TW201630726A - Optical laminate - Google Patents

Abstract

The present invention provides an optical laminate comprising a polarizing plate comprising a polarizer, an antistatic layer, an adhesive layer and a metal-containing layer in this order. The metal-containing layer preferably comprises at least one metal element selected from the group consisting of aluminum, copper, silver, iron, tin, nickel, and indium.

Description

Optical laminate

The present invention relates to an optical laminate comprising a polarizing plate.

In recent years, touch-sensitive liquid crystal display devices are rapidly becoming popular, centering on smart phones and tablet-type portable information terminals. As for the touch input type liquid crystal display device, there are various methods, such as a layered touch input element on the viewing side of the liquid crystal cell, and a polarizing plate disposed on the touch input element, thereby inputting the touch input element The "On-Cell" method incorporated in the liquid crystal panel (for example, Japanese Laid-Open Patent Publication No. 2012-043394).

Including touch input elements used in the On-Cell touch input type liquid crystal display device, generally, the touch input element is provided with tin-doped indium oxide on the surface of two light-transmitting substrates, respectively. The transparent conductive film formed of ITO) is formed by arranging the transparent conductive films in a direction opposite to each other via a spacer. However, in response to the recent increase in the price of indium and the demand for low resistance of transparent conductive films, ITO is being sought. Alternative technology. As one of the alternative technologies, the development of metal grids is underway. The metal mesh is formed on a transparent substrate to form a metal into a minute grid shape. The metal mesh has excellent electrical conductivity and light transmittance, and at the same time, can reduce the manufacturing cost of the touch input element, and thus is highly regarded as a next generation transparent conductive film.

On the other hand, the present inventors have found that in the touch input element, if a metal-containing layer including a metal mesh is used instead of ITO as a transparent conductive film, it is found that the touch input type liquid crystal display device is used. A new subject with corrosion of metal layers. During corrosion, pitting will have a large effect on the metal grid causing wire breakage.

The present invention has been made in view of the above problems, and an object thereof is to provide an optical layered body comprising an optical layered body of a polarizing plate and preventing corrosion of a metal containing layer.

The present invention provides an optical laminate as shown below.

[1] An optical layered body comprising: a polarizing plate including a polarizing plate, an antistatic layer, an adhesive layer, and a metal containing layer, in the order described below.

[2] The optical layered product according to [1], wherein the metal-containing layer contains at least one metal element selected from the group consisting of aluminum, copper, silver, iron, tin, nickel, and indium.

[3] The optical layered body according to [1], wherein a protective layer is further provided between the pressure-sensitive adhesive layer and the metal-containing layer.

According to the present invention, a metal-containing layer can be provided Corrosive optical laminate.

10‧‧‧Polar plate

11‧‧‧ polarizer

21, 22‧‧‧ protective film

30‧‧‧Antistatic layer

40‧‧‧Adhesive layer

60‧‧‧Metal layer

70‧‧‧Transmissive substrate

100,300‧‧‧Antistatic polarizer

400, 500, 600‧‧‧ optical laminates

Fig. 1 is a schematic cross-sectional view showing an example of a layer structure of an optical layered body of the present invention.

Fig. 2 is a schematic cross-sectional view schematically showing another example of the layer structure of the optical layered body of the present invention.

Fig. 3 is a schematic cross-sectional view showing still another example of the layer structure of the optical layered body of the present invention.

[optical laminate] (1) Structure of optical laminate

As shown in Fig. 1, an optical layered body 400 according to an embodiment of the present invention includes a polarizing plate 10 including a polarizing plate 11, an antistatic layer 30, an adhesive layer 40, and a metal containing layer 60 in the following order. Further, the optical layered body 400 may include a light-transmitting substrate 70 disposed on a surface of the metal-containing layer 60 opposite to the surface on which the pressure-sensitive adhesive layer 40 is laminated. The optical layered body 400 includes a polarizing plate 10, an antistatic layer 30, and an adhesive layer 40, and the adhesive layer 40 of the antistatic polarizing plate 300 with an adhesive layer can be attached to the light-transmitting substrate 70. The surface of the surface is formed by the surface of the metal layer 60. In the optical layered body 400, the metal containing layer 60 is formed on the entire surface of the light-transmitting substrate 70. The antistatic polarizing plate 100 includes a polarizing plate 10 and an antistatic layer 30 laminated on one surface thereof.

Further, as shown in FIG. 2, the optical layered body 500 may include the covering layer 50 between the adhesive layer 40 and the metal containing layer 60. At this time, the adhesive layer 40 of the antistatic polarizing plate 300 with the adhesive layer can be bonded to the surface of the coating layer 50 laminated on the surface of the metal containing layer 60 to form the optical layered body 500. In the optical layered body 500, the metal containing layer 60 is formed on the entire surface of the light-transmitting substrate 70.

The other surface of the polarizing plate 10, that is, the surface opposite to the antistatic layer 30, is not particularly limited, and for example, the antistatic layer 31 may be further laminated.

(2) Polarizer

The polarizing plate 10 is a polarizing element including at least the polarizing plate 11, and generally further includes protective films 21 and 22 which are bonded to one or both sides of the polarizing plate 10. Although illustration is omitted, bonding of the polarizer 11 and the protective films 21 and 22 can be performed using an adhesive.

The polarizing plate 10 may include, in addition to the protective films 21, 22, another optical film such as a film having a different optical function from the polarizing plate 11, and a layer attached to a film such as an optical layer. Various optical films including a protective film can be attached via an adhesive layer or an adhesive.

(2-1) Polarizer

The polarizer 11 may be an absorptive polarizer having a property of absorbing linear polarized light having a vibration plane parallel to the absorption axis of the polarizer 11, and having a perpendicular intersection with the absorption axis (parallel to the transmission axis) Vibration The linear polarizing of the surface can be suitably used for a polarizing film in which a polyvinyl alcohol-based resin film adsorbs a directional dichroic dye. The polarizer 11 can be produced, for example, by a method comprising the steps of: stretching a polyvinyl alcohol-based resin film by one axis; and dyeing the polyvinyl alcohol-based resin film with a dichroic dye to adsorb a dichroic dye a step of treating a polyvinyl alcohol-based resin film having a dichroic dye adsorbed thereto with an aqueous solution of boric acid; and a step of washing with water after treatment with an aqueous solution of boric acid.

As the polyvinyl alcohol-based resin, those obtained by saponifying a polyvinyl acetate-based resin can be used. The polyvinyl acetate-based resin is a polyvinyl acetate of a homopolymer of vinyl acetate, and examples thereof include a copolymer of another monomer copolymerizable with vinyl acetate. Examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and (meth) acrylamides having ammonium groups.

The degree of saponification of the polyvinyl alcohol-based resin is usually about 85 to 100 mol%, preferably 98 mol% or more. The polyvinyl alcohol-based resin may be modified, and for example, an aldehyde-modified polyethylene formaldehyde or a polyvinyl acetal may be used. The average degree of polymerization of the polyvinyl alcohol-based resin is usually from about 1,000 to 10,000, preferably from about 1,500 to 5,000. The average degree of polymerization of the polyvinyl alcohol-based resin can be determined in accordance with JIS K 6726.

A film obtained by forming such a polyvinyl alcohol-based resin as a polarizing film 11 (polarizing film) can be used. The method for forming the polyvinyl alcohol-based resin is not particularly limited, and a known method can be employed. The thickness of the polyvinyl alcohol-based germplasm is, for example, about 10 to 150 μm.

One of the axis extensions of the polyvinyl alcohol resin film is available in two The coloring pigment is dyed before, simultaneously with, or after dyeing. When a one-axis extension is performed after dyeing, the one-axis extension can be performed before boric acid treatment or boric acid treatment. Moreover, one-axis extension can also be performed in a plurality of stages.

In the case of one-axis extension, it is possible to extend toward one axis between rolls having different peripheral speeds, or to extend to one axis using a heat roll. Further, the one-axis extension may be a dry stretching in which the film is stretched in the air, or may be a wet stretching in which the polyvinyl alcohol-based resin film is swollen using a solvent or water. The stretching ratio is usually about 3 to 8 times.

A method of dyeing a polyvinyl alcohol-based resin film with a dichroic dye is, for example, a method of immersing the film in an aqueous solution containing a dichroic dye. As the dichroic dye, iodine or a dichroic organic dye can be used. Further, the polyvinyl alcohol-based resin film is preferably subjected to a treatment of immersing in water before the dyeing treatment.

The dyeing treatment with iodine is usually carried out by immersing a polyvinyl alcohol-based resin film in an aqueous solution containing iodine and potassium iodide. The content of iodine in the aqueous solution may be about 0.01 to 1 part by weight per 100 parts by weight of the water. The content of potassium iodide may be from about 0.5 to 20 parts by weight per 100 parts by weight of water. Moreover, the temperature of the aqueous solution may be about 20 to 40 °C. On the other hand, a dyeing treatment by a dichroic organic dye is usually carried out by immersing a polyvinyl alcohol-based resin film in an aqueous solution containing a dichroic organic dye. An aqueous solution containing a dichroic organic dye may also contain an inorganic salt such as sodium sulfate as a dyeing auxiliary. The content of the dichroic organic dye in the aqueous solution may be about 1 × 10 ^-4 to 10 parts by weight per 100 parts by weight of the water. The temperature of this aqueous solution may be about 20 to 80 °C.

The boric acid treatment after dyeing with a dichroic dye is usually carried out by immersing the dyed polyvinyl alcohol-based resin film in an aqueous solution containing boric acid. When iodine is used as the dichroic dye, it is preferred that the aqueous solution containing boric acid contains potassium iodide. The amount of boric acid in the aqueous solution containing boric acid may be from about 2 to 15 parts by weight per 100 parts by weight of the water. The amount of potassium iodide in the aqueous solution may be from about 0.1 to 15 parts by weight per 100 parts by weight of the water. The temperature of the aqueous solution may be 50 ° C or higher, for example, 50 to 85 ° C.

The polyvinyl alcohol-based resin film after the boric acid treatment is usually washed with water. The water washing treatment can be carried out, for example, by immersing a boric acid-treated polyvinyl alcohol-based resin film in water. The temperature of the water in the water washing treatment is usually about 5 to 40 °C.

After the water washing, drying treatment is carried out to obtain a polarizing film 11. The drying treatment can be carried out using a hot air dryer or a far infrared heater. The thickness of the polarizer 11 is preferably 25 μm or less, more preferably 15 μm or less, and still more preferably 10 μm or less from the viewpoint of reducing the thickness of the antistatic polarizing plate. The thickness of the polarizer 11 is usually 2 μm or more.

The polarizer 11 can also be produced by applying a coating liquid containing a polyvinyl alcohol-based resin to a base film and drying it to form a polyvinyl alcohol-based resin layer, and forming the polyvinyl alcohol-based resin. The base film of the resin layer is stretched together with the polyvinyl alcohol-based resin layer, followed by a dyeing treatment with a dichroic dye to remove the base film. As the base film, for example, a polyester resin such as polyethylene terephthalate or a polycarbonate can be used. A thermoplastic resin film made of a thermoplastic resin such as a cellulose resin such as a resin such as triacetonitrile or a polyolefin resin such as a decene-based resin or a polystyrene resin. The extension process is typically a one-axis extension. This method is preferable in that it is easy to produce a polarizing plate having a small thickness, for example, a thickness of 7 μm or less.

(2-2) Protective film

The protective film 21, 22 which can be laminated on one or both sides of the polarizer 11 may be a film of a translucent (preferably optically transparent) thermoplastic resin such as a chain polyolefin resin (for example) a polyolefin-based resin such as a polypropylene-based resin or a cyclic polyolefin-based resin (such as a decene-based resin); a cellulose-based resin such as triacetyl cellulose or diethyl phthalocyanine; for example, poly-p-phenylene Ethylene glycol formate, polyester resin of polybutylene terephthalate; polycarbonate resin; (meth)acrylic resin such as methyl methacrylate resin; polystyrene resin; polychlorinated Vinyl resin; acrylonitrile/butadiene/styrene resin; acrylonitrile/styrene resin; polyvinyl acetate resin; polyvinylidene chloride resin; polyamine resin; polyacetal resin A modified polyphenylene resin; a polyfluorene-based resin; a polyether fluorene-based resin; a polyarylate-based resin; a polyamidoximine-based resin; a polyimide-based resin. In the present specification, the "(meth)acrylic resin" is at least one selected from the group consisting of an acrylic resin and a methacrylic resin. Other terms with "(methyl)" are also the same.

The chain-like polyolefin-based resin includes, in addition to a homopolymer of a chain olefin such as a polyethylene resin or a polypropylene resin, A copolymer of the above chain olefins.

The cyclic polyolefin resin is a general term for a resin obtained by polymerizing a cyclic olefin as a polymerization unit. Specific examples of the cyclic polyolefin-based resin include a ring-opening (co)polymer of a cyclic olefin, an addition polymer of a cyclic olefin, and a copolymer of a cyclic olefin and a chain olefin such as ethylene or propylene ( Representative examples are random copolymers) and such graft polymers modified with unsaturated carboxylic acids or derivatives thereof, and such hydrides. Among them, a norbornene-based resin having a norbornene-based monomer such as a norbornene or a polycyclic norbornene-based monomer as a cyclic olefin is preferably used.

The cellulose resin refers to a part or all of hydrogen atoms in the hydroxyl group of the cellulose obtained from the raw material cellulose such as cotton linters, wood pulp (broadwood pulp, and conifer pulp), and the like, and the acetamino group, the propyl group, and/or Or a cellulose organic acid ester or a cellulose mixed organic acid ester substituted with a butyl group. For example, it is composed of cellulose acetate, propionate, butyrate, and a mixed ester thereof. Among them, triacetonitrile cellulose, diacetyl cellulose, cellulose acetate propionate, and cellulose acetate butyrate are preferred.

The (meth)acrylic resin is a polymer containing a structural unit derived from a (meth)acrylic monomer. The polymer is typically a polymer comprising methacrylate. Preferred polymers are those containing a methacrylate-derived structural unit in a ratio of 50% by weight or more based on the entire structural unit. The (meth)acrylic resin may be a homopolymer of methacrylate or a copolymer containing structural units derived from other polymerizable monomers. At this time, the ratio of the structural unit derived from another polymerizable monomer is preferably 50% or less with respect to all the structural units.

A methacrylate of a (meth)acrylic resin may be formed, and an alkyl methacrylate is preferable. The alkyl methacrylate may, for example, be methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, or The alkyl methacrylate having a carbon number of 1 to 8 is an alkyl group of a third butyl acrylate, a 2-ethylhexyl methacrylate, a cyclohexyl methacrylate or a 2-hydroxyethyl methacrylate. The alkyl group contained in the alkyl methacrylate preferably has 1 to 4 carbon atoms. In the (meth)acrylic resin, the methacrylate may be used alone or in combination of two or more.

Examples of the other polymerizable monomer which can constitute the (meth)acrylic resin include acrylates and other compounds having a polymerizable carbon-carbon double bond in the molecule. The other polymerizable monomers may be used alone or in combination of two or more. The acrylate is preferably an alkyl acrylate. The alkyl acrylate may, for example, be methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, acrylic acid. The alkyl group of cyclohexyl ester or 2-hydroxyethyl acrylate having an alkyl group having 1 to 8 carbon atoms. The alkyl group contained in the alkyl acrylate preferably has 1 to 4 carbon atoms. In the (meth)acrylic resin, the acrylate may be used alone or in combination of two or more.

Examples of the compound having a polymerizable carbon-carbon double bond in another molecule include a vinyl compound such as ethylene, propylene or styrene, and an ethylene cyanide compound such as acrylonitrile. The compound having a polymerizable carbon-carbon double bond in the other molecule may be used alone or in combination of two or more.

The (meth)acrylic resin can improve the durability of the protective film and has a ring structure in the main chain. The ring structure is preferably a cyclic acid anhydride structure such as a glutaric anhydride structure or a succinic anhydride structure; a cyclic quinone imine structure such as a glutarylene imine structure and an amber quinone structure; a lactone ring such as butyrolactone and valerolactone Construction, etc.

The protective films 21, 22 may also be protective films having an optical function such as a phase difference film. For example, a film made of the above thermoplastic resin may be stretched (one-axis stretching or biaxial stretching or the like), or a liquid crystal layer or the like may be formed on the film, whereby a phase difference film imparting an arbitrary phase difference value may be used. Further, a thermoplastic resin (for example, (meth)acrylic resin) may be laminated on at least one of the phase difference display layers, and the extension may be a retardation film. At least one of the protective films 21 and 22 may have a hard coat layer, an antiglare layer, a light diffusion layer, and a phase difference layer (having 1/4 of the outer surface (the surface opposite to the polarizer 11). A phase difference layer of a phase difference of wavelengths, etc.), an antireflection layer, a surface treatment layer (coating layer) of an antifouling layer, or an optical layer.

The thickness of the protective films 21, 22 may be about 1 to 100 μm, preferably from 5 to 60 μm, more preferably from 5 to 50 μm from the viewpoint of strength, handleability, and the like. When the thickness is within this range, the polarizer 11 can be mechanically protected, and the polarizer 11 does not shrink even when exposed to a moist heat environment, and the stable optical characteristics can be maintained.

The protective film may be bonded only to one side of the polarizer 11 or may be bonded to both sides of the polarizer 11.

When the protective films 21 and 22 are bonded to both surfaces of the polarizer 11, the protective films may be composed of the same thermoplastic resin or different kinds of Made of thermoplastic resin. Moreover, the thicknesses may be the same or may be different. In addition, they may have the same phase difference characteristics and may have different phase difference characteristics.

The protective films 21 and 22 can be bonded to the polarizer 11 via, for example, an adhesive layer. As the adhesive for forming the adhesive layer, a water-based adhesive, an active energy ray-curable adhesive or a thermosetting adhesive can be used, and a water-based adhesive or an active energy ray-curable adhesive is preferable.

The water-based adhesive agent is an adhesive composition using a polyvinyl alcohol-based resin or an amine ester resin as a main component.

When a polyvinyl alcohol-based resin is used as a main component of a water-based adhesive, the polyvinyl alcohol-based resin is exemplified by acetic acid, except for a vinyl alcohol homopolymer obtained by saponifying polyvinyl acetate of a homopolymer of vinyl acetate. a copolymer of vinyl ester and other monomers copolymerizable with vinyl acetate, and the like. Examples of the other monomer copolymerizable with vinyl acetate include an unsaturated carboxylic acid, an unsaturated sulfonic acid, an olefin, a vinyl ether, and a (meth) acrylamide having an ammonium group. The polyvinyl alcohol-based resin used in the adhesive is preferably an aqueous solution having a suitable degree of polymerization, for example, a concentration of 4% by weight, and a viscosity of 4 to 50 mPa. Within the range of sec, it is more preferably 6 to 30 mPa. Within the scope of sec.

Further, it is also preferred to use a modified polyvinyl alcohol-based resin. Examples of suitable modified polyvinyl alcohol-based resins include polyvinyl alcohol-based resins modified with acetamidine, polyvinyl alcohol-based resins modified with anions, and polyvinyl alcohol-based resins modified with cations. . When such a modified polyvinyl alcohol-based resin is used, it is easy to obtain water resistance of the adhesive layer. The effect.

The water-based adhesive used in the present invention may of course be composed of two or more kinds of the modified polyvinyl alcohol-based resins, and may be an unmodified polyvinyl alcohol-based resin (specifically, polyacetic acid). Both the fully or partially saponified product of vinyl ester and the above modified polyvinyl alcohol resin.

The polyvinyl alcohol-based resin constituting the water-based adhesive can be appropriately selected from commercially available products. Specifically, for example, "PVA-117H", "KL-318, "KM-118", and "CM-318" sold by Kuraray Co., Ltd., which are sold by Japan Synthetic Chemical Industry Co., Ltd., may be mentioned. "Gohsenol NH-20", "GOHSEFIMER Z" series, "GOHSEFIMER K-210" and "GOHSENAL T-330" (all of which are trade names).

A water-based adhesive containing a polyvinyl alcohol-based resin as a main component may contain a crosslinking agent. When a compound which can be a crosslinking agent is listed depending on the functional group type, there are an isocyanate compound having at least two isocyanato groups (-NCO) in the molecule; and at least two epoxy groups in the molecule (crosslinking) -O-) epoxy compound; mono- or di-aldehyde; organotitanium compound; inorganic salt of divalent or trivalent metal such as magnesium, calcium, iron, nickel, zinc and aluminum; metal salt of glyoxylic acid ; methylol melamine and the like.

Among these crosslinking agents, an epoxy compound, an aldehyde, methylol melamine, an alkali metal or an alkaline earth metal salt of glyoxylic acid, or the like, which is the above-mentioned water-soluble polyamine epoxy resin, is suitably used.

The crosslinking agent is preferably dissolved in water together with a polyvinyl alcohol-based resin to form an adhesive. However, as described below, the crosslinking agent in the aqueous solution The amount may be a small amount, so that it can be used as a crosslinking agent if it has a solubility of, for example, at least about 0.1% by weight with respect to water. Of course, those having a solubility in water generally referred to as water solubility are suitable as the crosslinking agent used in the present invention.

The blending amount of the cross-linking agent is appropriately designed depending on the type of the polyvinyl alcohol-based resin, and is usually about 5 to 60 parts by weight, preferably 10 to 50 parts by weight, per 100 parts by weight of the polyvinyl alcohol-based resin. If the crosslinking agent is blended in this range, good adhesion can be obtained. If the amount of the crosslinking agent is too large, the crosslinking agent will react in a short time, and the adhesive tends to gel at an early stage. As a result, the pot life becomes extremely short and it is difficult to use it in the industry. .

In the aqueous binder, a conventionally known additive such as a decane coupling agent, a plasticizer, an antistatic agent, or fine particles can be blended in a range that does not inhibit the effects of the present invention.

When an amine ester resin is used as a main component of the water-based adhesive, an example of a suitable adhesive is a mixture of a polyester-based ionic polymer-type amine ester resin and a compound having a glycidoxy group. Here, the polyester-based ionic polymer-type amine ester resin is a polyester ester resin having a polyester skeleton, and a small amount of an ionic component (hydrophilic component) is introduced into the amine ester resin. Since the ionic polymer type amine ester resin is directly emulsified in water to form an emulsion without using an emulsifier, it is suitably used for a water-based adhesive. For example, Japanese Laid-Open Patent Publication No. 2005-070140, Japanese Patent No. 4,342,487, and JP-A-2005-208456 disclose the use of a polyester-based ionic polymer-type amine ester resin between a polarizer and a protective film. Then the agent layer.

The active energy ray-curable adhesive refers to an adhesive which is cured by irradiation with an active energy ray such as ultraviolet rays or electron rays. The sclerosing adhesive is classified into a cationic polymerization type adhesive containing a cationically polymerizable compound as the curable compound, and a radical polymerization type adhesive containing a radically polymerizable compound as the curable compound, and includes A form-hardening adhesive or the like of a cationically polymerizable compound and a radically polymerizable compound. Specific examples of the cationically polymerizable compound include an epoxy compound having one or more epoxy groups in the molecule, an oxetane compound having one or more oxetane rings in the molecule, and a vinyl compound. . Further, specific examples of the radically polymerizable compound include a (meth)acrylic compound having one or more (meth)acrylinyl groups in the molecule, and a vinyl compound. In the active energy ray-curable adhesive, a sensitizer, a sensitizer, a leveling agent, a decane coupling agent, an antistatic agent, an ultraviolet absorber, a thermal polymerization initiator can be blended in a range that does not inhibit the effects of the present invention. Such additives as conventionally known.

When the active energy ray-curable adhesive is used, after the polarizer 11 and the protective films 21 and 22 are bonded, the drying step is performed as needed, and then the active energy ray is irradiated, whereby the active energy ray-curable adhesive is hardened. Hardening step. Therefore, when an active energy ray-curable adhesive is used, the adhesive layer is a cured layer. The light source of the active energy ray is not particularly limited, but ultraviolet light having a light-emitting distribution at a wavelength of 400 nm or less is preferable. Specifically, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, and a fluorescent lamp can be used. Light, black light, microwave excited mercury lamp, metal halide lamp, etc.

The thickness of the adhesive layer obtained after drying or hardening is usually about 0.01 to 5 μm, but may be 1 μm or less when a water-based adhesive is used. On the other hand, when an active energy ray-curable adhesive is used, it is preferably 3 μm or less, more preferably 2 μm or less, and still more preferably 1 μm or less. If the adhesive layer is too thin, it may become insufficient subsequently. On the other hand, if the adhesive layer is too thick, the appearance of the polarizing plate may be poor.

When the polarizer 11 and the protective films 21 and 22 are bonded, in order to improve the adhesion, saponification treatment, corona treatment, plasma treatment, flame treatment, primer treatment, and the like may be applied to at least one of the bonding surfaces. Anchor coating treatment and the like.

When the protective film is bonded to both surfaces of the polarizer 11, the adhesive for bonding the protective films may be the same kind of adhesive or a different type of adhesive.

(2-3) Other optical films

The antistatic polarizing plate 100 may include an optical film other than the polarizing plate 11 and the protective films 21 and 22, and a representative example thereof is a brightness enhancement film and a retardation film. Other optical films may be laminated via an adhesive layer or an adhesive layer.

(3) Antistatic layer

The antistatic layer 30 is used for the purpose of suppressing the influence of static electricity on the functions of the optical layered bodies 400 and 500. Examples of the material for forming the antistatic layer 30 include conductive fine particles coated with fine particles such as a conductive polymer, metal fine particles, metal oxide fine particles or metal, and the like. An ion conductive composition composed of a salt and an organic polyoxyalkylene, an ionic compound, various surfactants (cationic, anionic, and amphoteric surfactants). By including these materials in the antistatic layer 30, the electrical resistance of the antistatic layer 30 is lowered, so that the antistatic layer 30 and even the optical laminates 400, 500 can be given an antistatic function.

Examples of the conductive polymer include polyacetylene, a polyphenyl group bonded to a para or meta position, and a polymer obtained by linking a phenyl group via a divalent group (for example, a benzene bonded via -CH=CH-) a polyphenylene sulfide formed by stretching a phenyl group, a polyphenylene sulfide formed by a -S-linked phenyl group, and a polyphenylene ether formed by a -O-linked phenyl group, and an element constituting a five-membered ring a polymer in which C and H are connected at 2, 5 positions (for example, a 5-membered ring containing NH is a 2,5-position polypyrrole, and a S-containing five-membered ring is 2,5 Polythiophene, a 5-membered ring containing O, a polyfuran linked at 2, 5, a 5-membered ring containing Se, a selenium phenanthene linked at 2, 5, and a member containing Te A polymer obtained by polymerizing an aromatic amine such as a polyphenylene group in which a ring is bonded at 2 or 5 positions (for example, polyaniline or polyamino sulfonium), polystyrene sulfonic acid, or the like. Among these, polyaniline, polythiophene, and polypyrrole are preferred, and polyaniline and polythiophene are more preferred. Commercial products of the conductive polymer include "Denatron" (registered trademark) manufactured by Nagasechemtex Co., Ltd., "ORMECON" (registered trademark) manufactured by Nissan Chemical Industries, Ltd., and "CLEVIOUS" manufactured by HC Stark Co., Ltd. "SEPLEGYDA" (registered trademark) manufactured by Shin-Etsu Polymer Co., Ltd., "Baytron" manufactured by Bayer Co., Ltd., etc.

As the conductive fine particles, for example, silver powder, copper powder, nickel powder, zinc oxide (ZnO), tin oxide (SnO ₂ ), antimony-doped tin oxide (ATO), tin-doped indium oxide (ITO), or the like can be used.

The ion conductive composition is composed of, for example, an electrolyte salt and an organic polyoxane represented by the following formula.

Wherein, R ¹¹ represents a monovalent organic group, R ¹² to R ¹⁴ represents a alkylene group, R ¹⁵ represents hydrogen or a monovalent organic group. m is an integer from 0 to 100, and n is an integer from 1 to 100. The arrangement of the -(-Si(R ¹¹ R ¹¹ )O-)- unit and the -(-Si(R ¹¹ R ¹² )O-)- unit is in any order. a and b are each an integer from 0 to 100, and are not 0 at the same time. The arrangement of -(-R ¹³ O-)- and -(-R ¹⁴ O-)- is in any order.

The electrolyte salt may, for example, be an electrolyte salt of a metal cation belonging to Group I or Group II of the periodic table. Examples of the cation include cations such as lithium, sodium, potassium, magnesium, calcium, and barium.

The ionic compound is, for example, a compound having an inorganic cation or an organic cation, an inorganic anion or an organic anion.

The inorganic cation may, for example, be an alkali metal ion such as a lithium cation [Li ⁺ ], a sodium cation [Na ⁺ ], a potassium cation [K ⁺ ], such as a ^phosphonium cation [Be ²⁺ ], a magnesium cation [Mg ²⁺ ], calcium. An alkaline earth metal ion of a cation [Ca ²⁺ ] or the like.

Examples of the organic cation include an imidazolium cation and a pyridyl group. Pyridinium cation, pyrrolidinium cation, ammonium cation, phosphonium cation, phosphonium cation, piperidinium cation, and the like.

Examples of the inorganic anion include a chloride anion [Cl ^- ], a bromine anion [Br ^- ], an iodine anion [I ^- ], a tetrachloroaluminate anion [AlCl ₄ ^- ], a heptachlorodisuccinate anion [Al ₂ Cl ₇ ^- ], tetrafluoroborate anion [BF ₄ ^- ], hexafluorophosphate anion [PF ₆ ^- ], perchlorate anion [ClO ₄ ^- ], nitrate anion [NO ₃ ^- ], hexafluoroarsenate anion [AsF ₆ ^-], hexafluoroantimonate anion [SbF ₆ ^-], niobium hexafluorophosphate anion [NbF ₆ ^-], six tantalum fluoride anion [TaF ₆ ^-], dicyanamide anion [(CN) ₂ N ^-], etc. .

The organic anion may, for example, be an acetate anion [CH ₃ COO ^- ], a trifluoroacetate anion [CF ₃ COO ^- ], a methanesulfonate anion [CH ₃ SO ₃ ^- ], a triflate anion [CF ₃ SO] ₃ ^- ], p-toluenesulfonate anion [p-CH ₃ C ₆ H ₄ SO ₃ ^- ], bis(fluorosulfonyl) quinone anion [(FSO ₂ ) ₂ N ^- ], bis (trifluoro Methanesulfonyl) sulfoximine anion [(CF ₃ SO ₂ ) ₂ N ^- ], ginseng (trifluoromethanesulfonyl) methanide anion [(CF ₃ SO ₂ ) ₃ C ^- ], dimethyl Phosphonate anion [(CH ₃ ) ₂ POO ^- ], (poly)fluorohydrofluoric acid anion [F(HF) _n ^- ] (n is about 1 to 3), thiocyanate anion [SCN ^- ], perfluorobutane alkyl sulfonate anion ^{_{[C 4 F 9 SO 3 -}} ], bis (pentafluoroethane sulfonyl acyl) acyl imide anion _{[(C 2 F 5 SO 2} ) 2 N -], perfluoro acid anions [C ₃ F ₇ COO ^- ], (trifluoromethanesulfonyl) (trifluoromethanecarbonyl) quinone anion [(CF ₃ SO ₂ )(CF ₃ CO)N ^- ], perfluoropropane-1,3- a disulfonate anion [ ^- O ₃ S(CF ₂ ) ₃ SO ₃ ^- ], a carbonate anion [CO ₃ ^2- ], and the like. Among the above anion components, it is advantageous to use an anion component containing a fluorine atom in terms of antistatic property.

Specific examples of the ionic compound can be appropriately selected from the combination of the above cationic component and anionic component. When each of the examples in which an ionic compound having an organic cation is classified into an organic cation, the following ones are mentioned.

Pyridinium salt: N-hexylpyridinium hexafluorophosphate, N-octylpyridinium hexafluorophosphate, N-octyl-4-methylpyridinium hexafluorophosphate, N-butyl-4-methyl Pyridinium hexafluorophosphate, N-decylpyridinium bis(fluorosulfonyl) quinone imine, N-dodecylpyridinium bis(fluorosulfonyl) quinone imine, N-tetradecylpyridinium double (fluorosulfonyl) quinone imine, N-hexadecylpyridinium bis(fluorosulfonyl) quinone imine, N-dodecyl-4-methylpyridinium bis(fluorosulfonyl) quinone imine , N-tetradecyl-4-methylpyridinium bis(fluorosulfonyl) quinone imine, N-hexadecyl-4-methylpyridinium bis(fluorosulfonyl) quinone imine, N-benzene Methyl-2-methylpyridinium bis(fluorosulfonyl) quinone imine, N-benzyl-4-methylpyridinium bis(fluorosulfonyl) quinone imine, N-hexylpyridinium bis ( Trifluoromethanesulfonyl) quinone imine, N-octylpyridinium bis(trifluoromethanesulfonyl) quinone imine, N-octyl-4-methylpyridinium bis(trifluoromethanesulfonyl) Yttrium imine, N-butyl-4-methylpyridinium bis(trifluoromethanesulfonyl) quinone imine.

Imidazolium salt: 1-ethyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium p-toluenesulfonate, 1-ethyl-3-methylimidazolium bis(fluorosulfonyl) quinone imine, 1-ethyl-3-methylimidazole Bis(trifluoromethanesulfonyl) quinone imine, 1-butyl-3-methylimidazolium methanesulfonic acid, 1-butyl-3-methylimidazolium bis(fluorosulfonyl) quinone imine .

Pyrrolidinium salt: N-butyl-N-methylpyrrolidinium hexafluorophosphate, N-butyl-N-methylpyrrolidinium bis(fluorosulfonyl) quinone imine, N-butyl- N-methylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine.

Grade 4 ammonium salt: tetrabutylammonium hexafluorophosphate, tetrabutylammonium p-toluenesulfonate, (2-hydroxyethyl)trimethylammonium bis(trifluoromethanesulfonyl) ruthenium, 2-Hydroxyethyl)trimethylammonium dimethylphosphinate.

Further, examples of the ionic compound having an inorganic cation include the following.

Lithium bromide, lithium iodide, lithium tetrafluoroborate, lithium hexafluorophosphate, lithium thiocyanate, lithium perchlorate, lithium triflate, lithium bis(fluorosulfonyl) ruthenium, Lithium bis(trifluoromethanesulfonyl) sulfonium imide, lithium bis(pentafluoroethanesulfonyl) ruthenium, lithium methanide (trifluoromethanesulfonyl), lithium p-toluenesulfonate, hexafluoro Sodium phosphate, sodium bis(fluorosulfonyl) phthalimide, sodium bis(trifluoromethanesulfonyl) sulfoximine, sodium p-toluene sulfonate, potassium hexafluorophosphate, bis(fluorosulfonyl)pyrene Potassiumamine, potassium bis(trifluoromethanesulfonyl) sulfoximine, potassium p-toluenesulfonate.

These ionic compounds may be used alone or in combination of two or more.

For example, an ionic compound, a conductive fine particle, a conductive polymer, or the like may be used alone or in combination of two or more kinds. In addition, it is a matter of course that two or more types of antistatic agents classified as ionic compounds may be used in combination, or two or more kinds of antistatic agents classified as conductive fine particles may be used in combination, or may be classified as a conductive polymer. Two or more kinds of antistatic agents are used in combination.

The antistatic layer 30 may contain at least one of a hydrolyzable organic hydrazine compound and a polycondensate thereof as an antistatic agent. The antistatic layer 30 also functions as an antistatic agent by at least one of a hydrolyzable organic hydrazine compound and a polycondensate thereof, and the antistatic layer 30 may have an antistatic function.

The hydrolyzable organic hydrazine compound is a compound in which a non-hydrolyzable organic group and a hydrolyzable organic or inorganic group are bonded to a ruthenium atom, or a hydrolyzable organic group is bonded to a ruthenium atom, wherein the organic group may be a carbon atom. The one located at the bonding position may also be the one where the other atoms are located at the bonding position. , The formula may represent a hydrolyzable organic silicon compound of _{^{specifically: Si (T 1) q (}} T 2) 4-q. In the formula, T ¹ represents a hydrogen atom or a non-hydrolyzable organic group, T ² represents a hydrolyzable group, and q represents an integer of 0 to 3.

In the above formula, as shown at T, non-hydrolyzable organic group of ^1, as typically include those having a carbon number of 1 to about 4 alkyl groups, of about 2 to 4 carbon atoms, an alkenyl group, an aryl group a phenyl. Further, the hydrolyzable group represented by T ² may, for example, be an alkoxy group having a carbon number of from 1 to 5 such as a methoxy group or an ethoxy group, such as an ethoxy group having an ethoxy group or a propyloxy group. For example, a chlorine atom or a halogen atom of a bromine atom, such as a substituted mercaptoamine group of a trimethylsulfonylamino group. Specifically, the hydrolyzable organic hydrazine compound may be an alkoxydecane compound, a halogenated decane compound, a decyloxydecane compound, a decazane compound or the like. The hydrolyzable organic ruthenium compound may have a substituent such as an aryl group, a vinyl group, an allyl group, a (meth) propylene fluorenyl group, an epoxy group, an amine group, a decyl group or a fluoroalkyl group as the above formula T ¹ Or part of T ² .

Specific examples of the hydrolyzable organic hydrazine compound include, for example, a halogenated decane compound such as methyl trichlorodecane, such as tetramethoxy decane, tetraethoxy decane, methyl trimethoxy decane, phenyl trimethoxy decane, Phenyltriethoxydecane, dimethyldimethoxydecane, dimethyldiethoxydecane, vinyltrimethoxydecane, vinyltriethoxydecane, γ- Aminopropyltriethoxydecane, N-(β-aminoethyl)-γ-aminopropyltrimethoxydecane, N-(β-aminoethyl)-γ-aminopropyl A Dimethoxydecane, γ-mercaptopropyltrimethoxydecane, γ-mercaptopropylmethyldimethoxydecane, γ-methylpropenyloxypropyltrimethoxydecane, γ-methylpropene Alkoxydecane compounds such as methoxypropylmethyldimethoxydecane, γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropylmethyldimethoxydecane, such as six a decane compound of methyl diazoxide or the like. These may be used alone or in combination of two or more.

As the hydrolyzable organic hydrazine compound, a hydrolyzed product obtained by partial hydrolysis of the above hydrolyzable organic hydrazine compound can also be used. Further, as the hydrolyzable organic ruthenium compound, a polymer obtained by condensing the hydrolysis product to form an oligomer or a polymer can also be used. The hydrolyzed product or polymer can be produced by adding an acid such as hydrochloric acid, phosphoric acid, acetic acid or sulfuric acid or a base such as sodium hydroxide or sodium acetate to the hydrolyzable organic hydrazine compound.

As the antistatic agent, a polycondensate obtained by subjecting the hydrolyzable organic hydrazine compound as described above to hydrolysis or polycondensation reaction can also be used. The method of hydrolyzing the hydrolyzable organic hydrazine compound may be carried out by a conventional method. That is, the hydrolyzable organic ruthenium compound is dissolved in a predetermined amount of the organic solvent in an amount required to have a predetermined solid concentration to form a uniform solution, and hydrolyzed in the presence of a catalyst. Further, when an organic solvent is not used, the hydrolyzable organic ruthenium compound may be added in an amount required for a predetermined solid content concentration in a homogeneous solution of water and a catalyst, and hydrolysis may be carried out. In general, as long as it is in the presence of an acid or base catalyst, the addition is expected The amount of water required for the hydrolysis rate can be hydrolyzed. The catalyst for hydrolysis may be an acid such as hydrochloric acid, phosphoric acid, sulfuric acid or acetic acid, such as an alkaline hydroxide catalyst such as LiOH, NaOH or KOH, and may be used in an amount of 0.01 to 10 by weight based on the hydrolyzable organic hydrazine compound. %. The reaction temperature for hydrolysis is sufficient from room temperature to 50 ° C, and the reaction time varies depending on the reaction temperature and the amount of the catalyst, but it is generally from 1 to 24 hours. The polycondensate of the hydrolyzable organic hydrazine compound is prepared by the above hydrolysis reaction. Further, as is well known, when the polycondensate of the hydrolyzable organic hydrazine compound is gelled on the coated surface, the oxime has a plurality of hydroxyl group-containing sterol groups (Si-OH) on the surface, which is effective for exhibiting an antistatic function. . Further, since the polycondensate of the hydrolyzable organic hydrazine compound can be prepared by hydrolysis, the terminal group of the polycondensate contains an OH group, which also becomes an effective antistatic function.

The hydrolyzable organic hydrazine compound and its polycondensate may be used singly or in the form of a mixture of a hydrolyzable organic hydrazine compound and a condensate thereof. Hydrolyzable organic hydrazine compounds and condensates thereof which can be used as an antistatic agent are, for example, sold by Colcoat Co., Ltd.

The thickness of the antistatic layer 30 may be 10 nm or more and 1000 nm or less. However, from the viewpoint of thinning of the antistatic polarizing plate 100, it is preferably 800 nm or less. When the thickness of the antistatic layer 30 is less than 10 nm, the adhesion, the antistatic property, and the strength may be insufficient. When the thickness exceeds 1000 nm, the adhesion and the transparency may be insufficient, and defects such as cracks may occur.

The antistatic layer 30 can be formed, for example, by applying a coating liquid containing an antistatic agent to the surface of the polarizing plate 10. The coating liquid usually contains an antistatic agent, a solvent (including water), and a curable resin as required. The curable resin is a curable resin which is cured by irradiation with heat or active energy rays, such as a (meth)acrylic compound. On the surface of the polarizing plate 10, activation treatment such as corona treatment, plasma treatment, primer treatment, anchor coating treatment, or the like may be performed as needed. Thereby, the adhesion between the antistatic layer 30 and the polarizing plate 10 is improved, and the wettability of the coating liquid to the polarizing plate 10 is improved.

The solvent is used to adjust the concentration, viscosity, film thickness of the coating layer, and the like of the coating liquid. The solvent to be used may be appropriately selected, and examples thereof include methanol, ethanol, propanol, isopropanol, n-butanol, 2-butanol, isobutanol, and a third-butanol alcohol such as 2 - ethoxyethanol, 2-butoxyethanol, 3-methoxypropanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol alkoxy alcohols, such as a ketone alcohol of acetol, such as acetone, methyl ethyl ketone, a ketone of methyl isobutyl ketone, an aromatic hydrocarbon such as toluene or xylene, such as an ester of ethyl acetate or butyl acetate, such as two An alkane, an ether of tetrahydrofuran, and the like. The amount of the solvent to be used is appropriately selected depending on the material and shape of the polarizing plate 10, the coating method, the film thickness of the coating film, and the like, and is usually about 20 to 10,000 parts by weight based on 100 parts by weight of the total amount of the antistatic agent.

Examples of the method of applying the coating liquid to the surface of the polarizing plate 10 include a micro gravure coating method, a roll coating method, a dip coating method, a flow coating method, a spin coating method, a die coating method, and a casting transfer method. , spraying method, etc.

Then, the coating layer can also be dried. The drying temperature varies depending on the type of the solvent and the adherend, but is usually from 25 to 120 ° C, more preferably from about 30 to 110 ° C. Further, the hydrolyzable organic hydrazine compound may be hydrolyzed and condensed by heating the coating layer after drying or before drying. The heating temperature is usually about 50 to 120 ° C, and the heating time is usually 1 minute to About 5 hours. When the coating layer contains a solvent, the heat treatment may be carried out directly in a state in which the coating film contains a solvent, or may be carried out after volatilization of the solvent.

(4) Adhesive layer

The adhesive layer 40 functions to adhere to a member (including the metal layer 60, the cover layer 50, and the like) in which the antistatic polarizing plate 100 is adjacent to each other.

Examples of the adhesive composition used for forming the adhesive layer 40 include a (meth)acrylic adhesive composition, an amine ester adhesive composition, a polyoxynoxy adhesive composition, and a polyester adhesive. The composition of the agent, the composition of the polyamine-based adhesive, the composition of the polyether-based adhesive, the composition of the fluorine-based adhesive, and the composition of the rubber-based adhesive. Among them, a (meth)acrylic adhesive using a (meth)acrylic resin as a matrix polymer is preferably used from the viewpoints of transparency, adhesion, reliability, and reworkability.

A specific example of a (meth)acrylic resin which can be suitably used as a matrix polymer of a (meth)acrylic adhesive composition is a (meth)acrylic resin (A-1), and the above (meth)acrylic acid The resin (A-1) is a polymer having a structural unit derived from (meth) acrylate represented by the following formula (I) as a main component (containing 50% by weight or more):

In the formula (I), R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 1 to 14 carbon atoms which may be substituted by an alkoxy group having 1 to 10 carbon atoms, or an alkyl group which may be 1 to 10 carbon atoms. An aryl group substituted with an aryl group having 7 to 21 carbon atoms. R ^{2 is} preferably an alkyl group having 1 to 14 carbon atoms which may be substituted by an alkoxy group having 1 to 10 carbon atoms.

The (meth) acrylate represented by the formula (I) may, for example, be an alkyl (meth) acrylate, and specific examples thereof include, for example, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, n-octyl acrylate. The alkyl moiety of lauryl acrylate is a linear alkyl acrylate; for example, isopropyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, alkyl moiety is branched acrylic An alkyl ester; such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, n-octyl methacrylate, and the alkyl moiety of lauryl methacrylate are linear An alkyl methacrylate; such as isopropyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, isooctyl methacrylate, alkyl moiety of branched alkyl methacrylate Ester and the like. The alkyl group of the alkyl (meth)acrylate preferably has a carbon number of from 1 to 8, more preferably from 1 to 6.

Specific examples of the (meth) acrylate represented by the formula (I) when R ² is an alkyl group substituted by an alkoxy group, that is, ² -methoxy acrylate Ester, ethoxymethyl acrylate, 2-methoxyethyl methacrylate, ethoxymethyl methacrylate, and the like. The alkyl group in the above alkoxyalkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms. The alkoxy group in the above alkoxyalkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. When R ² is an aralkyl group having 7 to 21 carbon atoms, specific examples of the (meth) acrylate represented by the formula (I) include benzyl acrylate, benzyl methacrylate and the like. The above aralkyl group preferably has 7 to 11 carbon atoms.

The (meth) acrylate represented by the formula (I) may be used alone or in combination of two or more. Among them, the (meth) acrylate is preferably an alkyl (meth) acrylate, more preferably an alkyl acrylate, and even more preferably a n-butyl acrylate. The (meth)acrylic resin (A-1) preferably contains 50% by weight or more of n-butyl acrylate in all of the monomers constituting the (meth)acrylic resin (A-1). Of course, in addition to n-butyl acrylate, a (meth) acrylate represented by the formula (I) other than n-butyl acrylate may be used in combination.

The (meth)acrylic resin (A-1) is usually a copolymer of at least one other monomer represented by the (meth) acrylate of the above formula (I) and a monomer having a polar functional group. A single system having a polar functional group is preferably a (meth)acrylic compound having a polar functional group. Examples of the polar functional group include a heterocyclic group including a free carboxyl group, a hydroxyl group, an amine group, and an epoxy group.

Specific examples of the monomer having a polar functional group include a monomer having a free carboxyl group such as (meth)acrylic acid or β-carboxyethyl (meth)acrylate; such as 2-hydroxyethyl (meth)acrylate; 3-hydroxypropyl methacrylate, 4-hydroxybutyl (meth) acrylate, 2-(2-hydroxyethoxy)ethyl (meth) acrylate, 2- or 3-chloro (meth) acrylate a hydroxy-containing alkyl ester of a (meth) acrylate of 2-hydroxypropyl group, or an incomplete ester of a (meth)acrylic acid such as diethylene glycol mono(meth)acrylate, and an incomplete esterified product of (meth)acrylic acid a monomer of a hydroxyl group; such as acryloylmorpholine, vinyl caprolactam, N-vinyl-2-pyrrolidone, vinylpyridine, tetrahydrofurfuryl (meth)acrylate, caprolactone modification a monomer having a heterocyclic group; tetrahydrofurfuryl acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, glycidyl (meth) acrylate, 2,5-dihydrofuran; A single amine group having a different amino group than a hetero ring, such as aminoethyl (meth) acrylate, N,N-dimethylaminoethyl (meth) acrylate, or dimethylaminopropyl (meth) acrylate Body and so on. The monomer having a polar functional group may be used alone or in combination of two or more.

Among the above, from the viewpoint of the reactivity of the (meth)acrylic resin (A-1), it is preferred to use a monomer having a hydroxyl group as a constituent of the (meth)acrylic resin (A-1). One of the monomers of a polar functional group. In addition to the monomer having a hydroxyl group, it is also effective to use a monomer having other polar functional groups, for example, a monomer having a free carboxyl group. From the viewpoint of the adhesion between the adhesive layer 40 and the antistatic polarizing plate 100 and the durability of the adhesive layer 40, a single system having a hydroxyl group is preferably a (meth) acrylate having a hydroxyl group, and contains The alkyl hydroxy group of (meth)acrylic acid is more preferred. In the alkyl group containing a hydroxyl group of (meth)acrylic acid, the alkyl group preferably has a carbon number of from 1 to 8, more preferably from 1 to 6.

The (meth)acrylic resin (A-1) may further contain a monomer derived from one olefinic double bond and at least one aromatic ring in the molecule (however, it is represented by the above formula (I) A structural unit other than the monomer and the above monomer having a polar functional group. A suitable example of the (meth)acrylic compound having an aromatic ring is exemplified. A suitable example of the (meth)acrylic compound having an aromatic ring, such as a phenoxyethyl group-containing (meth) acrylate having an aryloxyalkyl group as shown by the following formula (II) ester.

The monomer having one olefinic double bond and at least one aromatic ring in the molecule, such as a phenoxyethyl group-containing (meth) acrylate, may be used alone or in combination of two or more.

In the above formula (II), R ³ represents a hydrogen atom or a methyl group, n represents an integer of 1 to 8, and R ⁴ represents a hydrogen atom, an alkyl group, an aralkyl group or an aryl group. When R ⁴ is an alkyl group, the carbon number thereof may be about 1 to 9; when it is an aralkyl group, the carbon number thereof may be about 7 to 11, or when it is an aryl group, the carbon number thereof may be about 6 to 10.

In the formula (II), examples of the alkyl group having 1 to 9 carbon atoms constituting R ⁴ include a methyl group, a butyl group and a decyl group; and examples of the aralkyl group having 7 to 11 carbon atoms include a benzyl group and a benzene group. Ethyl, naphthylmethyl or the like; and examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a tolyl group, and a naphthyl group.

Specific examples of the phenoxyethyl group-containing (meth) acrylate represented by the formula (II) include 2-phenoxyethyl (meth)acrylate and 2-(2-phenoxy) (meth)acrylate. (Ethyl ethoxy) ethyl ester, ethylene oxide modified (meth) acrylate of nonyl phenol, 2-(o-phenylphenoxy) ethyl (meth) acrylate, etc. Wherein the (meth) acrylate containing a phenoxyethyl group includes 2-phenoxyethyl (meth)acrylate, 2-(o-phenylphenoxy)ethyl (meth)acrylate, and / or 2-(2-phenoxyethoxy)ethyl (meth)acrylate is preferred.

The (meth)acrylic resin (A-1) is a structure derived from the (meth) acrylate represented by the above formula (I) based on the total amount of the solid content. The ratio of the unit is preferably from 60 to 99.9% by weight, more preferably from 80 to 99.6% by weight; the ratio of the structural unit derived from the monomer having a polar functional group is preferably from 0.1 to 20% by weight, more It is preferably 0.4 to 10% by weight; the ratio of the structural unit derived from a monomer having one olefinic double bond and at least one aromatic ring in the molecule is preferably from 0 to 40% by weight, more preferably contained 6 to 12% by weight.

The (meth)acrylic resin (A-1) may further contain a structural unit derived from a monomer other than the following monomer (hereinafter also referred to as "another monomer"): a methyl group represented by the formula (I) An acrylate, a monomer having a polar functional group, and a monomer having one olefinic double bond and at least one aromatic ring in the molecule. Specific examples of the other monomer include a structural unit derived from a (meth) acrylate having an alicyclic structure in a molecule, a structural unit derived from a styrene monomer, and a structural unit derived from a vinyl monomer. And a structural unit derived from a monomer having a plurality of (meth) acrylonitrile groups in the molecule, a structural unit derived from a (meth) acrylamide monomer, and the like. The other monomers may be used alone or in combination of two or more.

The alicyclic structure has a carbon number of usually 5 or more, preferably about 5 to 7. Specific examples of the (meth) acrylate having an alicyclic structure include: isodecyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, (methyl) Cyclodecyl acrylate, methylcyclohexyl (meth) acrylate, trimethylcyclohexyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate Phenyl ester, α-ethoxycyclohexyl acrylate, and the like.

Specific examples of the styrene monomer include: styrene; Such as methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl styrene, g Alkyl styrene of styrene and octyl styrene; halogenated styrene such as fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, iodine styrene; nitrostyrene, acetyl styrene , methoxy styrene, divinyl benzene, and the like.

Specific examples of the vinyl monomer include: vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl acetate of lauric acid; such as vinyl chloride or vinyl bromide a halogenated ethylene; a vinylidene halide such as vinylidene chloride; a nitrogen-containing aromatic vinyl such as vinyl pyridine, vinyl pyrrolidone or vinyl carbazole; such as butadiene, isoprene, chloroprene A conjugated diene monomer; acrylonitrile, methacrylonitrile, or the like.

Specific examples of the monomer having a plurality of (meth) acrylonitrile groups in the molecule include, for example, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylic acid. Ester, 1,9-nonanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylic acid Ester, tripropylene glycol di(meth) acrylate having two (meth) acrylonitrile groups in the molecule; for example, trimethylolpropane tri(meth) acrylate having 3 in the molecule ( A monomer such as a methyl methacrylate group.

Specific examples of the (meth) acrylamide compound include: N-methylol (meth) acrylamide, N-(2-hydroxyethyl) (meth) acrylamide, N-(3-hydroxyl Propyl) (meth) acrylamide, N-(4-hydroxybutyl)(meth) acrylamide, N-(5-hydroxypentyl)(meth) acrylamide, N-(6- Hydroxyhexyl) (meth) propylene Indoleamine, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-(3 -Dimethylaminopropyl)(meth)acrylamide, N-(1,1-dimethyl-3-oxobutyl)(meth)acrylamide, N-[2-( 2-Sideoxy-1-imidazolidinyl)ethyl](meth)acrylamide, 2-propenylamino-2-methyl-1-propanesulfonic acid, N-(methoxymethyl) Acrylamide, N-(ethoxymethyl)(meth)acrylamide, N-(propyloxymethyl)(meth)acrylamide, N-(1-methylethoxymethyl) (Meth) acrylamide, N-(1-methylpropoxymethyl)(meth) acrylamide, N-(2-methylpropoxymethyl)(methyl) decylamine [alias: N-(isobutoxymethyl)(methyl)acrylamide], N-(butoxymethyl)(meth)acrylamide, N-(1,1-dimethylethyl) Oxymethyl)(meth)acrylamide, N-(2-methoxyethyl)(meth)acrylamide, N-(2-ethoxyethyl)(methyl)propenamide , N-(2-propoxyethyl)(meth)acrylamide, N-[2-(1-methylethoxy)ethyl](methyl)propenamide, N-[2- (1-methylpropoxy)ethyl](methyl)propenylamine, N-[2-(2-A Propoxy)ethyl](meth)acrylamide [alias: N-(2-isobutoxyethyl)(methyl) acrylamide], N-(2-butoxyethyl) ( Methyl) acrylamide, N-[2-(1,1-dimethylethoxy)ethyl](methyl) acrylamide, and the like.

The (meth)acrylic resin (A-1) is usually contained in an amount of from 0 to 20% by weight, preferably from 0 to 0, based on the total amount of the solid content. 10% by weight.

From the viewpoint of the adhesion between the adhesive layer and the adjacent member, the (meth)acrylic resin (A-1) has a weight average molecular weight in terms of standard polystyrene by gel permeation chromatography (GPC) ( Mw) is preferably 500,000 or more, and more preferably 600,000 or more. (meth)acrylic resin (A-1) Mw is usually less than 1.7 million.

The matrix polymer of the (meth)acrylic adhesive composition may contain two or more kinds of (meth)acrylic resins (A-1). Further, the matrix polymer may contain a (meth)acrylic resin different from the (meth)acrylic resin (A-1) in addition to the (meth)acrylic resin (A-1), for example, having the formula ( a (meth)acrylic resin (A-2) derived from a (meth) acrylate structural unit and having no polar functional group, or a methyl group derived from the above formula (I) The (meth)acrylic resin (A-3) having a structural unit of acrylate as a main component and having a Mw of from 0.5 to 120,000.

The adhesive composition may further contain a crosslinking agent (B). The crosslinking agent is a compound which reacts with a matrix polymer such as a (meth)acrylic resin, particularly a structural unit derived from a monomer having a polar functional group, to crosslink the matrix polymer. Specific examples thereof include an isocyanate compound, an epoxy compound, an aziridine compound, and a metal chelate compound. Among these, the isocyanate compound, the epoxy compound, and the aziridine compound have at least two functional groups capable of reacting with a polar functional group in the matrix polymer in the molecule. The crosslinking agent (B) may be used alone or in combination of two or more.

The isocyanate compound is a compound having at least two isocyanato groups (-NCO) in the molecule. Specific examples of the isocyanate-based compound include methylphenyl diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, benzoyl diisocyanate, hydrogenated xylylene diisocyanate, and diphenylmethane Isocyanate, hydrogenated diphenylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, and the like. and Further, an adduct obtained by reacting the isocyanate compound with a polyol such as glycerin and trimethylolpropane, and an isocyanate compound as a dimer or a trimer may also be used as a crosslinking agent (B). ).

The epoxy compound is a compound having at least two epoxy groups in the molecule. Specific examples of the epoxy compound include: bisphenol A type epoxy resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerol triglycidyl ether 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, N,N-diglycidylaniline, N,N,N',N'-tetraglycidyl- M-xylylenediamine, 1,3-bis(N,N'-diglycidylaminomethyl)cyclohexane, and the like.

The aziridine-based compound is also called a compound of ethyleneimine having at least two three-membered ring-shaped cells in the molecule, and the three-membered ring-shaped skeleton is composed of one nitrogen atom and two carbon atoms. Specific examples of the aziridine-based compound include: diphenylmethane-4,4'-bis(1-aziridinecarboxamide), toluene-2,4-bis(1-aziridinecarboxamide), Triethylene melamine, isodecyl bis-1-(2-methylaziridine), gin-1-aziridine phosphine oxide, hexamethylene-1,6-bis(1-aziridine) Carboxylamidine), trimethylolpropane-gin-β-aziridine propionate, tetramethylolmethane-para-β-aziridine propionate, and the like.

Specific examples of the metal chelate compound include: a polyvalent metal such as aluminum, iron, copper, zinc, tin, titanium, nickel, ruthenium, magnesium, vanadium, chromium, and zirconium coordinated with ethyl acetoacetate and ethyl acetate Ester compounds and the like.

The content ratio of the crosslinking agent (B) is 100 parts by weight based on 100 parts by weight of the solid content of the matrix polymer (when two or more are used) It is usually 0.05 to 5 parts by weight, preferably 0.1 to 5 parts by weight. When the content of the crosslinking agent (B) is 0.05 parts by weight or more, the durability of the pressure-sensitive adhesive layer tends to increase.

The adhesive layer 40 may contain an antistatic agent. As the antistatic agent, conductive fine particles, an ion conductive composition containing an electrolyte salt and an organic polysiloxane, an ionic compound, or the like can be used, and the conductive fine particles are metal fine particles, metal oxide fine particles or coated with a metal. Wait for the particles.

When the adhesive layer 40 contains an ionic compound, the compounding ratio of the ionic compound is preferably from 0.1 to 8 parts by weight based on 100 parts by weight of the solid content of the matrix polymer (in total of two or more kinds). More preferably, it is 0.2 to 5 parts by weight. When the content of the ionic compound is 0.2 parts by weight or more, it is advantageous in improving the antistatic property, and when it is 8 parts by weight or less, it is advantageous in improving the durability of the adhesive layer. However, when the antistatic polarizing plate 300 with the adhesive layer is applied to the On-Cell type touch input type liquid crystal display device, the touch input element is formed to suppress the ionic compound contained in the adhesive layer 40. The corrosion of the metal-containing layer is preferably 0.2 parts by weight or less, more preferably 0.1 parts by weight or less, still more preferably 0.05 parts by weight or less based on 100 parts by weight of the solid content of the matrix polymer. It is particularly preferably 0.01 parts by weight or less.

In the adhesive composition, other ingredients may be formulated as needed. Other components which can be adjusted include a decane coupling agent, a crosslinking catalyst, a weathering stabilizer, a binder, a plasticizer, a softener, a dye, a pigment, an inorganic filler, a resin other than a matrix polymer, an organic bead, etc. Light diffusing micro Particles, rust inhibitors, etc. Further, an ultraviolet curable compound is blended in the adhesive composition to form an adhesive layer, which is then cured by irradiation with ultraviolet rays, and can also be used to form a harder adhesive layer.

Examples of the rust inhibitor include a benzotriazole-based compound and other triazole-based compounds; a benzothiazole-based compound and another thiazole-based compound; a benzimidazole-based compound; another imidazole-based compound; an imidazoline-based compound; and a quinoline-based compound. a compound; a pyridine compound; a pyrimidine compound; an anthraquinone compound; an amine compound; a urea compound; a sodium benzoate; a benzylsulfonyl compound; a di-second-butyl sulfide;

The adhesive composition may contain a rust inhibitor, and the content thereof is preferably as small as possible, and is a solid component with respect to the matrix polymer constituting the adhesive composition (when two or more types are used) The content of the rust inhibitor is usually 15 parts by weight or less, preferably 0.01 parts by weight or less, based on 100 parts by weight, and preferably 0.

The adhesive composition is usually prepared as an adhesive liquid obtained by dissolving or dispersing a compounding component by containing an organic solvent. The organic solvent is preferably selected depending on the kind of the matrix polymer. Specific examples of the organic solvent include aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as hexane, heptane and pentane; ketones such as methyl ethyl ketone and methyl isobutyl ketone; Ethyl ester, ester of butyl acetate. The concentration of the matrix polymer in the adhesive liquid is usually from 3 to 40% by weight.

The method of forming the adhesive layer 40 on the antistatic layer 30 may be performed by, for example, applying a spacer film as a substrate, applying the above adhesive composition to form an adhesive layer 40, and transferring the obtained adhesive layer 40 to the adhesive layer 40. A method of applying the surface of the antistatic layer 30 to the surface of the antistatic layer 30 to form the adhesive layer 40 directly on the surface of the antistatic layer 30, and a method of bonding the separator to the outside of the adhesive 40. Further, after the adhesive layer 40 is formed on one of the separator films, another separator film may be further bonded to the pressure-sensitive adhesive layer 40 to form a double-sided separator film type adhesive sheet. Such an adhesive sheet can be attached to the antistatic layer 30 by peeling off the separation film on one side as needed.

The separator is, for example, a film made of various resins such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyarylate, polypropylene or polyethylene as a substrate. On the joint surface of the substrate and the adhesive layer 40, a release treatment such as a polyoxygen treatment is applied.

The adhesive layer 40 obtained by applying an adhesive solution and drying the solvent is aged for about 1 to 20 days in an environment of a temperature of 23 ° C and a relative humidity of 65%, and the reaction of the crosslinking agent is sufficiently carried out, and then used. Attached to a liquid crystal cell, a touch input element, and the like.

The thickness of the adhesive layer 40 is preferably 10 to 45 μm, more preferably 15 to 35 μm. The thickness of the adhesive layer 40 is 45 μm or less, which is advantageous for adhesion to an adjacent member. Further, when the thickness is 10 μm or more, the followability of the adhesive layer 40 to the dimensional change of the adjacent members becomes good.

(5) Metal-containing layer

As the metal-containing layer 60, a film of ITO (indium/tin oxide), tin/bismuth oxide, or the like, or aluminum, gold, silver, copper, titanium, or the like can be used. A metal-containing layer composed of a thin film of a metal such as palladium, chromium, nickel, tungsten, platinum, iron, indium, tin, antimony, bismuth, molybdenum or the like. Among them, from the viewpoint of excellent electrical conductivity and low cost, it is preferred to use aluminum, gold, silver, copper, titanium, palladium, chromium, nickel, tungsten, platinum, iron, indium, tin, antimony, antimony, A metal-containing layer composed of a thin film of a metal such as ruthenium, molybdenum or the like. The metal containing layer 60 may be a continuous film formed on the entire surface of the light-transmitting substrate 70, or may be a metal wiring layer formed of a metal mesh.

The method for forming the metal-containing layer 60 is not particularly limited, and may be formed on the surface of the light-transmitting substrate 70 by a vacuum deposition method, an ion beam evaporation method, a sputtering method, an ion plating method, or the like. Further, examples of the method of forming the metal-containing layer 60 include an inkjet printing method and a gravure printing method. The metal-containing layer 60 may be formed by providing the metal-containing layer 60 obtained by processing the metal foil.

The metal-containing layer 60 formed by the sputtering method is generally inferior in corrosion resistance as compared with the metal-containing layer 60 obtained by processing the metal foil, but the optical laminate of the present invention is used only by The metal-containing layer formed by such a sputtering method can also suppress corrosion. Therefore, the optical laminate of the present invention is particularly effective when the metal-containing layer 60 is formed by a sputtering method.

The thickness of the metal-containing layer 60 is preferably 3 μm or less, more preferably 1 μm or less, still more preferably 0.8 μm or less, and usually 0.01 μm or more in terms of thinning. Even in the metal-containing layer 60 having such a thickness, the corrosion of the metal-containing layer 60 can be suppressed in the optical layered body of the present invention.

When the metal-containing layer 60 is a metal-containing wiring layer made of a metal mesh, the line width is usually 10 μm or less, preferably 5 μm or less. More preferably, it is 3 μm or less, and usually 0.5 μm or more. Even in the case of such a metal-containing layer 60 having a narrow line width, the optical layered body of the present invention can suppress corrosion of the metal-containing layer 60.

According to the optical layered body of the present invention, the metal-containing layer 60 is, for example, a metal-containing layer having a thickness of 3 μm or less and a line width of 10 μm or less, or a metal having a thickness of 3 μm or less and a line width of 10 μm or less, and formed by sputtering. The wiring layer (metal mesh) also suppresses corrosion.

Further, when the optical layered body 400, 500 is applied to an On-Cell type touch input type liquid crystal display device or the like, it can also be used as a metal mesh formed by processing a metal into a fine mesh shape on the light-transmitting substrate 70. Containing a metal layer 60. As the metal forming the metal mesh, aluminum, gold, silver, copper, titanium, palladium, chromium, nickel, tungsten, platinum, iron, indium, tin, antimony, bismuth, antimony, molybdenum, or the like may be used.

As the metal forming the metal mesh, among the metals, aluminum, copper, silver, or an alloy of one or more selected metals is preferable from the viewpoint of excellent conductivity and cost. . The metal component constituting the metal mesh is preferably composed mainly of aluminum, copper and/or silver, that is, the total content of these is preferably 30% by weight or more, more preferably 50% by weight or more.

When the metal containing layer 60 is a metal mesh, the metal containing layer 60 may have a single layer structure or a multilayer structure of two or more layers. The metal-containing layer (metal mesh) of the multilayer structure may, for example, be a metal-containing layer (metal mesh) having a three-layer structure represented by molybdenum/aluminum/molybdenum.

It can also have a metal containing layer 60 and gold by ITO It is a transparent electrode layer composed of an oxide.

When the metal-containing layer 60 is patterned into a metal wiring layer (metal mesh) of a predetermined shape as shown in FIG. 3, when the adhesive layer 40 is directly laminated on the metal wiring layer, The adhesive layer 40 may also have a portion that does not contact the metal containing layer 60 but directly contacts the light transmissive substrate 70 under the metal containing layer 60.

When the metal-containing layer 60 contains at least one metal element selected from the group consisting of aluminum, copper, silver, iron, tin, nickel, and indium, when used together with the adhesive layer 40 containing an ionic compound, optical The use of the laminates 400, 500, 600 has the concern of corroding the metal-containing layer 60. According to the optical layered body 400, 500, 600 of the present invention, since the antistatic layer 30 is contained, the adhesive layer 40 can be made to contain no ionic compound, and the content of the ionic compound in the adhesive layer 40 can be greatly reduced, thereby preventing Corrosion of the metal containing layer 60.

(6) coating layer

The cover layer 50 has a function of protecting the transparent electrode layer 60. Any coating layer 50 may be used as long as it does not impair the function of the transparent electrode layer 60, and any known curable resin can be used. The resin constituting the coating layer 50 may, for example, be the same resin as the active energy ray-curable adhesive for the adhesive layer between the protective films 21 and 22 and the polarizing film 11. Specifically, a cured product of an active energy ray curable resin such as a polyfunctional (meth) acrylate, an amine ester (meth) acrylate, a polyester (meth) acrylate, or an epoxy (meth) acrylate may be used. Composition.

(7) Translucent substrate

A glass substrate can be used for the light-transmitting substrate 70. The material of the glass substrate is, for example, soda lime glass glass, low alkali glass, alkali-free glass, or the like. The light-transmitting substrate 70 may be a transparent substrate constituting a liquid crystal cell of a touch input type liquid crystal display device.

(8) Liquid crystal display device

The optical laminate of the present invention can be assembled and used in a touch input type liquid crystal display device. The touch input type liquid crystal display device can be an Out-Cell type, an On-Cell type, or an In-Cell type. The operation of the touch input can be a resistive film type, or an electrostatic capacitance type such as a surface type electrostatic capacitance type or a projection type electrostatic capacitance type. The optical layered body of the present invention may be disposed on the viewing side of the liquid crystal cell constituting the touch input type liquid crystal display device, or may be disposed on the back side (usually on the backlight side) or on the side of the viewing side and the back side. square. The driving method of the liquid crystal cell is not particularly limited, and examples thereof include a TN type, a VA type, an IPS type, a multi-domain type, and an OCD method.

(Example)

The invention will be further specifically described by way of examples. However, the invention is not limited to the embodiments. The following are the "parts" and "%" of the usage and the content, and are based on weight unless otherwise stated.

[Production of optical laminate] (production of polarizer)

A polyvinyl alcohol film having a thickness of 30 μm (average degree of polymerization of about 2400, a degree of saponification of 99.9 mol% or more) was extended to about 5 times by the longitudinal direction of the dry stretching, and then kept in a tight state, impregnated with pure water at 60 ° C. After a minute, it was immersed in an aqueous solution of iodine/potassium iodide/water at a weight ratio of 0.05/5/100 at 28 ° C for 60 seconds. Thereafter, it was immersed in an aqueous solution of 72 ° C in a weight ratio of potassium iodide/boric acid/water of 8.5/8.5/100 for 300 seconds. Subsequently, the mixture was washed with pure water at 26 ° C for 20 seconds, and then dried at 65 ° C to obtain a polarizer having a thickness of 11 μm in which oriented iodine was adsorbed on a polyvinyl alcohol film.

<Preparation of protective film>

Protective film A: A cyclic polyolefin-based resin film (thickness: 23 μm) manufactured by Zeon Co., Ltd., Japan was prepared.

Protective film B: A triacetyl cellulose film (thickness: 25 μm) manufactured by Konica Minolta Opto Co., Ltd., which was subjected to saponification treatment on the surface.

<Preparation of coating liquid for antistatic layer>

Coating liquid for antistatic layer # 1: Preparation of a coating liquid containing a hydrolyzable organic hydrazine compound ("colcoat N-103X" manufactured by Colcoat Co., Ltd., solid content concentration: 2% by weight, solvent: 2-propanol (40) % by weight), 1-butanol (50% by weight), ethanol (4% by weight), water (4% by weight).

Coating liquid for antistatic layer # 2: A solution containing a polythiophene-based conductive polymer ("verazol WED-SM" manufactured by Amika Chemical Co., Ltd., a solid concentration of 1.5%, a solvent of water) and polyvinyl alcohol Water soluble The liquid (solid content concentration: 6.2%) was mixed at a ratio of 1:3 to prepare a coating liquid. The solid content concentration in the coating liquid was 2.5%.

Coating liquid for antistatic layer #3: A solution containing a polythiophene-based conductive polymer ("Denatron P-502RG" manufactured by Nagasechemtex Co., Ltd., a solid concentration of 4%, a solvent of water) and a diluent ( A coating liquid was prepared by mixing water and 2-propanol in a volume ratio of 2:8 and diluting it by 11 times. The solid content concentration in the coating liquid was 0.36%.

<Preparation of Adhesive Layer>

Adhesive layer #7: An adhesive layer (25 μm thick, manufactured by Lintec Co., Ltd.) to which a separator film is attached to both surfaces is prepared.

Adhesive layer # A: Adhesive layer # A was prepared in the following order.

In a reaction vessel equipped with a cooling tube, a nitrogen gas introduction tube, a thermometer, and a stirrer, 81.8 parts of ethyl acetate, 70.4 parts of butyl acrylate, 20.0 parts of methyl acrylate, 8.0 parts of 2-phenoxyethyl acrylate, and acrylic acid 2 were charged. A mixed solution of 1.0 part of hydroxyethyl ester and 0.6 part of acrylic acid, replacing the air in the apparatus with nitrogen to form oxygen-free, and raising the internal temperature to 55 °C. Thereafter, a total amount of a solution of 0.14 parts of azobisisobutyronitrile as a polymerization initiator dissolved in 10 parts of ethyl acetate was added. One hour after the addition of the initiator, ethyl acetate was continuously added to the reaction vessel at an addition rate of 17.3 parts/hour in such a manner that the concentration of the acrylic resin was 35%, while maintaining the internal temperature at 54 to 56 ° C for 12 hours. Finally, ethyl acetate was added to adjust the concentration of the acrylic resin to 20%. The resulting acrylic resin is polymerized by GPC The weight average molecular weight Mw in terms of styrene was 1.42 million, and Mw/Mn was 5.2. This was taken as the acrylic resin A.

With respect to 100 parts of the solid content of the acrylic resin A, 2.0 parts of the following ionic compound, 0.5 part of a crosslinking agent (solid content), and 0.5 part of a decane compound were mixed in the amounts indicated, and ethyl acetate was further added so that The solid content concentration was 13% as an adhesive composition.

(ionic compound)

N-octyl-4-methylpyridinium hexafluorophosphate (having the structure of the following formula, melting point 44 ° C)

(crosslinking agent)

CORONATE L: an ethyl acetate solution (solid content concentration: 75%) of a trimethylolpropane adduct of methyl phenyl diisocyanate manufactured by Polyurethane Co., Ltd., Japan.

(decane compound)

KBM-403: 3-glycidoxypropyltrimethoxydecane (liquid) manufactured by Shin-Etsu Chemical Co., Ltd.

The obtained adhesive composition was applied to the release-treated polyparaphenylene by a coater so that the thickness after drying became 20 μm. A release film of a polyethylene dicarboxylate film ("PLR-382052" manufactured by Lintec Co., Ltd.; hereinafter also referred to as a separator film) was dried at 100 ° C for 1 minute to obtain a sheet-like adhesive layer # A.

<Modulation of water-based adhesive>

Ethyl acetonitrile modified polyvinyl alcohol ("GOHSEFIMER Z-200" manufactured by Nippon Synthetic Chemical Co., Ltd., viscosity of 4% aqueous solution = 12.4 mPa.sec, saponification degree = 99.1 mol%) was dissolved in pure Water, a 10% strength aqueous solution was prepared. Mixing the ethyl hydrazide-based modified polyvinyl alcohol aqueous solution with the sodium glyoxylate as a crosslinking agent: the latter has a solid weight ratio of 1:0.1, and further 100 parts with respect to water, The water-based adhesive was prepared by diluting with a pure water in a manner of making 2.5 parts of the modified polyvinyl alcohol.

<Preparation of a light-transmitting substrate with a metal layer>

A layer having an aluminum layer having a thickness of 500 nm was prepared on the surface of the glass substrate.

<Example 1>

An optical layered body 400 having the same layer structure as that of Fig. 1 was produced in the following order. First, the water-based adhesive was applied to both sides of the polarizer 11 in a gas atmosphere of 23 ° C, and the respective corona-treated surfaces were used as an adhesive device ("LPA3301" manufactured by FUJIPLA Co., Ltd.). The protective film A subjected to the corona treatment is bonded to one of the adhesive application surfaces, and the corona treatment is performed, in such a manner that the polarizing film 11 is bonded to the surface. The protective film B is bonded to the other adhesive-coated surface. The obtained product was dried at 80 ° C for 5 minutes to prepare a polarizing plate.

Then, the exposed surface of the protective film A was subjected to a corona treatment, and the coating liquid for an antistatic layer was applied to a thickness of 180 nm after drying using a coater (a bar coater, manufactured by First Chemical Co., Ltd.). After the cloth, use kapton adhesive tape to attach to the glass. The obtained product was placed in an oven at a temperature of 120 ° C for 1 minute, and then taken out from the oven and allowed to stand at a temperature of 23 ° C and a relative humidity of 50% for 24 hours. Thereby, the antistatic layer 30 is formed on the surface of the protective film A.

Then, after removing one of the separator films as the adhesive layer #7 of the adhesive layer 40, the antistatic layer 30 is bonded to the surface of the exposed adhesive layer 40 to form an adhesive layer. Electrostatic polarizing plate 300.

Next, after peeling off the other separator film of the adhesive layer #7, the light-transmitting substrate (the light-transmitting substrate 70 having the metal layer 60 on which the aluminum layer is formed on the main surface) is attached thereto. The metal-containing layer 60 side was bonded to the surface of the adhesive layer 40 exposed by peeling, and subjected to pressure bonding treatment at a temperature of 50 ° C and a pressure of 5 kg/cm ² (490.3 kPa) for 20 minutes to prepare an optical layered body.

<Example 2>

An optical laminate was produced in the same manner as in Example 1 except that the coating liquid #2 for the antistatic layer was used instead of the coating liquid #1 for the antistatic layer and the thickness was 225 nm after drying. .

<Example 3>

An optical layer was produced in the same manner as in Example 1 except that the coating liquid #1 for the antistatic layer was used instead of the coating liquid #1 for the antistatic layer and the thickness was 324 nm after drying. body.

<Example 4>

An optical layered body 500 having the same layer structure as that of Fig. 2 was produced in the following order. An antistatic polarizing plate 300 with an adhesive layer was produced in the same manner as in Example 1. A coating layer made of an acrylic resin having a thickness of 2 μm is formed on the metal-containing layer 60 of the light-transmitting substrate (the light-transmissive substrate 70 having the metal layer 60 on which the aluminum layer is formed on the main surface). A laminate of the light-transmitting substrate 70 and the metal-containing layer 60 and the coating layer 50 is obtained.

After peeling off the other separator film of the adhesive layer #7, the layered body is bonded to the surface of the adhesive layer 40 exposed by peeling with the coating layer 50 side at a temperature of 50 ° C and a pressure of 5 kg / cm. ² (490.3 kPa) was subjected to a pressure bonding treatment for 20 minutes to prepare an optical laminate.

<Comparative Example 1>

A polarizing plate was produced in the same manner as in Example 1. Next, after bonding the surface of the adhesive layer A of the adhesive layer A to the surface opposite to the separator (adhesive surface) by the laminator, the temperature is 23 ° C and the relative humidity is 65%. On the 7th day of aging, a polarizing plate with an adhesive layer was obtained.

Next, after peeling off the separator film of the adhesive layer #A, the light-transmitting substrate (the light-transmitting substrate 70 having the metal layer 60 on which the aluminum layer is formed on the main surface) is attached to the metal-containing layer The 60 side was bonded to the surface of the exposed adhesive layer by peeling, and pressure-bonding treatment was carried out for 20 minutes at a temperature of 50 ° C and a pressure of 5 kg/cm ² (490.3 kPa) to prepare an optical layered product.

<Comparative Example 2>

A laminate was produced in the same manner as in Example 1 except that the antistatic layer 30 was not formed on the surface of the protective film 22.

[assessment] (surface resistance)

The surface of the polarizing plate (the surface of the antistatic layer 30 or the surface of the protective film 22) before the adhesive layer 40 is bonded, and the adhesive layer 40 is bonded, and the light-transmitting substrate with the metal layer is attached thereto. The surface of the polarizing plate with the adhesive layer (the surface of the adhesive layer 40 in a state where the separator was peeled off) was measured using a "Hirest-up MCP-HT450" manufactured by Mitsubishi Chemical Analytech Co., Ltd. The measurement temperature was 23 ° C and the relative humidity was 50%. The results are shown in Table 1.

(corrosion of aluminum layer)

The optical laminates obtained in Examples 1 to 4 and Comparative Examples 1 to 2 were placed in an oven at a temperature of 80 ° C and a relative humidity of 90% for 72 hours. After the optical laminate was taken out, the polarizing plate of the adhesive layer was peeled off from the aluminum layer (metal-containing layer) to visually confirm the corrosion of the aluminum layer. The surface of the aluminum layer will produce white Those who are turbid or pitting are judged to be corroded. The results are shown in Table 1.

In Examples 1 to 4, corrosion of the aluminum layer was prevented, and the surface resistance value was reduced to the same level as in Comparative Example 1.

<Example 5>

A glass substrate (manufactured by Geomatec Co., Ltd.) having an aluminum layer (metal layer) having a thickness of about 200 nm laminated on the surface of the alkali-free glass substrate by a sputtering method is used as a light-transmitting substrate with a metal layer. An optical laminate was produced in the same manner as in Example 1.

<Example 6>

A glass substrate (a metal layer) having a thickness of about 200 nm laminated by a sputtering method on the surface of an alkali-free glass substrate (Geomatec Corporation) An optical laminate was produced in the same manner as in Example 2 except that the light-transmitting substrate was provided with a metal layer.

<Example 7>

A glass substrate (manufactured by Geomatec Co., Ltd.) having an aluminum layer (metal layer) having a thickness of about 200 nm laminated on the surface of the alkali-free glass substrate by a sputtering method is used as a light-transmitting substrate with a metal layer. An optical laminate was produced in the same manner as in Example 3.

<Comparative Example 3>

A glass substrate (manufactured by Geomatec Co., Ltd.) having an aluminum layer (metal layer) having a thickness of about 200 nm laminated on the surface of the alkali-free glass substrate by a sputtering method is used as a light-transmitting substrate with a metal layer. An optical laminate was produced in the same manner as in Comparative Example 1.

<Example 8>

A glass substrate (Geomatec company containing a layer of palladium and copper alloy, APC) (metal layer containing) having a thickness of about 200 nm and having a thickness of about 200 nm is deposited by sputtering on the surface of the alkali-free glass substrate. An optical laminate was produced in the same manner as in Example 1 except that the light-transmitting substrate with a metal layer was attached.

<Example 9>

In addition to the surface used for the alkali-free glass substrate, there is a layer deposited by sputtering. A glass substrate (manufactured by Geomatec) having a silver alloy (an alloy containing silver as a main component) having a thickness of about 200 nm (manufactured by Geomatec Co., Ltd.) was produced in the same manner as in Example 2 except that it was a light-transmitting substrate with a metal layer. Optical laminate.

<Example 10>

A glass substrate (manufactured by Geomatec) having a thickness of about 200 nm (an alloy containing silver as a main component) layer (metal layer) is deposited as a metal-containing layer by sputtering on the surface of the alkali-free glass substrate. An optical layered body was produced in the same manner as in Example 3 except for the light-transmitting substrate.

(Evaluation of corrosion of metal containing layers)

(1) The optical laminates obtained in Examples 5 to 7 and Comparative Example 3 were placed in an oven at a temperature of 80 ° C and a relative humidity of 90% for 72 hours. Thereafter, the optical laminate was taken out to the atmosphere, and allowed to cool, and the backlight was illuminated by the back side, and the state of the metal layer of the optical laminate was visually observed (visually), and no holes were observed in the metal-containing layer. The etch, that is, the hole having a diameter of 0.1 mm or more is set to "no" corrosion, and the hole corrosion (a hole having a diameter of 0.1 mm or more) is observed as "having" corrosion, and evaluation is performed separately. The results are shown in Table 2.

(2) The optical laminate obtained in Example 8 to Example 10 was placed in an oven at a temperature of 80 ° C and a relative humidity of 90% for 160 hours, and then taken out to the atmosphere and allowed to cool, from the back. The side is backlit, and the state of the metal-containing layer of the optical layered body is visually observed (visually), and no pitting corrosion is observed in the metal-containing layer, that is, the occurrence of the hole having a diameter of 0.1 mm or more is set to "no" corrosion. When the pitting corrosion (a hole having a diameter of 0.1 mm or more) was observed, it was set to "exist" corrosion and evaluated separately. The results are shown in Table 3.

10‧‧‧Polar plate

11‧‧‧ polarizer

21, 22‧‧‧ protective film

30‧‧‧Antistatic layer

40‧‧‧Adhesive layer

60‧‧‧Metal layer

70‧‧‧Transmissive substrate

100,300‧‧‧Antistatic polarizer

400‧‧‧Optical laminate

Claims (3)

An optical laminate comprising: a polarizing plate comprising a polarizer, an antistatic layer, an adhesive layer, and a metal containing layer, in the order described below. The optical layered product according to claim 1, wherein the metal-containing layer contains at least one metal element selected from the group consisting of aluminum, copper, silver, iron, tin, nickel, and indium. The optical layered product according to the first or second aspect of the invention, wherein the coating layer is further provided between the pressure-sensitive adhesive layer and the metal-containing layer.