is not sufficient. There was also a side.

Moreover, as a method of pasting a conventional thin film glass and a functional layer, for example, in the above patent document, a method (Patent Documents 1 and 2) performed by applying or pasting an organic resin or a double-sided adhesive seal, or photocuring Describes a technique (Patent Document 3) using an adhesive resin as an adhesive layer.

However, an adhesive layer using an organic resin or a photocurable resin that has been conventionally used has a problem that the elastic modulus of the adhesive layer is low and the surface hardness is lowered. In addition, there is a problem that the adhesion strength of the adhesive layer is reduced in a high temperature and high humidity environment.

JP 2010-125719 A JP 2002-79610 A JP 2010-275385 A

The present invention has been made in view of such circumstances, and even when the functional layer is in direct contact with the adhesive and laminated on the thin film glass, the adhesion strength is reduced due to environmental fluctuations during the wet heat durability test. It aims at providing the glass with a function which can suppress, and can improve film thickness, surface hardness, toughness, and handleability.

As a result of intensive studies, the present inventor has found that the above problem can be solved by a glass with a function having the following configuration, and has further completed the present invention based on such knowledge.

That is, in the glass with function according to one aspect of the present invention, a resin film in which a functional layer is laminated and a thin film glass are laminated through an adhesive layer, and the adhesive layer has a reactive metal compound and a high hydroxyl group content. It contains a condensate with a molecular compound.

It is sectional drawing which shows one structural example of the glass with a function which concerns on the embodiment of this invention. It is sectional drawing which shows one structural example in the case of using the glass with a function which concerns on the embodiment of this invention for a touchscreen. It is sectional drawing which shows another structural example in the case of using the glass with a function which concerns on the embodiment of this invention for a touchscreen.

Hereinafter, embodiments according to the present invention will be described in detail, but the present invention is not limited thereto.

[About glass with functions]
FIG. 1 is a cross-sectional view showing a configuration example of the glass with function 1 according to the present embodiment. The glass with function 1 of this embodiment is configured by laminating an adhesive layer 3, a resin film 4, and a functional layer 5 in this order on a thin film glass 2.

The functional layer 5 is preferably a hard coat layer, an antireflection layer or an antiglare layer, for example. The functional layer 5 can be laminated on the resin film 4 by a known method such as a gravure coater.

The adhesive layer 3 is an organic-inorganic hybrid adhesive layer (HB glue) containing a condensate of a reactive metal compound (inorganic compound) and a hydroxyl group-containing polymer compound (organic compound). The metal component contained in the reactive metal compound tends to be strongly bonded to the material component of the glass by a chemical bond such as a covalent bond. Moreover, since the hydroxyl group-containing polymer compound contains a hydroxyl group, the affinity with the resin film 4 can be improved and the adhesiveness can be improved. Further, the organic compound and the inorganic compound are poorly compatible, but by forming these condensates, the adhesive layer 3 having both characteristics in a single layer structure can be formed. Furthermore, since the hydroxyl group-containing polymer compound is a silanol group-containing low molecular component before sol-gel curing, it can penetrate into and penetrate into the molecule of the resin film on which the functional layer is laminated, so that the adhesive layer penetrates the film. Therefore, it does not have a thickness and can be made thinner than before.

Then, by using the organic-inorganic hybrid adhesive layer 3 described above, the adhesion between the thin film glass 2 and the resin film 4 on which the functional layer 5 is laminated can be improved through the adhesive layer 3. As a result, the interlayer adhesion strength is less likely to deteriorate due to environmental fluctuations during the durability test. Moreover, the hardness and toughness of glass with a function can be improved simultaneously by improving the adhesion between the thin film glass 2 and the resin film 4 on which the functional layer 5 is laminated.

The thickness of the resin film 4 is preferably 40 μm or less. In this case, since the resin film 4 on which the functional layer 5 is laminated becomes thin, the glass with function 1 can be made thinner.

The hydroxyl group-containing polymer compound is preferably a cellulose ester having a total acyl group substitution degree of 1.0 to 2.6. As such a cellulose ester, for example, triacetyl cellulose (TAC), diacetyl cellulose (DAC), cellulose acetate propionate (CAP), or the like can be used. Such a cellulose ester is very effective as a material for improving interlayer adhesion in the glass with function 1 because it contains a hydroxyl group and improves the affinity with the resin film 4 on which the functional layer 5 is laminated.

[About each layer of glass with function]
(Thin glass)
As thin film glass which comprises glass with a function, what was shape | molded by various shaping | molding methods can be used. For example, a thin film glass formed by a rollout method, a redraw method, a downdraw method, a float method, or the like can be used.

The shape of the thin film glass is not particularly limited and may be a chip cut shape, but is preferably a roll shape from the viewpoint of suitability for production on a roll-to-roll basis.

The average thickness of the thin film glass is preferably 5 to 200 μm, and more preferably 5 to 100 μm. When the thickness is less than 5 μm, handling such as conveyance is difficult, and when the thickness exceeds 200 μm, the value of the thin film is diminished.

The thin film glass is not particularly limited as long as it is a multi-component oxide glass. For example, alkali-free glass, borosilicate glass, aluminosilicate glass and the like are particularly suitable as the thin film glass, and among them, alkali-free glass is most preferred.

(Functional layer)
As described above, in the present embodiment, the functional layer is preferably a hard coat layer, an antireflection layer, or an antiglare layer, but is not limited thereto.

[Hard coat layer]
Although it does not specifically limit as a hard-coat layer, For example, a curable acrylic resin etc. can be used. In particular, a layer containing an ultraviolet curable compound (resin) that is cured by ultraviolet rays is preferable, and a glass excellent in scratch resistance can be obtained.

The ultraviolet curable resin layer of the hard coat layer is preferably a resin layer formed by polymerizing a component containing an ethylenically unsaturated monomer. Here, the ultraviolet curable resin layer refers to a layer mainly composed of a resin which is cured through a crosslinking reaction or the like by irradiation with an active ray such as an electron beam in addition to ultraviolet rays. Typical examples of the ultraviolet curable resin include an ultraviolet curable resin and an electron beam curable resin. However, a resin that is cured by irradiation with active rays other than ultraviolet rays and electron beams may be used. Examples of the ultraviolet curable resin include an ultraviolet curable acrylic urethane resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, and an ultraviolet curable epoxy resin. be able to.

In general, UV-curable acrylic urethane resins are obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer and further adding 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate (hereinafter referred to as acrylate, methacrylate). And can be easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate (see, for example, JP-A-59-151110).

UV curable polyester acrylate resins can be easily obtained by reacting polyester polyol with 2-hydroxyethyl acrylate and 2-hydroxy acrylate monomers (see, for example, JP-A-59-151112). .

Specific examples of ultraviolet curable epoxy acrylate resins include those obtained by reacting epoxy acrylate with an oligomer, a reactive diluent and a photoreaction initiator added thereto (for example, JP-A-1- No. 105738). As the photoinitiator, one or more kinds selected from benzoin derivatives, oxime ketone derivatives, benzophenone derivatives, thioxanthone derivatives and the like can be selected and used.

Specific examples of ultraviolet curable polyol acrylate resins include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate (PETA), pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate (DPHA), alkyl Examples thereof include modified dipentaerythritol pentaacrylate.

Particularly preferred resins are dipentaerythritol hexaacrylate (DPHA), pentaerythritol triacrylate (PETA), pentaerythritol tetraacrylate (PETTA) and the like.

These resins are usually used together with known photosensitizers. Moreover, the said photoinitiator can also be used as a photosensitizer. Specific examples include acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and the like. Further, when using an epoxy acrylate photoreactive agent, a sensitizer such as n-butylamine, triethylamine, tri-n-butylphosphine can be used. The photoreaction initiator or photosensitizer contained in the ultraviolet curable resin composition excluding the solvent component that volatilizes after coating and drying can be added in an amount of usually 1 to 10% by mass of the composition, and 2.5 to 6 It is preferable that it is mass%.

Examples of the resin monomer may include general monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, vinyl acetate, benzyl acrylate, cyclohexyl acrylate, and styrene as monomers having one unsaturated double bond. Monomers having two or more unsaturated double bonds include ethylene glycol diacrylate, propylene glycol diacrylate, divinylbenzene, 1,4-cyclohexane diacrylate, 1,4-cyclohexyldimethyl adiacrylate, and the above-mentioned trimethylolpropane. Examples thereof include triacrylate and pentaerythritol tetraacryl ester.

For example, as an ultraviolet curable resin, Adekaoptomer KR / BY series: KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B (above, manufactured by Asahi Denka Kogyo Co., Ltd.) Or KOHEI Hard A-101-KK, A-101-WS, C-302, C-401-N, C-501, M-101, M-102, T-102, D-102, NS-101, FT -102Q8, MAG-1-P20, AG-106, M-101-C (from Guangei Chemical Industry Co., Ltd.), or Seika Beam PHC2210 (S), PHCX-9 (K-3), PHC2213, DP-10 , DP-20, DP-30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, SCR900 (above, large Manufactured by Seika Kogyo Co., Ltd.), or KRM7033, KRM7039, KRM7130, KRM7131, UVECRYL29201, UVECRYL29202 (above, Daicel UCB Corporation), or RC-5015, RC-5016, RC-5020, RC-5031, RC- 5100, RC-5102, RC-5120, RC-5122, RC-5152, RC-5171, RC-5180, RC-5181 (manufactured by Dainippon Ink & Chemicals, Inc.) or Aulex No. 340 clear (manufactured by China Paint Co., Ltd.), Sunrad H-601 (manufactured by Sanyo Chemical Industries, Ltd.), SP-1509, SP-1507 (manufactured by Showa Polymer Co., Ltd.), or RCC-15C (Grace Japan Ltd.) (Manufactured by the company), Aronix M-6100, M-8030, M-8060 (above, manufactured by Toagosei Co., Ltd.) or other commercially available products.

The UV curable resin layer can be applied by a known method. As the solvent for coating the ultraviolet curable resin layer, for example, it can be appropriately selected from hydrocarbons, alcohols, ketones, esters, glycol ethers, and other solvents, or a mixture thereof can be used. . Preferably, propylene glycol mono (alkyl group having 1 to 4 carbon atoms) alkyl ether, preferably propylene glycol mono (alkyl group having 1 to 4 carbon atoms) alkyl ether ester is 5% by mass or more, more preferably 5 to 80% by mass. The solvent contained above is used.

As a light source for forming a cured film layer by photocuring reaction of an ultraviolet curable resin, any light source that generates ultraviolet rays can be used. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. The irradiation conditions vary depending on individual lamps, but the amount of light irradiated may if 20 ~ 10000mJ / cm ² degrees, preferably 50 ~ 2000mJ / cm ^2. In the near ultraviolet region to the visible light region, it can be used by using a sensitizer having an absorption maximum in that region.

The UV curable resin composition is coated and dried and then irradiated with UV light from a light source. The irradiation time is preferably 0.5 seconds to 5 minutes, and 3 seconds to 2 from the curing efficiency and work efficiency of the UV curable resin. Minutes are more preferred.

It is preferable to add inorganic or organic fine particles to the cured film layer thus obtained in order to prevent blocking and to improve scratch resistance. Examples of the inorganic fine particles include silicon oxide, titanium oxide, aluminum oxide, tin oxide, zinc oxide, calcium carbonate, barium sulfate, talc, kaolin, calcium sulfate, and the like, and examples of the organic fine particles include polymethacrylic acid. Methyl acrylate resin powder, acrylic styrene resin powder, polymethyl methacrylate resin powder, silicon resin powder, polystyrene resin powder, polycarbonate resin powder, benzoguanamine resin powder, melamine resin powder, polyolefin resin powder, polyester resin powder Polyamide-based resin powder, polyimide-based resin powder, or polyfluorinated ethylene-based resin powder, and the like can be added to the ultraviolet curable resin composition. The average particle size of these fine particle powders is preferably 0.005 to 5 μm, more preferably 0.1 to 5.0 μm, and further preferably 0.1 to 4.0 μm added to the coating composition for forming the hard coat layer. It is particularly preferable from the viewpoint of the stability of the composition.

Desirably, the proportion of the ultraviolet curable resin composition and the fine particle powder is 0.1 to 30 parts by mass with respect to 100 parts by mass of the resin composition.

The layer formed by curing the ultraviolet curable resin formed in this way is a hard coat layer having a center line average roughness Ra of 1 to 50 nm as defined in JISB 0601. An antiglare layer of about 1 μm may be used.

(Antireflection layer)
The antireflection layer is preferably laminated in consideration of the refractive index, the film thickness, the number of layers, the layer order, and the like so that the reflectance is reduced by optical interference. The antireflection layer is composed of a low refractive index layer having a refractive index lower than that of the protective film as a support, or a combination of a high refractive index layer and a low refractive index layer having a higher refractive index than the protective film as a support. Preferably it is. Particularly preferably, it is an antireflection layer composed of three or more refractive index layers, and three layers having different refractive indexes from the support side are divided into medium refractive index layers (high refractive index layers having a higher refractive index than the support). Are preferably laminated in the order of a layer having a lower refractive index) / a high refractive index layer / a low refractive index layer. Alternatively, an antireflection layer having a layer structure of four or more layers in which two or more high refractive index layers and two or more low refractive index layers are alternately laminated is also preferably used.

As the layer structure of the resin film laminated with the antireflection layer, the following structure can be considered, but it is not limited to this.

Resin film / Anti-glare layer / Low refractive index layer Resin film / Anti-glare layer / Medium refractive index layer / Low refractive index layer Resin film / Anti-glare layer / Medium refractive index layer / High refractive index layer / Low refractive index layer Resin film / Anti-glare layer / High refractive index layer (conductive layer) / Low refractive index layer Resin film / Intermediate layer / Anti-glare layer / Low refractive index layer

Low Refractive Index Layer The low refractive index layer preferably contains silica-based fine particles, and the refractive index is preferably in the range of 1.30 to 1.45 when measured at 23 ° C. and wavelength of 550 nm. The film thickness of the low refractive index layer is preferably 5 nm to 0.5 μm, more preferably 10 nm to 0.3 μm, and most preferably 30 nm to 0.2 μm.

The composition for forming a low refractive index layer preferably contains at least one kind of particles having an outer shell layer and porous or hollow inside as silica-based fine particles. In particular, the particles having the outer shell layer and having a porous or hollow interior are preferably hollow silica-based fine particles.

Note that the composition for forming a low refractive index layer may contain an organosilicon compound represented by the following general formula (OSi-1), a hydrolyzate thereof, or a polycondensate thereof.

General formula (OSi-1): Si (OR) ₄

In the organic silicon compound represented by the general formula, R represents an alkyl group having 1 to 4 carbon atoms. Specifically, tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), tetraisopropoxysilane and the like are preferably used.

In addition, a solvent, and if necessary, a silane coupling agent, a curing agent, a surfactant and the like may be added. Further, it may contain a thermosetting and / or photocurable compound mainly containing a fluorine-containing compound containing a fluorine atom in a range of 35 to 80% by mass and containing a crosslinkable or polymerizable functional group. Specifically, a fluorine-containing polymer or a fluorine-containing sol-gel compound is used. Examples of the fluorine-containing polymer include hydrolysates and dehydration condensates of perfluoroalkyl group-containing silane compounds [eg (heptadecafluoro-1,1,2,2-tetrahydrodecyl) triethoxysilane], and fluorine-containing monomers. Examples thereof include fluorine-containing copolymers having units and cross-linking reactive units as constituent units. In addition, you may add a solvent, a silane coupling agent, a hardening | curing agent, surfactant, etc. as needed.

High refractive index layer The refractive index of the high refractive index layer is preferably adjusted to a refractive index in the range of 1.4 to 2.2 by measuring at 23 ° C. and a wavelength of 550 nm. The thickness of the high refractive index layer is preferably 5 nm to 1 μm, more preferably 10 nm to 0.2 μm, and most preferably 30 nm to 0.1 μm. The means for adjusting the refractive index can be achieved by adding metal oxide fine particles and the like. Metal oxide The metal oxide fine particles used preferably have a refractive index of 1.80 to 2.60, more preferably 1.85 to 2.50.

The kind of metal oxide fine particles is not particularly limited, and Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P and S A metal oxide having at least one element selected from the group consisting of Al, In, Sn, Sb, Nb, a halogen element, Ta and the like is doped with a minute amount of atoms. May be. A mixture of these may also be used. In this embodiment, at least one metal oxide fine particle selected from among zirconium oxide, antimony oxide, tin oxide, zinc oxide, indium-tin oxide (ITO), antimony-doped tin oxide (ATO), and zinc antimonate. It is particularly preferable to use as the main component. In particular, it is preferable to contain zinc antimonate particles.

The average particle diameter of the primary particles of these metal oxide fine particles is in the range of 10 nm to 200 nm, and is particularly preferably 10 to 150 nm. The average particle diameter of the metal oxide fine particles can be measured from an electron micrograph taken with a scanning electron microscope (SEM) or the like. You may measure by the particle size distribution meter etc. which utilize a dynamic light scattering method, a static light scattering method, etc. If the particle size is too small, aggregation tends to occur and the dispersibility deteriorates. If the particle size is too large, the haze is remarkably increased. The shape of the metal oxide fine particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape, a needle shape, or an indefinite shape.

The metal oxide fine particles may be surface-treated with an organic compound. By modifying the surface of the metal oxide fine particles with an organic compound, the dispersion stability in an organic solvent is improved, the dispersion particle size can be easily controlled, and aggregation and sedimentation over time can be suppressed. . Therefore, the amount of surface modification with a preferable organic compound is 0.1% by mass to 5% by mass, more preferably 0.5% by mass to 3% by mass with respect to the metal oxide particles. Examples of the organic compound used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Of these, silane coupling agents are preferred. Two or more kinds of surface treatments may be combined. The high refractive index layer may contain a π-conjugated conductive polymer. The π-conjugated conductive polymer can be used as long as it is an organic polymer having a main chain composed of a π-conjugated system. Examples thereof include polythiophenes, polypyrroles, polyanilines, polyphenylenes, polyacetylenes, polyphenylene vinylenes, polyacenes, polythiophene vinylenes, and copolymers thereof. From the viewpoint of ease of polymerization and stability, polythiophenes, polyanilines, and polyacetylenes are preferable.

The π-conjugated conductive polymer can provide sufficient conductivity and solubility in a binder resin even if it is not substituted, but in order to further improve conductivity and solubility, an alkyl group, a carboxy group, a sulfo group, an alkoxy group. A functional group such as a group, a hydroxy group, or a cyano group may be introduced.

Moreover, you may contain an ionic compound. Examples of the ionic compound include imidazolium-based, pyridium-based, alicyclic amine-based, aliphatic amine-based, aliphatic phosphonium-based cations and inorganic ion-based compounds such as BF ₄ -and PF _6- , CF ₃ SO _2-, and the like. , (CF ₃ SO ₂ ) ₂ N—, CF ₃ CO ₂ —, etc. The ratio of the polymer to the binder is preferably 10 to 400 parts by mass with respect to 100 parts by mass of the polymer, and particularly preferably 100 to 200 parts by mass of the binder with respect to 100 parts by mass of the polymer.

[Anti-glare layer]
In the present embodiment, the antiglare layer is preferably basically composed of a binder layer mainly composed of a transparent resin and fine particles in order to control the ratio of the scattering reflectance within the above range. As the fine particles, fluorine-containing acrylic resin particles are preferable because the ratio of the scattering reflectance is easily controlled within the above range. Next, the fluorine-containing acrylic resin particles will be described.

Fluorine-containing acrylic resin particles are, for example, particles formed from a fluorine-containing acrylic ester or methacrylic ester polymer.

Specific examples of fluorine-containing acrylic acid ester or methacrylic acid ester include 1H, 1H, 3H-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 7H- Dodecafluoroheptyl (meth) acrylate, 1H, 1H, 9H-hexadecafluorononyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (Meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, 2-perfluorodecylethyl (Meth) acrylate, 3-par Fluorobutyl-2-hydroxypropyl (meth) acrylate, 3-perfluorohexyl-2-hydroxypropyl (meth) acrylate, 3-perfluorooctyl-2-hydroxypropyl (meth) acrylate, 2- (perfluoro-3-methylbutyl) ) Ethyl (meth) acrylate, 2- (perfluoro-5-methylhexyl) ethyl (meth) acrylate, 2- (perfluoro-7-methyloctyl) ethyl (meth) acrylate, 3- (perfluoro-3-methylbutyl) ) -2-hydroxypropyl (meth) acrylate, 3- (perfluoro-5-methylhexyl) -2-hydroxypropyl (meth) acrylate, 3- (perfluoro-7-methyloctyl) -2-hydroxypropyl (meth) ) Acrylate, 1H-1 (Trifluoromethyl) trifluoroethyl (meth) acrylate, 1H, 1H, 3H-hexafluorobutyl (meth) acrylate, trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, perfluorooctylethyl acrylate, 2- (perfluorobutyl) And ethyl-α-fluoroacrylate.

Further, among the fluorine-containing acrylic resin particles, particles made of 2- (perfluorobutyl) ethyl-α-fluoroacrylate, fluorine-containing polymethyl methacrylate particles, and fluorine-containing methacrylic acid in the presence of a crosslinking agent are vinyl monomers. Particles copolymerized with are preferred, more preferably fluorine-containing polymethyl methacrylate particles.

Commercially available products include Negami Kogyo Co., Ltd .: MF-0043, Nippon Paint: S-4000, FS-701, and the like. These fluorine-containing acrylic resin particles may be used alone or in combination of two or more. These fluorine-containing acrylic resin particles may be added in any state such as powder or emulsion. Further, fluorine-containing crosslinked particles described in paragraphs 0028 to 0055 of JP-A-2004-83707 may be used.

The refractive index of the fluorine-containing acrylic resin particles is preferably 1.38 to 1.44. The content of the fluorine-containing acrylic resin particles is preferably 0.01 to 500 parts by mass, more preferably 0.1 to 100 parts by mass, particularly preferably 100 parts by mass of the transparent resin constituting the antiglare layer. 1 to 60 parts by mass.

The average particle diameter of the fluorine-containing acrylic resin particles is 1.5 to 6 μm, and preferably 2.0 to 4.0 μm. Besides the fluorine-containing acrylic resin particles, silica fine particles are also preferably used. Examples of the silica fine particles include product names such as Nippon Aerosil Co., Ltd., Aerosil 200, 200V, 300, Degussa, Aerosil OX50, TT600, etc., Nippon Shokubai Co., Ltd., KEP-10, KEP-50, KEP-100 and the like. Colloidal silica may be used as the silica fine particles. Colloidal silica is obtained by dispersing silicon dioxide in water or an organic solvent in a colloidal form, and is not particularly limited, and is spherical, acicular or beaded. Such colloidal silica is commercially available and includes, for example, the Snowtex series of Nissan Chemical Industries, the Cataloid-S series of Catalytic Chemical Industries, and the Rebacil series of Bayer. Also, beaded colloidal silica in which primary particles of cation-modified with alumina sol or aluminum hydroxide are bonded in a bead shape by bonding the particles with divalent or higher metal ions. Examples of beaded colloidal silica include Snowtex-AK series, Snowtex-PS series, Snowtex-UP series, etc., manufactured by Nissan Chemical Industries, Ltd. Specifically, IPS-ST-L (isopropanol silica sol, particle size 40-50 nm) , Silica concentration 30%), MEK-ST-MS (methyl ethyl ketone silica sol, particle size 17-23 nm, silica concentration 35%), etc. MEK-ST (methyl ethyl ketone silica sol, particle size 10-15 nm, silica concentration 30%), MEK- ST-L (methyl ethyl ketone silica sol, particle diameter 40 to 50 nm, silica concentration 30%), MEK-ST-UP (methyl ethyl ketone silica sol, particle diameter 9 to 15 nm (chain structure), silica concentration 20%) and the like. The silica fine particles may be reactive silica fine particles surface-treated with an organic compound having a polymerizable unsaturated group. The polymerizable unsaturated group preferably has an ethylenically unsaturated group, and further has a group represented by the following general formula (a) and a compound having a silanol group in the molecule or a compound that generates a silanol group by hydrolysis. Is preferred.

Specifically, [—UC (═V) —NH—] includes [—O—C (═O) —NH—], [—O—C (═S) —NH—], [—S. —C (═O) —NH—], [—NH—C (═O) —NH—], [—NH—C (═S) —NH—], and [—S—C (═S) — NH-]. These groups can be used individually by 1 type or in combination of 2 or more types. Among them, from the viewpoint of thermal stability, [—O—C (═O) —NH—] group, [—O—C (═S) —NH—] group and [—S—C (═O) — It is preferable to use in combination with at least one of the NH— groups.

The amount of the organic compound bonded to the silica fine particles is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and particularly preferably 1% by mass or more, based on 100% by mass of the silica fine particles.

Other fine particles include UV-curable resin compositions such as polystyrene resin powder, polycarbonate resin powder, polyolefin resin powder, polyester resin powder, polyamide resin powder, polyimide resin powder, or polyfluorinated ethylene resin powder. Can be added. If necessary, it may further contain particles described in JP-A No. 2000-241807. The refractive index of the other particles is preferably 1.45 to 1.70, more preferably 1.45 to 1.65. Note that the refractive index of the particles is measured by measuring the turbidity by dispersing the same amount of particles in a solvent in which the refractive index is changed by changing the mixing ratio of two types of solvents having different refractive indexes. The refractive index of the solvent can be measured by measuring with an Abbe refractometer.

The amount of fine particles added is preferably 10 to 90% of the total mass of the antiglare layer, more preferably 20 to 80%, and particularly preferably 30 to 75%. In addition, particles having an average particle diameter of 0.01 to 1 μm have a content of 100% by mass of the transparent resin constituting the antiglare layer because of the stability of the coating liquid forming the antiglare layer and the dispersibility of the dispersion. The amount is preferably 0.01 to 500 parts by weight, more preferably 0.1 to 100 parts by weight with respect to parts. Further, when the antiglare layer contains a transparent resin described later and the fine particles, it is preferable that the content ratio is transparent resin: fine particles = 99: 1 to 70:30.

(Functional layer properties and manufacturing method)
The pencil hardness of the functional layer as described above is preferably about 2H to 6H. This is because it is an important characteristic for maintaining the quality of the visibility of the display, which is highly resistant to surface scratches.

As a method for applying a hard coat layer, an antiglare layer or an antireflection layer to a resin film as described later, a gravure coater, a spinner coater, a wire bar coater, a roll coater, a reverse coater, an extrusion coater, an air doctor coater, etc. are known. This method can be used. The liquid film thickness (also referred to as wet film thickness) during coating is about 1 to 100 μm, preferably 0.1 to 30 μm, more preferably 0.5 to 30 μm. The dry film thickness is an average film thickness of 0.1 to 30 μm, preferably 1 to 20 μm.

(Resin film)
In the present embodiment, the resin film is a base material for the functional layer, and at the same time, is used for the purpose of preventing scattering when the glass breaks under impact.

The resin contained in the resin film is not particularly limited as long as it is an optically transparent resin. For example, cellulose resin, acrylic resin, polycarbonate resin, cycloolefin resin, polyester resin, polylactic acid resin Polyvinyl alcohol resin can be used. Among these, it is preferable to use a cellulose-based resin from the viewpoint of high heat resistance, high transparency, low retardation, high surface quality, and the like.

The resin film preferably has a small in-plane direction retardation (retardation) Ro and thickness direction retardation (retardation) Rt.

Retardation Ro and Rt are expressed by the following equations.

Ro = (nx−ny) × d
Rt = {(nx + ny) / 2−nz} × d
In the formula, nx represents the refractive index in the slow axis direction in the plane of the resin film, ny represents the refractive index in the direction perpendicular to the slow axis in the plane of the resin film, and nz represents the thickness of the resin film. The refractive index of a direction is shown, d shows the thickness (nm) of a film. The measurement wavelength of the refractive index is 590 nm.

Further, the retardations Ro and Rt can also be obtained by the following method.

1) The obtained resin film is conditioned at 23 ° C. and 55% RH. The average refractive index of the resin film after humidity adjustment is measured with an Abbe refractometer.

2) Ro is measured with KOBRA 21ADH (manufactured by Oji Scientific Instruments) when light having a measurement wavelength of 590 nm is incident on the resin film after humidity adjustment from the normal direction of the resin film.

3) Retardation value R (θ) when light having a measurement wavelength of 590 nm is incident from the angle θ (incident angle (θ)) with respect to the normal direction of the resin film by KOBRA 21ADH (manufactured by Oji Scientific Instruments). ). θ can be preferably 30 ° to 50 °.

4) nx, ny, and nz are calculated from the measured Ro and R (θ) and the above-described average refractive index and film thickness by KOBRA 21ADH (manufactured by Oji Scientific Instruments), and the measurement wavelength is 590 nm. Rt at is calculated. The retardation can be measured after tempering for about 12 hours, for example, at 23 ° C. and 55% RH.

A resin film prepared in advance in a film shape may be prepared and adhered to glass via an adhesive layer, or after an adhesive layer is formed on glass, the resin is directly applied or cast. It may be formed.

<Cellulosic resin>
Cellulose resins suitable for the resin film of the present embodiment include cellulose ethers such as methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, cyanoethyl cellulose, triacetyl cellulose (TAC), diacetyl cellulose (DAC), and cellulose acetate. Examples include cellulose esters such as propionate (CAP), cellulose acetate butyrate (CAB), cellulose acetate phthalate, cellulose acetate trimellitate, and cellulose nitrate, preferably cellulose esters, particularly triacetyl cellulose (TAC). ), Diacetylcellulose (DAC), and cellulose acetate propionate (CAP). Alternatively, aromatic carboxylic acid esters described in paragraph numbers [0010] to [0027] of JP-A No. 2002-179701 are used, and in particular, celluloses of paragraph numbers [0028] to [0036] of JP-A No. 2002-17979. Acylate is preferably used.

The cellulose used as the raw material for the cellulose resin is not particularly limited, and examples thereof include cotton linter, wood pulp, and kenaf. Moreover, although the cellulose resin obtained from these can be used individually or in mixture of arbitrary ratios, it is preferable to use 50 mass% or more of cotton linters.

When the molecular weight of the cellulose ester is large, the elastic modulus is increased. However, when the molecular weight is excessively increased, the viscosity of the solution of the cellulose ester becomes too high, and the productivity is lowered. The molecular weight of the cellulose ester is preferably 70000-200000 in terms of number average molecular weight, more preferably 100000-200000. The cellulose ester used in the present embodiment preferably has a weight average molecular weight of Mw, a number average molecular weight of Mn, and a Mw / Mn ratio of 1.4 to 3.0, more preferably 1.4 to 2. 3.

Since the average molecular weight and molecular weight distribution of cellulose ester can be measured using high performance liquid chromatography, the number average molecular weight (Mn) and the weight average molecular weight (Mw) are calculated using this, and the ratio is calculated. be able to. Measurement conditions are as follows.

Solvent: Methylene chloride Column: Shodex K806, K805, K803G (Used by connecting three Showa Denko Co., Ltd.)
Column temperature: 25 ° C
Sample concentration: 0.1% by mass
Detector: RI Model 504 (manufactured by GL Sciences)
Pump: L6000 (manufactured by Hitachi, Ltd.)
Flow rate: 1.0ml / min
Calibration curve: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Co., Ltd.) Mw = 1,000,000-500 calibration curves with 13 samples were used. The 13 samples are preferably used at approximately equal intervals.

The total acyl group substitution degree of the cellulose ester is preferably 2.4 to 2.9, more preferably 2.6 to 2.9. The total degree of acyl group substitution can be measured according to ASTM-D817-96.

Further, a film containing an acrylic resin and a cellulose ester resin and having a mass ratio of the acrylic resin and the cellulose ester resin of acrylic resin: cellulose ester resin = 95: 5 to 50:50 may be used.

(Adhesive layer)
As the adhesive layer, a condensate of an inorganic reactive metal compound and an organic hydroxyl group-containing polymer compound is used. By the condensation reaction, the thin film glass and the functional layer-attached resin film can be bonded. The condensation reaction may be performed by a generally known method, may be hydrolytic condensation by addition of a catalyst, or may be dehydration condensation by heating. As described above, the adhesive layer of this embodiment does not have a thickness because it penetrates into the film, and can be made thinner than before.

<Hydrolysis catalyst>
The reactive polycondensable reactive metal compound that is an inorganic compound can use an acid such as hydrochloric acid, acetic acid, or citric acid as a hydrolysis catalyst, but a solid catalyst is preferably used. Further, water and another catalyst as required may be added to cause hydrolysis to accelerate the condensation reaction. The hydrolysis may be complete hydrolysis in which all hydrolyzable groups are hydrolyzed, but is particularly preferably partial hydrolysis in which only a part is hydrolyzed.

The water added for hydrolysis is preferably used in the range of 0.5 to 10 mol per 1 mol of the reactive metal compound, and hydrolyzed with the solid catalyst. If the amount of water used for the hydrolysis is small, the hydrolysis of the alkoxy group becomes insufficient, resulting in a problem that only a few hydroxyl groups are generated. Preferably, the amount of water used is 0.5-4 moles per mole of reactive metal compound.

It is also preferable to use ion exchange water as water. Ion-exchanged water is preferable for hydrolyzing the reactive metal compound, and ion-exchanged water having an electric conductivity of 10 ¹⁰ MΩ or more is preferably used. If the electrical conductivity is lower than this, the ions contained in the ion exchange resin and the hydrolyzed water will undergo ion exchange, the pH of the hydrolyzed water will fluctuate greatly, and the hydrolyzed polycondensate generated will be present with great stability. This is not preferable. The electric conductivity of ion exchange water is more preferably 10 ¹² MΩ or more, and further preferably 10 ¹⁵ MΩ or more.

In addition, when water is added to a hydrophobic hydrolytic polycondensable reactive metal compound, methanol, ethanol, acetonitrile, etc. are used so that the hydrolytic polycondensable reactive metal compound and water can be easily mixed. It is preferable that a hydrophilic organic solvent is also added. In addition, when a hydroxyl group-containing polymer compound (for example, a cellulose derivative) and a reactive metal compound capable of hydrolysis polycondensation are mixed, a good solvent for the cellulose derivative is preferably added so that the cellulose derivative does not precipitate. . In addition, a good solvent means the organic solvent which has favorable solubility with respect to a cellulose derivative.

The solid catalyst as the hydrolysis catalyst is not particularly limited, and those listed below can be used.

(1) Cation exchange resin:
Amberlite 15, Amberlite 200C, Amberlist 15 (above, Rohm &Haas); Dowex MWC-1-H, Dowex 88, Dowex HCR-W2 (above, Dow Chemical); Levacit SPC-108, Levacit SPC-118 (manufactured by Bayer); Diaion RCP-150H (Mitsubishi Kasei); Sumikaion KC-470, Duolite C26-C, Duolite C-433, Duolite-464 (The above is manufactured by Sumitomo Chemical Co., Ltd.); Nafion-H (manufactured by DuPont) and the like.

(2) Anion exchange resin:
Amberlite IRA-400, Amberlite IRA-45 (above, manufactured by Rohm and Haas), etc.

(3) Inorganic solid in which a group containing a protonic acid group is bonded to the surface:
Such as _{Zr (O 3 PCH 2 CH 2} SO 3 H) 2, Th (O 3 PCH 2 CH 2 COOH) 2.

(4) Polyorganosiloxane containing protonic acid groups:
Polyorganosiloxane having a sulfonic acid group.

(5) Heteropoly acid:
Cobalt tungstic acid, phosphomolybdic acid, etc.

(6) Isopolyacid:
Niobic acid, tantalum acid, molybdic acid, etc.

(7) Unitary metal oxide:
Alumina, chromia, zirconia, CaO, MgO, etc.

(8) Composite metal oxide:
Silica-alumina, silica-magnesia, silica-zirconia, zeolites, etc.

(9) Clay mineral:
Acid clay, activated clay, montmorillonite, kaolinite, etc.

(10) Metal sulfate:
LiSO ₄ , MgSO _{4 and the} like.

(11) Metal phosphate:
Zirconia phosphate, lanthanum phosphate, etc.

(12) Metal nitrate:
Such as _{LiNO 3, Mn (NO 3)} 2.

(13) Inorganic solid in which a group containing an amino group is bonded to the surface:
Solids obtained by reacting aminopropyltriethoxysilane on silica gel.

(14) Polyorganosiloxane containing amino groups:
Amino-modified silicone resin.

Among these, in the present embodiment, a cation exchange resin is particularly preferable. As a kind of cation exchange resin, first, a suspension polymer of polystyrene or divinylbenzene as a skeleton is preferable. The types of ion exchange resins are classified into a gel type and a macroporous type. However, the gel type resin does not have pores, and it is difficult for a substance involved in the reaction to enter the inside of the resin, so that the active sites are not effectively used. The macroporous resin has large pores, and a substance involved in the reaction can easily reach the active site, and the active site is effectively used. For this reason, it is preferable that the cation exchange resin used in this embodiment is a macroporous material whose pore volume is 0.1 ml / g or more as measured by a mercury injection method. In addition, the acidic group attached to the resin is a sulfone group, an acrylic group, or the like, preferably an H + type, and more preferably a sulfone group. Examples of ion exchange resins that satisfy these requirements include Amberlyst 15 (manufactured by Rohm and Hers), Diaion PK-208H, PK-216H, PK-228H (manufactured by Mitsubishi Kasei), Burolite CT-175, CT -171, CT-169 (manufactured by Burolite) and the like. Of these, Burolite CT-175 (manufactured by Burolite) is particularly preferable.

In this embodiment, after the addition of the ion exchange resin, stirring is performed to hydrolyze the reactive metal compound to obtain a hydrolyzate or a condensate thereof. In this case, the stirring time (reaction time) ) Is preferably 3 minutes or more, particularly preferably 5 minutes or more. Moreover, it is preferable that reaction temperature shall be 0 degreeC or more. However, if the reaction time is too long, the molecular weight of the condensate becomes so large that haze may be increased. The same applies to the case where the reaction temperature is high, and the reaction temperature is preferably 0 to 50 ° C.

The particle size of the cation exchange resin used in the present embodiment is not particularly limited, but the average particle size is preferably in the range of 10 to 2000 μm. When the average particle size is less than 10 μm, filterability and liquid breakage may be deteriorated during the resin separation after the treatment. When the average particle size exceeds 2000 μm, the surface area per mass decreases, and the hydrolysis efficiency There is a problem that is low. Although it is preferable that the particle diameters are uniform, a chipped or cracked particle may be partially mixed.

The ion exchange capacity of the ion exchange resin is preferably 0.1 milliequivalent / ml or more. If it is less than 0.1 milliequivalent / ml, the hydrolysis efficiency is lowered and productivity may be lowered.

In the present embodiment, the addition amount of the ion exchange resin as a solid catalyst is preferably 0.00001 to 30% by mass, more preferably 0.001 based on the reactive metal compound capable of hydrolysis polycondensation. ~ 20% by weight. If the amount of the ion exchange resin is too large, the condensation proceeds preferentially, and the molecular weight of the condensate becomes too large. Moreover, when there is too little quantity of an ion exchange resin, sufficient activity required for a hydrolysis cannot be obtained, and a hydrolyzate or its condensate cannot fully be obtained.

In the hydrolysis method using the solid catalyst in the present embodiment, water and alcohol are mixed in advance, a reactive metal compound is added and mixed therein, and then the solid catalyst is added and stirred to proceed the hydrolysis. It is preferable. In addition, it is also preferable that water and alcohol are mixed in advance and the solid catalyst is added thereto, and then the reactive metal compound is further added with stirring to proceed the hydrolysis.

<Reactive metal compound>
In the present embodiment, the term “metal” refers to “Chemistry of the Periodic Table” by Iwanami Shoten, Kazuo Saito, p. 71. A metal according to 71, that is, a metal containing a semimetallic atom.

Examples of reactive metal compounds capable of hydrolytic polycondensation used in this embodiment include metal alkoxides, metal diketonates, metal alkyl acetoacetates, metal isocyanates, and reactive metal halides. Preferably, the metal species is an alkoxide of Si, Ti, Zr or Al, and particularly preferably an alkoxide of Si.

Such a reactive metal compound capable of hydrolytic polycondensation has M as the central metal, q as the number of atoms, A as the non-hydrolyzed substituent, p as the number of substituents, B as the hydrolyzable substituent, When r is the number of substituents, the reaction is ideally completed as shown in the following formula (1), and a metal oxide is obtained.

Equation _{(1) A p M q B} r → A p M q O r / 2

The hydrolyzable polycondensable reactive metal compound, in A _p M _q B _r shown in equation (1), such that p = 0, all being substituted with hydrolyzable substituents However, from the viewpoint of reducing the moisture permeability of the base film, a compound substituted with one, two, or three per atom of the metal by a non-hydrolyzed substituent may be included. . The amount of the metal compound having a substituent that is not hydrolyzed is preferably 50 mol% or less of the metal compound to be added. Moreover, you may use together 2 or more types of different types of metal alkoxide in the range of the said addition amount.

As such a non-hydrolyzed substituent, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group is preferable. As the substituent of the alkyl group or aryl group, an alkyl group (for example, methyl group, ethyl group) Group), cycloalkyl group (eg cyclopentyl group, cyclohexyl group etc.), aralkyl group (eg benzyl group, 2-phenethyl group etc.), aryl group (eg phenyl group, naphthyl group etc.), heterocyclic group (eg furan, Thiophene, pyridine etc.), alkoxy group (eg methoxy group, ethoxy group etc.), aryloxy group (eg phenoxy group etc.), acyl group, halogen atom, cyano group, amino group, alkylthio group, glycidyl group, vinyl group, fluorine Examples thereof include an atom-containing alkyl group and a fluorine atom-containing aryl group.

Examples of reactive metal compounds capable of polycondensation used in this embodiment include silicon compounds such as tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), tetraisopropoxysilane, tetra-n-butoxysilane, Examples thereof include tetra-t-butoxysilane, tetrakis (methoxyethoxy) silane, tetrakis (methoxypropoxy) silane, tetrachlorosilane, and tetraisocyanate silane.

Examples of silicon compounds having substituent groups that are not hydrolyzed include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiisopropoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldiisopropoxysilane, and diethyldiisosilane. Butoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldiisopropoxysilane, diphenyldibutoxysilane, 3-glycidoxypropylmethyldimethoxysilane, dichlorodimethylsilane, dichlorodiethylsilane, methyltrimethoxysilane, methyltriethoxysilane , Methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri Propoxysilane, ethyltributoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, phenyltributoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, ( 3-acryloxypropyl) trimethoxysilane, acetoxytriethoxysilane, (heptadecafluoro-1,1,2,2-tetrahydrodecyl) trimethoxysilane, (3,3, -Trifluoropropyl) trimethoxysilane, methyltrichlorosilane, ethyltrichlorosilane, phenyltrichlorosilane, (3,3,3-trifluoropropyl) triethoxysilane, pentafluorophenylpropyltrimethoxysilane, (heptadecafluoro-1, 1,2,2-tetrahydrodecyl) triethoxysilane, (3,3,3-trifluoropropyl) trichlorosilane, pentafluorophenylpropyltrichlorosilane, (heptadecafluoro-1,1,2,2-tetrahydrodecyl) tri Examples include chlorosilane, methyl triisocyanate silane, phenyl triisocyanate silane, and vinyl triisocyanate silane. In addition, quantified silicon compounds such as silicate 40, silicate 45, silicate 48, and M silicate 51 manufactured by Tama Chemical, which are partially condensed with these compounds, may be used.

Examples of titanium compounds include titanium methoxide, titanium ethoxide, titanium isopropoxide, titanium-n-butoxide, tetrachlorotitanium, titanium diisopropoxide (bis-2,4-pentanedionate), titanium diiso Propoxide (bis-2,4-ethylacetoacetate), titanium di-n-butoxide (bis-2,4-pentanedionate), titanium acetylacetonate, titanium lactate, titanium triethanolaminate, butyl titanate dimer, etc. Can be mentioned.

Zirconium compounds include zirconium-n-propoxide, zirconium-n-butoxide, zirconium tri-n-butoxide acetylacetonate, zirconium di-n-butoxide bisacetylacetonate, zirconium acetylacetonate, zirconium acetate, etc. Is mentioned.

Aluminum compounds include aluminum ethoxide, aluminum isopropoxide, aluminum-n-butoxide, aluminum-s-butoxide, aluminum-di-s-butoxide ethylacetylacetonate, aluminum-t-butoxide, almatrane, aluminum phenoxide. , Aluminum acetylacetonate, aluminum ethylacetylacetonate and the like.

Examples of the other metal compound include barium isopropoxide, calcium ethoxide, copper ethoxide, magnesium ethoxide, manganese methoxide, strontium isopropoxide, tin ethoxide, zinc methoxyethoxide, trimethoxyborane, Triethoxyborane, antimony ethoxide, arsenic triethoxide, bismuth t-pentoxide, chromium isopropoxide, erbium methoxyethoxide, gallium ethoxide, indium methoxyethoxide, iron ethoxide, lanthanum isopropoxide, neodymium methoxyethoxide, praseodymium methoxy Ethoxide, samarium isopropoxide, vanadium triisobutoxide oxide, yttrium isopropoxide, tetramethoxygermane, teto Ethoxygermane, tetraisopropoxygermane, tetra-n-butoxygermane, cerium-t-butoxide, hafnium ethoxide, hafnium-n-butoxide, tellurium ethoxide, molybdenum ethoxide, niobium ethoxide, niobium-n-butoxide, tantalum Examples include methoxide, tantalum ethoxide, tantalum-n-butoxide, tungsten (V) ethoxide, tungsten (VI) ethoxide, tungsten (VI) phenoxide, and the like.

The reactive metal compound capable of polycondensation used in this embodiment may be a compound called double metal alkoxide having two metal atoms in the molecular species. Examples of such double metal alkoxides include aluminum copper alkoxide, aluminum titanium alkoxide, aluminum yttrium alkoxide, aluminum zirconium alkoxide, barium titanium alkoxide, barium yttrium alkoxide, barium zirconium alkoxide, indium tin alkoxide, lithium nickel alkoxide manufactured by Gerest Co., Ltd. Lithium niobium alkoxide, lithium tantalum alkoxide, magnesium aluminum alkoxide, magnesium titanium alkoxide, magnesium zirconium alkoxide, strontium titanium alkoxide, strontium zirconium alkoxide, etc., but at least silicon, aluminum, titanium, zirconium Preferably one that contains any metal.

<Hydroxyl-containing polymer compound>
The hydroxyl group-containing polymer compound only needs to contain a hydroxyl group in the molecule, and examples thereof include synthetic polymers such as polyvinyl alcohol, polysaccharides such as starch, cellulose, carboxymethyl cellulose, sodium alginate, and derivatives thereof. It is done. These hydroxyl group-containing polymer compounds can be used singly or in appropriate combination of two or more.

Synthetic polymers include, for example, vinyl-based, polystyrene-based, polyacrylic-based, polyurethane-based, alkyd-based, melamine-based, urea-based, phenol-based, polyester-based, polyglycerol-based polymer compounds having a hydroxyl group, and multi-branched shapes. A high molecular compound having a hydroxyl group having can be used. Further, the polymer having a hydroxyl group may be a polymer into which a monomer having a hydroxyl group is introduced. In this case, the amount of hydroxyl groups and the introduction position of the polymer can be adjusted.

Examples of the monomer having a hydroxyl group include styrenes having a hydroxyl group such as 3-vinylphenol, hydroxymethylstyrene, 4-vinylbenzyl-4-hydroxybutyl ether, 4- (hydroxymethylsilylphenyl) styrene, and hydroxyethyl methacrylate. An acrylic resin having a hydroxyl group such as N- (4- (4-hydroxyphenylsulfonyl) phenoxycarbonyl) methacrylamide may be used, and a vinyl monomer is preferable. Two or more kinds of these monomers having a hydroxyl group may be mixed and used.

Polysaccharides include starch, hydroxymethyl starch, hydroxyethyl starch, hydroxypropyl starch, glycogen, inulin, lichenin, cellulose, hemicellulose, amylopectin, heparin, heparitin sulfate, chondroitin sulfate, hyaluronic acid, keratosulfate, chitin, chitosan, agar , Carrageenan, alginic acid, fur celerane, locust bean gum, galactomannan, guar gum, syrup gum, tamarind gum, gum arabic, tragacanth gum, caraya gum, pectin, arabinogalactan, xanthan gum, gellan gum, pullulan, dextran, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxy Propyl methyl cellulose, carboxymethyl cellulose, methyl cell Over scan, ethyl cellulose, and the cationic compound, and the like.

As the hydroxyl group-containing polymer compound used in the present embodiment, cellulose derivatives are preferably used. Among them, diacetyl cellulose (DAC), cellulose acetate propionate (CAP), cellulose acetate butyrate (CAB), cellulose acetate phthalate, cellulose Cellulose esters such as acetate trimellitate and cellulose nitrate are preferred. More preferably, the acyl group substitution degree is 1.0 to 2.6, and more preferably the acyl group substitution degree is 2.0 to 2.5.

(Cover glass for touch panel)
The glass with a function of this embodiment is TN, IPS, FLC (Ferroelectric Liquid Crystal), AFLC (Anti-ferroelectric Liquid Crystal), OCB (Optically Compensated Bend), STN (SuperHedVN). In particular, it is preferably used as a cover glass for a touch panel.

When using the glass with a function of this embodiment as a cover glass for a touch panel, the thin film glass 2 may be bonded so as to come into contact with the touch panel 6 as shown in FIG. 2, or the function as shown in FIG. The layer 5 side may be bonded to the touch panel 6.

When the glass with a function of this embodiment is used as a cover glass for a touch panel, the surface smoothness, hardness and toughness are excellent, and the adhesion strength between layers does not decrease even in a high temperature / high humidity environment. A touch panel having excellent properties can be obtained, which is very advantageous.

This specification discloses various modes of technology as described above, and the main technologies are summarized below.

That is, in the glass with function according to one aspect of the present invention, a resin film in which a functional layer is laminated and a thin film glass are laminated through an adhesive layer, and the adhesive layer has a reactive metal compound and a high hydroxyl group content. It contains a condensate with a molecular compound.

With such a configuration, first, the soft layer as in the case of using a conventional adhesive (for example, an acrylic adhesive) can be eliminated, and film deformation can be suppressed. Moreover, since the adhesive layer according to the present invention penetrates into the film, it does not have a thickness, can be made thinner than before, and can also improve hardness and adhesion strength. In particular, adhesion between layers can be maintained even under high temperature and high humidity. Furthermore, uneven pasting can be reduced, and surface smoothness can be ensured. Moreover, compared with the case where the conventional adhesive agent is used, the bonding area can be increased and the glass which improved the toughness (cracking property) with the thin film can be obtained.

Furthermore, in the glass with a function, it is desirable that the functional layer is a hard coat layer, an antireflection layer or an antiglare layer. This is because the effect of the present invention is more exhibited when the functional layer is such a layer.

Moreover, in the glass with a function, it is desirable that the resin film contains a cellulosic resin. This is because the cellulose-based resin has a strong hydrophilicity, so that the affinity between the adhesive layer containing a hydroxyl group and the resin film is further improved, and the adhesion between the thin film glass and the resin film having a functional layer is further improved.

Furthermore, in the glass with a function, it is preferable that the thickness of the resin film is 40 μm or less. Thereby, a thinner film can be achieved in the functional glass.

In the functional glass, the hydroxyl group-containing polymer compound is preferably a cellulose ester having a total acyl group substitution degree of 1.0 to 2.6. By setting it as such a structure, the effect of this invention mentioned above is acquired more reliably.

Furthermore, in the glass with function, it is preferable that the functional layer has a pencil hardness of 2H to 6H. This is because in such a case, the effect of the present invention is more exhibited.

Furthermore, the glass with a function is preferably used as a cover glass for a touch panel.

Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the examples. In the following description, “parts” or “%” indicates “parts by mass” or “mass%” unless otherwise specified.

<Example 1>
[Manufacture of functional glass]
(Preparation of adhesive A)
The materials were mixed at the following ratios and stirred at room temperature for 2 hours, and then the solid catalyst was separated by filtration to prepare an adhesive A.

Acetone 100 parts by mass Tetramethoxysilane (TMOS) 10 parts by mass Amberlyst 15 (solid catalyst) 2 parts by mass Cellulose ester (DAC) 10 parts by mass

(Manufacture of resin film with functional layer (hard coat layer) laminated)
As the resin film, a triacetyl cellulose film (Konica Minolta Tack KC4UA, manufactured by Konica Minolta Co., Ltd.) having a film thickness of 40 μm was used. The resin composition of the hard coat layer is composed of 100 parts by mass of pentaerythritol triacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: light acrylate PE-3A), isocyanuric acid EO-modified triacrylate (manufactured by Toagosei Co., Ltd .: Aronix M-315) 15 parts by mass and 3 parts by mass of the photopolymerization initiator were adjusted to a solid content of 50% with a methyl ethyl ketone (MEK) solvent. The stirred mixed solution is applied and dried by a gravure coating method so as to have a wet film thickness of 20 μm (dry film thickness after drying is 10 μm), and irradiated with UV light of 200 mJ / cm ² by a high-pressure mercury lamp. A laminated resin film was obtained.

As a photopolymerization initiator, 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba Specialty Chemicals Co., Ltd .: Irgacure 184) was used in this example and in all the following examples and comparative examples.

(Manufacture of laminates)
A 30 μm-thick thin film glass manufactured by Nippon Electric Glass Co., Ltd. is prepared, and adhesive A is sandwiched between them so that one side of the glass and the side on which the functional layer of the resin film is not laminated face each other. After bonding in a shape with a laminator, it was heat-pressed in an oven to obtain a functional glass. After thermocompression bonding, the adhesive A penetrated into the resin film and the thickness of the adhesive layer disappeared, so that a very thin glass with a function (thickness 70 μm) could be obtained. The glass with function of Example 1 is referred to as glass 1 with function.

<Example 2>
(Manufacture of resin film with functional layer (antireflection layer) laminated)
First, a low refractive index layer composition having the following composition was prepared.

(Low refractive index layer composition)
(Cationically polymerizable compound)
[1- (3-Ethyl-3-oxetanyl) methyl] ether 4.5 parts by mass 3-glycidoxypropyltrimethoxysilane 2.5 parts by mass Fluorine-containing epoxy compound 1 2 parts by mass (photocation polymerization initiator)
4-Methylphenyl [4- (1-methylethyl) phenyl] iodonium tetrakis (pentafluorophenyl) borate 0.2 parts by mass (Lordsil 2074, produced by Rhodia Japan)
(Silica particles)
Hollow silica particle dispersion 35 parts by mass (additive)
0.9 parts by mass of 10% propylene glycol monomethyl ether solution of a silicone compound (FZ-2207, manufactured by Toray Dow Corning Co., Ltd.) (solvent)
Methyl isobutyl ketone 30 parts by weight Methyl ethyl ketone 90 parts by weight

In addition, the fluorine-containing epoxy compound 1 and the hollow silica-based particle dispersion were prepared as follows.

(Preparation of fluorine-containing epoxy compound 1)
81.03 g of 1,3-dihydroxyhexafluoroisopropylbenzene and 185 g of epichlorohydrin were mixed, 16.27 g of sodium hydroxide and 40 ml of water were added, and the mixture was heated to reflux with stirring. After reacting at 130 ° C. for 3 hours, the mixture was naturally cooled, and the produced sodium chloride was removed by suction filtration. The obtained filtrate was extracted with chloroform-water, and the organic layer was dried, filtered and concentrated to obtain 95.7 g of fluorine-containing epoxy compound 1.

(Preparation of hollow silica-based particle dispersion)
A mixture of 100 g of silica sol having an average particle diameter of 5 nm and a SiO ₂ concentration of 20% by mass and 1900 g of pure water was heated to 80 ° C. The pH of this reaction mother liquor is 10.5. In the mother liquor, 9000 g of 0.98 mass% sodium silicate aqueous solution as SiO ₂ and 9000 g of 1.02 mass% sodium aluminate aqueous solution as Al ₂ O ₃ were simultaneously added. Added. Meanwhile, the temperature of the reaction solution was kept at 80 ° C. The pH of the reaction solution rose to 12.5 immediately after the addition and hardly changed thereafter. After completion of the addition, the reaction solution was cooled to room temperature and washed with an ultrafiltration membrane to prepare a SiO ₂ · Al ₂ O ₃ core particle dispersion with a solid content concentration of 20% by mass (step a).

1700 g of pure water is added to 500 g of this core particle dispersion and heated to 98 ° C., and while maintaining this temperature, a silicate solution (SiO ₂₎ obtained by dealkalizing a sodium silicate aqueous solution with a cation exchange resin. A dispersion of core particles on which the first silica coating layer was formed was obtained by adding 3000 g (concentration: 3.5% by mass) (step b).

Next, 1125 g of pure water is added to 500 g of the core particle dispersion liquid on which the first silica coating layer having a solid content concentration of 13 mass% is formed by washing with an ultrafiltration membrane, and concentrated hydrochloric acid (35.5%) is further added dropwise. The pH was adjusted to 1.0 and dealumination was performed. Next, while adding 10 L of hydrochloric acid aqueous solution of pH 3 and 5 L of pure water, the aluminum salt dissolved in the ultrafiltration membrane was separated, and SiO _2. A dispersion of Al ₂ O ₃ porous particles was prepared (step c).

A mixture of 1500 g of the above porous particle dispersion, 500 g of pure water, 1750 g of ethanol, and 626 g of 28% ammonia water was heated to 35 ° C., and then 104 g of ethyl silicate (SiO ₂ 28 mass%) was added. The surface of the porous particles on which the silica coating layer was formed was coated with a hydrolyzed polycondensate of ethyl silicate to form a second silica coating layer. Subsequently, a hollow silica-based particle dispersion having a solid content concentration of 20% by mass was prepared by replacing the solvent with ethanol using an ultrafiltration membrane.

The thickness of the first silica coating layer of the hollow silica-based particles was 3 nm, the average particle size was 45 nm, MOX / SiO ₂ (molar ratio) was 0.0017, and the refractive index was 1.28. Here, the average particle diameter was measured by a dynamic light scattering method.

(Resin film with a functional layer (antireflection layer) laminated)
As the resin film, a triacetyl cellulose film (Konica Minolta Tack KC4UA, manufactured by Konica Minolta Co., Ltd.) having a film thickness of 40 μm was used. Using the above low refractive index composition as the resin composition of the antireflection layer, it was applied and dried to a wet film thickness of 20 μm (dry film thickness after drying of 10 μm) by a gravure coating method, and 200 mJ / cm by a high-pressure mercury lamp. ^The resin film on which the hard coat layer was laminated was obtained by irradiating the ultraviolet ray ² .

A functional glass (thickness 70 μm) was obtained in the same manner as in Example 1 except that the resin film was a resin film laminated with the antireflection layer obtained above. The glass with function of Example 2 is referred to as glass 2 with function.

<Example 3>
(Manufacture of resin film with functional layer (antiglare layer) laminated)
As the resin film, a triacetyl cellulose film (Konica Minolta Tack KC4UA, manufactured by Konica Minolta Opto Co., Ltd.) having a thickness of 40 μm was used. The resin composition of the antiglare layer is composed of 100 parts by mass of pentaerythritol triacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light Acrylate PE-3A), polystyrene particles, 60 parts by mass of SX-130H, and photopolymerization is started. 3 parts by mass of the agent was adjusted to a solid content of 50% with methyl ethyl ketone (MEK) solvent. The anti-glare layer is formed by applying and drying the stirred mixed solution so as to have a wet film thickness of 20 μm (dry film thickness after drying of 10 μm) by a gravure coating method, and then irradiating with 200 mJ / cm ² of ultraviolet light with a high-pressure mercury lamp. A laminated resin film was obtained.

A functional glass (thickness 70 μm) was obtained in the same manner as in Example 1 except that the resin film was a resin film laminated with the antiglare layer obtained above. The glass with function of Example 3 is referred to as glass 3 with function.

<Example 4>
A functional glass (thickness: 70 μm) was obtained in the same manner as in Example 1 except that a cellulose acetate propionate film having a thickness of 40 μm was used as the resin film. Let the glass with a function of Example 4 be the glass 4 with a function.

<Example 5>
A functional glass (thickness 70 μm) was obtained in the same manner as in Example 1 except that a TAC-acrylic hybrid film (preparation method will be described later) having a thickness of 40 μm was used as the resin film. Let the glass with a function of Example 5 be the glass 5 with a function.

[Preparation of TAC-acrylic hybrid film]
(Preparation of dope)
Acrylic resin (A) weight average molecular weight Mw 300,000 (copolymerization component MMA: methyl methacrylate monomer mass ratio 70% ACMO: acryloylmorpholine monomer mass ratio 30%) 90 parts by mass Cellulose ester resin (B) weight average molecular weight Mw 300,000 ( Acetyl substitution degree 2,87) 10 parts by mass UV absorber: 2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol ] (Molecular weight 659, LA31 made by ADEKA Corporation) 3.0 parts by weight Matting agent: R972V (manufactured by Nippon Aerosil Co., Ltd., silica particles, average particle size = 16 nm) 0.30 parts by weight Peeling aid: ELECUT S412 (Takemoto Yushi 0.50 parts by mass Methylene chloride 300 parts by mass Ethanol 40 parts by mass

The above respective compositions were sufficiently dissolved while stirring and heating to prepare a dope 1. The acrylic resin (A) and the cellulose ester resin (B) were prepared according to a conventional method.

(Film formation)
The prepared dope was uniformly cast on a stainless steel band support at a temperature of 22 ° C. and a width of 2 m using a belt casting apparatus. With the stainless steel band support, the solvent was evaporated until the amount of residual solvent reached 100%, and peeling was performed from the stainless steel band support with a peeling tension of 162 N / m.

Next, the solvent of the peeled dope 1 is evaporated at 35 ° C., slit to 1 m width, and then 2.0 times in the transport direction (MD direction) by zone stretching and the width direction (TD direction) by tenter stretching. The film was dried at a drying temperature of 135 ° C. while being stretched 2.0 times. At this time, the residual solvent amount when starting stretching with the tenter was 8%.

After stretching with a tenter, it was relaxed at 130 ° C for 5 minutes, and then dried while being transported by a large number of rolls at 120 ° C and 140 ° C, and slitted to a width of 1.5 m. Was subjected to a knurling process having a width of 10 mm and a height of 5 μm, and then wound around a core to prepare a TAC-acrylic hybrid film.

The amount of residual solvent of the produced film was 700 ppm, the film thickness was 40 μm, and the winding length was 4000 m.

<Example 6>
A functional glass (thickness 55 μm) was obtained in the same manner as in Example 1 except that the film thickness of the triacetyl cellulose film was changed to one having a thickness of 25 μm (Konica Minolta Tack KC2UA, manufactured by Konica Minolta Opto Co., Ltd.). Let the glass with a function of Example 6 be the glass 6 with a function.

<Example 7>
A functional glass (thickness: 45 μm) was obtained in the same manner as in Example 1, except that the film thickness of the triacetylcellulose film prepared according to a conventional method was changed to that of 15 μm. The glass with function of Example 7 is referred to as glass 7 with function.

<Comparative Example 1>
Except for using an acrylic pressure-sensitive adhesive sheet (PSA; Pressure Sensitive Adhesive, pressure-sensitive adhesive; manufactured by Nitto Denko Corporation, LUCIACS (registered trademark) CS9622) instead of the adhesive A, A glass with a function (thickness 120 μm) was obtained. The glass with function of Comparative Example 1 is referred to as glass 8 with function.

<Comparative example 2>
A functional glass (thickness: 90 μm) was obtained in the same manner as in Example 1 except that an acrylic adhesive (UV-3610, manufactured by Toa Gosei Co., Ltd.) was used instead of the adhesive A. Let the glass with a function of the comparative example 2 be the glass 9 with a function.

<Evaluation of functional glass>
With respect to the functional glasses 1 to 9 produced above, wet heat durability adhesion and pencil hardness were evaluated. The results are shown in Table 1.

The evaluation methods and evaluation criteria for wet heat durability adhesion and pencil hardness are as follows.

(Wet heat durability adhesion)
The adhesion between the resin film and the glass after being held for 500 hours in an environment of 60 ° C. and 90% was evaluated. In the tensile shear strength test, when the tensile stress was applied, the case where the gap between the adhesive layers was generated was evaluated as x, and the case where the gap was not generated was evaluated as ◯.

(Pencil hardness)
Test evaluation was performed in accordance with the standard of JIS K5600.

As shown in Table 1, for the functional glasses 1 to 7 of Examples 1 to 7, the pencil hardness was 2H or more, and the evaluations of wet heat durability adhesion were all good. This is because the organic-inorganic hybrid glue (HB glue) according to the present invention is used as the adhesive layer between the glass and the film with the functional layer, so that the adhesive layer is good for both glass and resin having different materials. This is considered to be due to improved adhesion and improved adhesion.

On the other hand, in the functional glasses 8 and 9 of Comparative Examples 1 and 2, the pencil hardness is HB or less, and the evaluation of wet heat durability adhesion is x. This is presumably because, when the adhesive layer was PSA or an acrylic adhesive, the adhesiveness between the adhesive layer and the thin film glass and the adhesiveness between the adhesive layer and the resin film with a functional layer could not be improved at the same time.

Furthermore, since the adhesive used in the comparative example does not penetrate into the film unlike the adhesive structure of the present invention, the functional glass of Example 1 can be made thinner compared to Comparative Example 1. It was.

This application is based on Japanese Patent Application No. 2013-95454 filed on Apr. 30, 2013, the contents of which are included in this application.

In order to express the present invention, the present invention has been described appropriately and sufficiently through the embodiments with reference to the drawings and the like. However, those skilled in the art can easily change and / or improve the above-described embodiments. It should be recognized that it can be done. Therefore, unless the modifications or improvements implemented by those skilled in the art are at a level that departs from the scope of the claims recited in the claims, the modifications or improvements are not limited to the scope of the claims. To be construed as inclusive.

The present invention has wide industrial applicability in the technical field of glass used for display devices and the like.

Claims (7)

1. The resin film laminated with the functional layer and the thin glass are laminated via the adhesive layer,
   The functional glass, wherein the adhesive layer contains a condensate of a reactive metal compound and a hydroxyl group-containing polymer compound.
2. The functional glass according to claim 1, wherein the functional layer is a hard coat layer, an antireflection layer or an antiglare layer.
3. The glass with a function according to claim 1 or 2, wherein the resin film contains a cellulose resin.
4. The functional glass according to any one of claims 1 to 3, wherein the resin film has a thickness of 40 µm or less.
5. The functional glass according to any one of claims 1 to 4, wherein the hydroxyl group-containing polymer compound is a cellulose ester having a total acyl group substitution degree of 1.0 to 2.6.
6. The functional glass according to any one of claims 1 to 5, wherein the functional layer has a pencil hardness of 2H to 6H.
7. The glass with a function according to any one of claims 1 to 6, which is a cover glass for a touch panel.

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