JP2016126348A - Optical laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an optical laminate comprising a polarizing plate which can prevent the corrosion of a metal layer.SOLUTION: 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 the stated order. Preferably, the metal-containing layer comprises at least one metal element selected from the group consisting of aluminum, copper, silver, iron, tin, nickel and indium.SELECTED DRAWING: Figure 1

Description

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

  2. Description of the Related Art In recent years, touch-input type liquid crystal display devices are rapidly spreading mainly in smartphones and tablet-type portable information terminals. There are various types of touch input type liquid crystal display devices. For example, a touch input element is stacked on the viewing side of a liquid crystal cell, and a polarizing plate is disposed on the touch input element. However, it is a so-called “on-cell” system (for example, Patent Document 1).

JP 2012-043394 A

  In general, including touch input elements used in on-cell touch input type liquid crystal display devices, the touch input elements are transparent conductive materials made of tin-doped indium oxide (ITO) on the surfaces of two light-transmitting substrates. A film is provided, and these are formed so that the transparent conductive films face each other with a spacer interposed therebetween. However, reflecting the recent increase in price of indium and the demand for lower resistance of the transparent conductive film, an alternative technology for ITO is required. Development of metal mesh is underway as one of the alternative technologies. The metal mesh is formed by finely processing a metal into a mesh shape on a transparent substrate. The metal mesh has excellent electrical conductivity and translucency, and can reduce the manufacturing cost of the touch input element, and thus has attracted attention as a next-generation transparent conductive film.

  On the other hand, in the touch input element, when using a metal-containing layer made of a metal mesh instead of ITO as the transparent conductive film, the metal-containing layer corrodes with the use of the touch-input type liquid crystal display device. I found a new problem. Among corrosion, pitting corrosion has a great influence on the metal mesh, such as disconnection.

  This invention is made | formed in view of the said subject, The objective is an optical laminated body containing a polarizing plate, Comprising: It is providing the optical laminated body which can prevent corrosion of a metal containing layer.

The present invention provides the following optical laminate.
[1] An optical laminate including a polarizing plate including a polarizer, an antistatic layer, an adhesive layer, and a metal-containing layer in the order described above.

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

  [3] The optical laminate according to [1] or [2], further comprising an overcoat layer between the pressure-sensitive adhesive layer and the metal-containing layer.

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the optical laminated body which can prevent the corrosion of a metal containing layer.

It is a schematic sectional drawing which shows typically an example of the layer structure of the optical laminated body which concerns on this invention. It is a schematic sectional drawing which shows typically another example of the layer structure of the optical laminated body which concerns on this invention. It is a schematic sectional drawing which shows typically another example of the layer structure of the optical laminated body which concerns on this invention.

[Optical laminate]
(1) Configuration of Optical Laminate As shown in FIG. 1, an optical laminate 400 according to an embodiment of the present invention includes a polarizing plate 10 including a polarizer 11, an antistatic layer 30, and an adhesive layer 40. And the metal-containing layer 60 in the order described above. In addition, the optical laminated body 400 can contain the translucent board | substrate 70 arrange | positioned on the surface on the opposite side to the surface where the adhesive layer 40 of the metal containing layer 60 was laminated | stacked. The optical layered body 400 includes the pressure-sensitive adhesive layer 40 of the antistatic polarizing plate 300 with the pressure-sensitive adhesive layer including the polarizing plate 10, the antistatic layer 30, and the pressure-sensitive adhesive layer 40 on the surface of the translucent substrate 70. It can be formed by bonding to the surface of the formed metal-containing layer 60. In the optical laminated body 400, the metal-containing layer 60 is formed over the entire surface of the translucent substrate 70. The antistatic polarizing plate 100 includes a polarizing plate 10 and an antistatic layer 30 laminated on one surface thereof.

  In addition, as shown in FIG. 2, the optical laminate 500 may include an overcoat layer 50 between the pressure-sensitive adhesive layer 40 and the metal-containing layer 60. In this case, the optical layered body 500 may be formed by bonding the pressure-sensitive adhesive layer 40 of the antistatic polarizing plate 300 with the pressure-sensitive adhesive layer to the surface of the overcoat layer 50 laminated on the surface of the metal-containing layer 60. it can. In the optical laminated body 500, the metal-containing layer 60 is formed over the entire surface of the translucent substrate 70.

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

(2) Polarizing plate The polarizing plate 10 is a polarizing element including at least the polarizer 11, and usually further includes protective films 21 and 22 bonded to one or both sides thereof. Although illustration is abbreviate | omitted, bonding with the polarizer 11 and the protective films 21 and 22 can be performed using an adhesive agent.

  In addition to the protective films 21 and 22, the polarizing plate 10 may include other optical films such as a film having an optical function different from that of the polarizer 11, and a layer added on the film such as an optical layer. it can. Various optical films including a protective film can be bonded via an adhesive layer or a pressure-sensitive adhesive.

(2-1) Polarizer The polarizer 11 absorbs linearly polarized light having a vibration plane parallel to the absorption axis and transmits linearly polarized light having a vibration plane orthogonal to the absorption axis (parallel to the transmission axis). A polarizing film in which a dichroic dye is adsorbed and oriented on a polyvinyl alcohol-based resin film can be suitably used. The polarizer 11 is, for example, a step of uniaxially stretching a polyvinyl alcohol resin film; a step of adsorbing a dichroic dye by dyeing the polyvinyl alcohol resin film with a dichroic dye; and a dichroic dye adsorbed It can be produced by a method comprising a step of treating a polyvinyl alcohol resin film with an aqueous boric acid solution; and a step of washing with water after the treatment with the boric acid aqueous solution.

  As the polyvinyl alcohol resin, a saponified polyvinyl acetate resin can be used. Examples of the polyvinyl acetate resin include, in addition to polyvinyl acetate, which is a homopolymer of vinyl acetate, copolymers with other monomers copolymerizable with vinyl acetate. Examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, (meth) acrylamides having ammonium groups, and the like.

  The saponification degree of the polyvinyl alcohol resin is usually about 85 to 100 mol%, preferably 98 mol% or more. The polyvinyl alcohol-based resin may be modified, and for example, polyvinyl formal or polyvinyl acetal modified with aldehydes may be used. The average degree of polymerization of the polyvinyl alcohol resin is usually about 1000 to 10000, preferably about 1500 to 5000. The average degree of polymerization of the polyvinyl alcohol resin can be determined according to JIS K 6726.

  What formed such a polyvinyl alcohol-type resin into a film is used as a raw film of the polarizer 11 (polarizing film). The method for forming the polyvinyl alcohol-based resin into a film is not particularly limited, and a known method is employed. The thickness of the polyvinyl alcohol-based raw film is, for example, about 10 to 150 μm.

  Uniaxial stretching of the polyvinyl alcohol-based resin film can be performed before, simultaneously with, or after dyeing the dichroic dye. When uniaxial stretching is performed after dyeing, this uniaxial stretching may be performed before boric acid treatment or during boric acid treatment. Moreover, you may uniaxially stretch in these several steps.

  In uniaxial stretching, it may be uniaxially stretched between rolls having different peripheral speeds, or may be uniaxially stretched using a hot roll. Further, the uniaxial stretching may be dry stretching in which stretching is performed in the air, or may be wet stretching in which stretching is performed in a state where a polyvinyl alcohol-based resin film is swollen using a solvent or water. The draw ratio is usually about 3 to 8 times.

  As a method for dyeing a polyvinyl alcohol-based resin film with a dichroic dye, for example, a method of immersing the film in an aqueous solution containing the dichroic dye is employed. As the dichroic dye, iodine or a dichroic organic dye is used. In addition, it is preferable that the polyvinyl alcohol-type resin film performs the immersion process to water before a dyeing process.

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

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

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

  A polarizer 11 is obtained by performing a drying process after washing with water. The drying process can be performed 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 even 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 is a base film in which a coating liquid containing a polyvinyl alcohol resin is applied on a base film and dried to form a polyvinyl alcohol resin layer, and the polyvinyl alcohol resin layer is formed. Can also be produced by a method of stretching the film together with the polyvinyl alcohol-based resin layer, then performing a dyeing treatment with a dichroic dye, and peeling and removing the base film. Examples of the base film include thermoplastic resins such as polyester resins such as polyethylene terephthalate, polycarbonate resins, cellulose resins such as triacetyl cellulose, polyolefin resins such as norbornene resins, and thermoplastic resins such as polystyrene resins. A film can be used. The stretching process is usually uniaxial stretching. This method is preferable in that a polarizer having a small thickness, for example, a thickness of 7 μm or less can be easily produced.

(2-2) Protective Film The protective films 21 and 22 that can be laminated on one or both sides of the polarizer 11 are light-transmitting (preferably optically transparent) thermoplastic resins such as chain polyolefins. -Based resins (polypropylene resins, etc.), polyolefin-based resins such as cyclic polyolefin resins (norbornene-based resins, etc.); cellulose-based resins such as triacetyl cellulose and diacetyl cellulose; Resin; Polycarbonate resin; (Meth) acrylic resin such as methyl methacrylate resin; Polystyrene resin; Polyvinyl chloride resin; Acrylonitrile butadiene styrene resin; Acrylonitrile styrene resin; Polyvinyl acetate resin ; Po Vinylidene chloride resin; polyamide resin; polyacetal resin; modified polyphenylene ether resin; polysulfone resin; polyethersulfone resin; polyarylate resin; polyamideimide resin; Can do. In this specification, “(meth) acrylic resin” represents at least one selected from the group consisting of acrylic resins and methacrylic resins. The same applies to other terms with “(meta)”.

  Examples of the chain polyolefin-based resin include a homopolymer of a chain olefin such as a polyethylene resin and a polypropylene resin, and a copolymer composed of two or more chain olefins.

  Cyclic polyolefin resin is a general term for resins that are polymerized using a cyclic olefin as a polymerization unit. Specific examples of cyclic polyolefin resins include ring-opening (co) polymers of cyclic olefins, addition polymers of cyclic olefins, copolymers of cyclic olefins and chain olefins such as ethylene and propylene (typically Are random copolymers), graft polymers obtained by modifying them with unsaturated carboxylic acids or derivatives thereof, and hydrides thereof. Among these, norbornene resins using norbornene monomers such as norbornene and polycyclic norbornene monomers as cyclic olefins are preferably used.

  Cellulosic resins are those in which some or all of the hydrogen atoms in the hydroxyl groups of cellulose obtained from raw material cellulose such as cotton linter and wood pulp (hardwood pulp, conifer pulp) are substituted with acetyl groups, propionyl groups and / or butyryl groups. Further, it refers to a cellulose organic acid ester or a cellulose mixed organic acid ester. For example, cellulose acetate, propionate, butyrate, and mixed esters thereof can be used. Among these, triacetyl cellulose, diacetyl cellulose, cellulose acetate propionate, and cellulose acetate butyrate are preferable.

  The (meth) acrylic resin is a polymer containing a structural unit derived from a (meth) acrylic monomer. The polymer is typically a polymer containing a methacrylic acid ester. Preferably, it is a polymer in which the proportion of structural units derived from methacrylic acid esters is 50% by weight or more based on the total structural units. The (meth) acrylic resin may be a methacrylic acid ester homopolymer or a copolymer containing structural units derived from other polymerizable monomers. In this case, the proportion of structural units derived from other polymerizable monomers is preferably 50% or less with respect to the total structural units.

  The methacrylic acid ester that can constitute the (meth) acrylic resin is preferably an alkyl methacrylate. Examples of alkyl methacrylates include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate. And alkyl methacrylate having 1 to 8 carbon atoms in the alkyl group, such as 2-hydroxyethyl methacrylate. Carbon number of the alkyl group contained in the methacrylic acid alkyl ester is preferably 1 to 4. In the (meth) acrylic resin, methacrylic acid esters may be used alone or in combination of two or more.

  As said other polymerizable monomer which can comprise a (meth) acrylic-type resin, the compound which has a polymerizable carbon-carbon double bond in an acrylate ester and another molecule | numerator can be mentioned. Other polymerizable monomers may be used alone or in combination of two or more. As the acrylic acid ester, an acrylic acid alkyl ester is preferable. Examples of the alkyl acrylate ester include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, and cyclohexyl acrylate. And alkyl acrylates having 1 to 8 carbon atoms in the alkyl group such as 2-hydroxyethyl acrylate. Carbon number of the alkyl group contained in the acrylic acid alkyl ester is preferably 1 to 4. In the (meth) acrylic resin, acrylic acid esters may be used alone or in combination of two or more.

  Other compounds having a polymerizable carbon-carbon double bond in the molecule include vinyl compounds such as ethylene, propylene and styrene, and vinylcyan compounds such as acrylonitrile. Other compounds having a polymerizable carbon-carbon double bond in the molecule may be used alone or in combination of two or more.

  Since the (meth) acrylic resin can improve the durability of the protective film, the main chain may have a ring structure. The ring structure is preferably a cyclic acid anhydride structure such as a glutaric anhydride structure and a succinic anhydride structure; a cyclic imide structure such as a glutarimide structure and a succinimide structure; a lactone ring structure such as butyrolactone and valerolactone.

  The protective films 21 and 22 can also be protective films having an optical function such as a retardation film. For example, a retardation film provided with an arbitrary retardation value by stretching a film made of the thermoplastic resin (uniaxial stretching or biaxial stretching) or by forming a liquid crystal layer or the like on the film. It can be. A retardation film can also be obtained by laminating a thermoplastic resin (for example, (meth) acrylic resin) on at least one of the retardation developing layers and stretching it. At least one of the protective films 21 and 22 has a hard coat layer, an antiglare layer, a light diffusing layer, a retardation layer (a quarter wavelength retardation) on the outer surface (the surface opposite to the polarizer 11). A retardation layer having a value), an antireflection layer, a surface treatment layer (coating layer) such as an antifouling layer, or an optical layer.

  Although the thickness of the protective films 21 and 22 can be about 1-100 micrometers, it is preferable that it is 5-60 micrometers from viewpoints, such as intensity | strength and handleability, and it is more preferable that it is 5-50 micrometers. When the thickness is within this range, the polarizer 11 is mechanically protected, and the polarizer 11 does not contract even when exposed to a moist heat environment, and stable optical characteristics can be maintained.

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

  In the case where the protective films 21 and 22 are bonded to both surfaces of the polarizer 11, these protective films may be made of the same kind of thermoplastic resin or different kinds of thermoplastic resins. . Moreover, the thickness may be the same or different. Furthermore, they may have the same phase difference characteristics or different phase difference characteristics.

  The protective films 21 and 22 can be bonded to the polarizer 11 through an adhesive layer, for example. As the adhesive 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 and an active energy ray-curable adhesive are preferable.

  Examples of the water-based adhesive include an adhesive composition using a polyvinyl alcohol resin or a urethane resin as a main component.

  When a polyvinyl alcohol resin is used as the main component of the water-based adhesive, the polyvinyl alcohol resin is a vinyl alcohol homopolymer obtained by saponifying polyvinyl acetate, which is a homopolymer of vinyl acetate, Examples thereof include copolymers with other monomers that can be copolymerized. Examples of other monomers copolymerized with vinyl acetate include unsaturated carboxylic acid, unsaturated sulfonic acid, olefin, vinyl ether, and (meth) acrylamide having an ammonium group. The polyvinyl alcohol resin used for the adhesive preferably has an appropriate degree of polymerization. For example, when the aqueous solution has a concentration of 4% by weight, the viscosity is in the range of 4 to 50 mPa · sec. More preferably, it is in the range of 6 to 30 mPa · sec.

  A modified polyvinyl alcohol resin can also be preferably used. Suitable modified polyvinyl alcohol resins include acetoacetyl group-modified polyvinyl alcohol resins, anion-modified polyvinyl alcohol resins, and cation-modified polyvinyl alcohol resins. If such a modified polyvinyl alcohol resin is used, the effect of improving the water resistance of the adhesive layer can be easily obtained.

  Of course, the water-based adhesive used in the present invention may contain two or more kinds of the above-mentioned modified polyvinyl alcohol resins, and may be an unmodified polyvinyl alcohol resin (specifically, a complete polyvinyl acetate resin). Or a partially saponified product) and the modified polyvinyl alcohol resin described above.

  The polyvinyl alcohol 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., sold by Nippon Synthetic Chemical Industry Co., Ltd. Examples include “GOHSENOL NH-20”, “GOHSEPHIMER Z” series, “GOHSEPIMAR K-210” and “GOHSENAL T-330” (all are trade names).

  A water-based adhesive mainly composed of a polyvinyl alcohol resin can contain a crosslinking agent. When compounds capable of forming a crosslinking agent are listed by functional group, an isocyanate compound having at least two isocyanato groups (—NCO) in the molecule; an epoxy compound having at least two epoxy groups (crosslinked —O—) in the molecule; Mono- or di-aldehydes; organic titanium compounds; inorganic salts of divalent or trivalent metals such as magnesium, calcium, iron, nickel, zinc and aluminum; metal salts of glyoxylic acid; methylol melamine.

  Among these crosslinking agents, epoxy compounds including the above-mentioned water-soluble polyamide epoxy resins, aldehydes, methylol melamine, alkali metal or alkaline earth metal salts of glyoxylic acid, and the like are preferably used.

  The crosslinking agent is preferably dissolved in water together with the polyvinyl alcohol resin to form an adhesive. However, since the amount of the crosslinking agent in the aqueous solution may be small as described below, any crosslinking agent having a solubility of, for example, at least about 0.1% by weight in water can be used. Of course, a compound having a solubility in water of a level generally called water solubility is more suitable as a crosslinking agent used in the present invention.

  The amount of the crosslinking agent is appropriately designed according to the type of the polyvinyl alcohol resin and the like, but is usually about 5 to 60 parts by weight, preferably 10 to 50 parts per 100 parts by weight of the polyvinyl alcohol resin. Parts by weight. When the crosslinking agent is blended within this range, good adhesiveness can be obtained. If the amount of the cross-linking agent is too large, the reaction of the cross-linking agent proceeds in a short time and the adhesive tends to gel early, resulting in extremely short pot life and industrial use. It becomes difficult.

  In the water-based adhesive, conventionally known appropriate additives such as a silane coupling agent, a plasticizer, an antistatic agent, and fine particles can be blended as long as the effects of the present invention are not impaired.

  When a urethane resin is used as the main component of the water-based adhesive, an example of a suitable adhesive is a mixture of a polyester ionomer type urethane resin and a compound having a glycidyloxy group. The polyester ionomer type urethane resin here is a urethane resin having a polyester skeleton, into which a small amount of ionic component (hydrophilic component) is introduced. Such an ionomer type urethane resin is suitably used for an aqueous adhesive because it is emulsified directly in water without using an emulsifier to form an emulsion. The use of a polyester-based ionomer type urethane resin in an adhesive layer between a polarizer and a protective film is described in, for example, JP-A-2005-070140, JP-A-4432487, and JP-A-2005-208456. Yes.

  The active energy ray-curable adhesive refers to an adhesive that is cured by irradiation with active energy rays such as ultraviolet rays and electron beams. The curable adhesive is classified according to its curing mode, a cationic polymerization adhesive containing a cationic polymerizable compound as the curable compound, a radical polymerizable adhesive containing a radical polymerizable compound as the curable compound, and cationic polymerizable. Examples thereof include a hybrid curable adhesive containing both a compound and a radical 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. Specific examples of the radical polymerizable compound include a (meth) acrylic compound and a vinyl compound having one or more (meth) acryloyl groups in the molecule. The active energy ray-curable adhesive has a sensitizer, a sensitization aid, a leveling agent, a silane coupling agent, an antistatic agent, an ultraviolet absorber, a thermal polymerization initiator, etc., as long as the effects of the present invention are not impaired. Conventionally known appropriate additives can be blended.

  When using an active energy ray-curable adhesive, the polarizer 11 and the protective films 21 and 22 are bonded together, and then a drying process is performed as necessary, followed by irradiation with active energy rays to cure the active energy ray. A curing step for curing the adhesive is performed. Therefore, when an active energy ray-curable adhesive is used, the adhesive layer is the cured product layer. The light source of the active energy ray is not particularly limited, but ultraviolet light having a light emission distribution at a wavelength of 400 nm or less is preferable. A wave excitation mercury lamp, a metal halide lamp, etc. can be used.

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

  In pasting the polarizer 11 and the protective films 21 and 22, in order to enhance the adhesiveness, saponification treatment, corona treatment, plasma treatment, flame treatment, and primer treatment are performed on at least one of the pasting surfaces. , Anchor coating treatment and the like can be performed.

  In the case where protective films are bonded to both sides of the polarizer 11, the adhesive for bonding these protective films may be the same type of adhesive or different types of adhesives.

(2-3) Other optical films The antistatic polarizing plate 100 can contain optical films other than the polarizer 11 and the protective films 21 and 22, and the representative examples are a brightness enhancement film and a retardation film. is there. Other optical films can 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 the static electricity on the performance of the optical laminates 400 and 500. Examples of the material for forming the antistatic layer 30 include conductive fine particles such as conductive polymer, metal fine particles, metal oxide fine particles, or fine particles coated with metal, ions made of an electrolyte salt and an organopolysiloxane. Examples thereof include conductive compositions, ionic compounds, and various surfactants (cationic, anionic and amphoteric surfactants). When the antistatic layer 30 contains these materials, the electric resistance of the antistatic layer 30 is lowered, and thus the antistatic layer 30 and, consequently, the optical laminates 400 and 500 can be provided with antistatic performance.

  Examples of the conductive polymer include polyacetylene, polyphenylene bonded in the para-position or meta-position, and a polymer in which a phenyl group is connected through a divalent group (for example, polyphenylene vinylene in which a phenyl group is connected through -CH = CH-. , Polyphenylene sulfide in which a phenyl group is connected through —S—, and polyphenylene oxide in which a phenyl group is connected through —O—.) The elements constituting the five-membered ring are elements other than C and H. Polymers containing two and five-positions (for example, polypyrrole in which a NH-containing five-membered ring is connected in the second and fifth positions, polythiophene in which a five-membered ring containing S is connected in the second and fifth positions, and five containing O Polyfuran with member rings connected in the 2nd and 5th positions, Polyselenophene with 5 membered rings including Se connected in the 2nd and 5th positions, Polyter with 5 membered rings including Te connected in the 2nd and 5th positions Lofen), polymers obtained by polymerizing aromatic amines (for example, polyaniline and polyaminopyrene), polystyrene sulfonic acid and the like. Of these, polyaniline, polythiophene, and polypyrrole are preferable, and polyaniline and polythiophene are more preferable. Examples of commercially available conductive polymers include “Denatron” (registered trademark) manufactured by Nagase ChemteX Corporation, “ORMECON” (registered trademark) manufactured by Nissan Chemical Industries, Ltd. C. There are “CLEVIOUS” manufactured by Stark Co., “Seprugida” (registered trademark) manufactured by Shin-Etsu Polymer Co., Ltd., “Vitron” manufactured by Bayer Co., Ltd. and the like.

Examples of the conductive fine particles include silver powder, copper powder, nickel powder, zinc oxide (ZnO), tin oxide (SnO ₂ ), antimony-doped tin oxide (ATO), and tin-doped indium oxide (ITO). Can do.

  The ion conductive composition is made of, for example, an electrolyte salt and an organopolysiloxane represented by the following formula.

In the formula, R ¹¹ represents a monovalent organic group, R ^{12 to} R ¹⁴ represent an alkylene group, and R ¹⁵ represents hydrogen or a monovalent organic group. m is an integer of 0 to 100, and n is an integer of 1 to 100. ^{- (- Si (R 11 R} 11) O -) - units and ^{- (- Si (R 11 R} 12) O -) - sequence the sequence of units is arbitrary. a and b are each an integer of 0 to 100 and are not 0 at the same time. The arrangement order of-(-R < ¹³ > O-)-and-(-R < ¹⁴ > O-)-is arbitrary.

  Examples of the electrolyte salt include an electrolyte salt whose cation is a cation of a metal 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 and an inorganic anion or an organic anion.

Examples of the inorganic cation include alkali metal ions such as lithium cation [Li ⁺ ], sodium cation [Na ⁺ ], and potassium cation [K ⁺ ], beryllium cation [Be ²⁺ ], and magnesium cation [Mg ²⁺ ]. And alkaline earth metal ions such as calcium cation [Ca ²⁺ ].

  Examples of the organic cation include an imidazolium cation, a pyridinium cation, a pyrrolidinium cation, an ammonium cation, a sulfonium cation, a phosphonium cation, and a piperidinium cation.

Examples of inorganic anions include chloride anions [Cl ⁻ ], bromide anions [Br ⁻ ], iodide anions [I ⁻ ], tetrachloroaluminate anions [AlCl ₄ ⁻ ], heptachlorodialuminate anions [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 ⁻ ], hexafluoro niobate anion [NbF ₆ ⁻ ], hexafluoro tantalate anion [TaF ₆ ⁻ ], dicyanamide anion [(CN) ₂ N ⁻ ] and the like. It is done.

Examples of the organic anion include acetate anion [CH ₃ COO ⁻ ], trifluoroacetate anion [CF ₃ COO ⁻ ], methanesulfonate anion [CH ₃ SO ₃ ⁻ ], trifluoromethanesulfonate anion [CF ₃ SO ₃ ⁻ ], p-toluenesulfonate anion [p-CH ₃ C ₆ H ₄ SO ₃ ⁻ ], bis (fluorosulfonyl) imide anion [(FSO ₂ ) ₂ N ⁻ ], bis (trifluoromethanesulfonyl) imide anion [(CF ₃ SO ₂ ) ₂ N ⁻ ], tris (trifluoromethanesulfonyl) methanide anion [(CF ₃ SO ₂ ) ₃ C ⁻ ], dimethyl phosphinate anion [(CH ₃ ) ₂ POO ⁻ ], (poly) hydrofluorofluoride anion [ F (HF) _n ⁻ ] (n is about 1 to 3), thiocyan anion [SC N ^-], perfluorobutane sulfonate anion [C ₄ F ₉ SO ₃ ^-], bis (pentafluoroethane sulfonyl) imide anion _{[(C 2 F 5 SO 2)} 2 N - ], perfluoro butanoate anion [C ₃ F ₇ COO ⁻ ], (trifluoromethanesulfonyl) (trifluoromethanecarbonyl) imide anion [(CF ₃ SO ₂ ) (CF ₃ CO) N ⁻ ], perfluoropropane-1,3-disulfonate anion [ ⁻ O ₃ S (CF ₂ ) ₃ SO ₃ ⁻ ], carbonate anion [CO ₃ ²⁻ ] and the like. Among the anionic components described above, anionic components containing fluorine atoms are advantageous in terms of antistatic properties.

  Specific examples of the ionic compound can be appropriately selected from a combination of the cation component and the anion component. Examples of ionic compounds having an organic cation are listed below according to the structure of the organic cation.

Pyridinium salt:
N-hexylpyridinium hexafluorophosphate,
N-octylpyridinium hexafluorophosphate,
N-octyl-4-methylpyridinium hexafluorophosphate,
N-butyl-4-methylrupyridinium hexafluorophosphate,
N-decylpyridinium bis (fluorosulfonyl) imide,
N-dodecylpyridinium bis (fluorosulfonyl) imide,
N-tetradecylpyridinium bis (fluorosulfonyl) imide,
N-hexadecylpyridinium bis (fluorosulfonyl) imide,
N-dodecyl-4-methylpyridinium bis (fluorosulfonyl) imide,
N-tetradecyl-4-methylpyridinium bis (fluorosulfonyl) imide,
N-hexadecyl-4-methylpyridinium bis (fluorosulfonyl) imide,
N-benzyl-2-methylpyridinium bis (fluorosulfonyl) imide,
N-benzyl-4-methylpyridinium bis (fluorosulfonyl) imide,
N-hexylpyridinium bis (trifluoromethanesulfonyl) imide,
N-octylpyridinium bis (trifluoromethanesulfonyl) imide,
N-octyl-4-methylpyridinium bis (trifluoromethanesulfonyl) imide,
N-butyl-4-methyllpyridinium bis (trifluoromethanesulfonyl) imide.

Imidazolium salt:
1-ethyl-3-methylimidazolium hexafluorophosphate,
1-ethyl-3-methylimidazolium p-toluenesulfonate,
1-ethyl-3-methylimidazolium bis (fluorosulfonyl) imide,
1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide,
1-butyl-3-methylimidazolium methanesulfonate,
1-butyl-3-methylimidazolium bis (fluorosulfonyl) imide.

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

Quaternary ammonium salt:
Tetrabutylammonium hexafluorophosphate,
Tetrabutylammonium p-toluenesulfonate,
(2-hydroxyethyl) trimethylammonium bis (trifluoromethanesulfonyl) imide,
(2-Hydroxyethyl) trimethylammonium dimethylphosphinate.

Examples of ionic compounds having inorganic cations are as follows.
Lithium bromide,
Lithium iodide,
Lithium tetrafluoroborate,
Lithium hexafluorophosphate,
Lithium thiocyanate,
Lithium perchlorate,
Lithium trifluoromethanesulfonate,
Lithium bis (fluorosulfonyl) imide,
Lithium bis (trifluoromethanesulfonyl) imide,
Lithium bis (pentafluoroethanesulfonyl) imide,
Lithium tris (trifluoromethanesulfonyl) methanide,
Lithium p-toluenesulfonate,
Sodium hexafluorophosphate,
Sodium bis (fluorosulfonyl) imide,
Sodium bis (trifluoromethanesulfonyl) imide,
Sodium p-toluenesulfonate,
Potassium hexafluorophosphate,
Potassium bis (fluorosulfonyl) imide,
Potassium bis (trifluoromethanesulfonyl) imide,
Potassium p-toluenesulfonate.

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

  For the antistatic layer 30, for example, ionic compounds, conductive fine particles, conductive polymers and the like can be used alone or in combination of two or more. Of course, two or more kinds of antistatic agents classified as ionic compounds can be used in combination, or two or more kinds of antistatic agents classified as conductive fine particles can be used in combination. Two or more kinds of antistatic agents classified into molecules can be used in combination.

  The antistatic layer 30 can contain at least one of a hydrolyzable organosilicon compound and a condensation polymer thereof as an antistatic agent. The antistatic layer 30 can also have antistatic performance when the antistatic layer 30 contains at least one of a hydrolyzable organosilicon compound and a condensation polymer thereof as an antistatic agent.

The hydrolyzable organosilicon compound is a compound in which a non-hydrolyzable organic group and a hydrolyzable organic or inorganic group are bonded to a silicon atom, or a compound in which a hydrolyzable organic group is bonded to a silicon atom. In this case, the organic group may have a carbon atom at the bonding position, or may have another atom at the bonding position. Specifically, the hydrolyzable organosilicon compound has the following formula:
Si (T ¹ ) _q (T ² ) _4-q
Can be shown. 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.

As the non-hydrolyzable organic group represented by T ¹ in the above formula, typically, an alkyl group having about 1 to 4 carbon atoms, an alkenyl group having about 2 to 4 carbon atoms, or an aryl group such as a phenyl group. Etc. Examples of the hydrolyzable group represented by T ² include an alkoxy group having about 1 to 5 carbon atoms such as a methoxy group and an ethoxy group, an acyloxy group such as an acetoxy group and a propionyloxy group, a chlorine atom, Examples thereof include a halogen atom such as a bromine atom and a substituted silylamino group such as a trimethylsilylamino group. Specifically, the hydrolyzable organosilicon compound can be an alkoxysilane compound, a halogenated silane compound, an acyloxysilane compound, a silazane compound, or the like. These hydrolyzable organosilicon compounds are aryl groups, vinyl groups, allyl groups, (meth) acryloyloxy groups, epoxy groups, amino groups, mercapto groups, fluoroalkyls as part of T ¹ or T ² in the above formula. It may have a substituent such as a group.

  Specific hydrolyzable organosilicon compounds include, for example, halogenated silane compounds such as methyltrichlorosilane, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and dimethyldimethoxy. Silane, dimethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -Γ-aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypro Methyl dimethoxy silane, .gamma.-glycidoxypropyltrimethoxysilane, .gamma. alkoxysilane compounds such as glycidoxypropyl methyl dimethoxy silane, silazane compounds such as hexamethyldisilazane and the like. These may be used alone or in combination of two or more.

  As the hydrolyzable organosilicon compound, a hydrolysis product obtained by partially hydrolyzing the hydrolyzable organosilicon compound as described above may be used. Further, as the hydrolyzable organosilicon compound, a multimer obtained by condensing the hydrolysis product into an oligomer or polymer may be used. These hydrolysis products and multimers are 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 a hydrolyzable organosilicon compound. be able to.

  As the antistatic agent, a condensation polymer obtained by hydrolyzing and polycondensing a hydrolyzable organosilicon compound as described above may be used. The method for hydrolyzing the hydrolyzable organosilicon compound may be a conventional method. That is, the hydrolyzable organosilicon compound may be hydrolyzed in the presence of a catalyst by dissolving a hydrolyzable organosilicon compound in a predetermined amount of an organic solvent and dissolving the amount required for a predetermined solid content concentration into a uniform solution. In the case where an organic solvent is not used, the hydrolyzable organosilicon compound may be hydrolyzed by adding an amount that requires a predetermined solid content concentration to a uniform solution of water and catalyst. In general, hydrolysis may be performed by adding an amount of water required for a desired hydrolysis rate in the presence of an acid or alkali catalyst. Examples of the hydrolysis catalyst include acids such as hydrochloric acid, phosphoric acid, sulfuric acid, and acetic acid, for example, basic hydroxide catalysts such as LiOH, NaOH, and KOH. 0.01 to 10% by weight is used. The reaction temperature for hydrolysis is from room temperature to 50 ° C., and the reaction time varies depending on the reaction temperature and the amount of catalyst, but is generally 1 to 24 hours. A condensation polymer of a hydrolyzable organosilicon compound is prepared by the above hydrolysis reaction. As is well known, when a condensation polymer of a hydrolyzable organosilicon compound is gelled on the coated surface, it has a lot of silanol groups (Si-OH) containing hydroxyl groups on the surface, which is antistatic performance. It becomes effective for the expression of. Further, since the condensation polymer of the hydrolyzable organosilicon compound is prepared by hydrolysis, the end group of the condensation polymer contains an OH group, which is also effective for the development of antistatic performance. .

  The hydrolyzable organosilicon compound and its condensation polymer may be used alone or in the form of a mixture of the hydrolyzable organosilicon compound and its condensate. Hydrolyzable organosilicon compounds and their condensates that can be used as antistatic agents are commercially available from, for example, Colcoat Co., Ltd.

  Although the thickness of the antistatic layer 30 can be 10 nm or more and 1000 nm or less, it is preferably 800 nm or less from the viewpoint of reducing the thickness of the antistatic polarizing plate 100. When the thickness of the antistatic layer 30 is less than 10 nm, the adhesion, antistatic property and strength may not be sufficient. When the thickness exceeds 1000 nm, the adhesion and transparency are not sufficient, and defects such as cracks occur. There is a possibility.

  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, if necessary, a curable resin that is cured by irradiation with heat or active energy rays such as a (meth) acrylic compound. If necessary, the surface of the polarizing plate 10 may be subjected to activation treatment such as corona treatment, plasma treatment, primer treatment, anchor coating treatment and the like. Thereby, the adhesiveness improvement of the antistatic layer 30 and the polarizing plate 10 and the wettability to the polarizing plate 10 of a coating liquid become favorable.

  A solvent is used in order to adjust the density | concentration and viscosity of a coating liquid, the film thickness of a coating layer, etc. The solvent to be used may be appropriately selected. For example, alcohols such as methanol, ethanol, propanol, isopropanol, n-butanol, 2-butanol, isobutanol and tert-butanol, 2-ethoxyethanol, 2-butoxyethanol , Alkoxy alcohols such as 3-methoxypropanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, ketols such as diacetone alcohol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, Examples thereof include aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate and butyl acetate, ethers such as dioxane and tetrahydrofuran, and the like. The amount of the solvent used is appropriately selected according to the material, shape, coating method, target film thickness, etc. of the polarizing plate 10, but usually 20 parts per 100 parts by weight of the total amount of the antistatic agent. About 10000 parts by weight.

  Examples of the method for applying the coating liquid to the surface of the polarizing plate 10 include a micro gravure coating method, a roll coating method, a dipping coating method, a flow coating method, a spin coating method, a die coating method, a cast transfer method, and a spray coating method. Is mentioned.

  Next, the coating layer may be dried. The drying temperature depends on the type of the solvent and the adherend, but is usually about 25 to 120 ° C, more preferably about 30 to 110 ° C. Further, the hydrolyzable organosilicon 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 about 1 minute to 5 hours. When the coating layer contains a solvent, the heat treatment may be performed while the coating film contains the solvent or after the solvent is volatilized.

(4) Pressure-sensitive adhesive layer The pressure-sensitive adhesive layer 40 plays a role for adhering the antistatic polarizing plate 100 to adjacent members (such as the metal-containing layer 60 and the overcoat layer 50).

  Examples of the pressure-sensitive adhesive composition used for forming the pressure-sensitive adhesive layer 40 include a (meth) acrylic pressure-sensitive adhesive composition, a urethane-based pressure-sensitive adhesive composition, a silicone-based pressure-sensitive adhesive composition, a polyester-based pressure-sensitive adhesive composition, Examples thereof include a polyamide-based pressure-sensitive adhesive composition, a polyether-based pressure-sensitive adhesive composition, a fluorine-based pressure-sensitive adhesive composition, and a rubber-based pressure-sensitive adhesive composition. Of these, a (meth) acrylic pressure-sensitive adhesive having a (meth) acrylic resin as a base polymer is preferably used from the viewpoints of transparency, adhesive strength, reliability, reworkability, and the like.

  Specific examples of the (meth) acrylic resin that can be suitably used as the base polymer of the (meth) acrylic pressure-sensitive adhesive composition include the following formula (I):

It is a (meth) acrylic resin (A-1) which is a polymer containing as a main component (containing 50% by weight or more) a structural unit derived from a (meth) acrylic acid ester represented by:

In Formula (I), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkyl group having 1 to 14 carbon atoms which may be substituted with an alkoxy group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms. Represents an aralkyl group having 7 to 21 carbon atoms which may be substituted with an alkoxy group. R ² is preferably an alkyl group having 1 to 14 carbon atoms which may be substituted with an alkoxy group having 1 to 10 carbon atoms.

  Examples of the (meth) acrylic acid ester represented by the formula (I) include (meth) acrylic acid alkyl ester, and specific examples thereof include methyl acrylate, ethyl acrylate, propyl acrylate, and n-butyl acrylate. Alkyl acrylates in which the alkyl moiety is linear, such as n-octyl acrylate and lauryl acrylate; branched alkyl moieties such as isopropyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, and isooctyl acrylate Methacrylic acid alkyl ester; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, n-octyl methacrylate, methacrylic acid alkyl ester having linear alkyl moiety such as lauryl methacrylate; Isopropyl acid, Methacrylic acid isobutyl, 2-ethylhexyl methacrylate, methacrylic acid alkyl ester the alkyl moiety is branched, such as methacrylic acid isooctyl and the like. Carbon number of the alkyl part in (meth) acrylic acid alkyl ester becomes like this. Preferably it is 1-8, More preferably, it is 1-6.

When R ² is an alkyl group substituted with an alkoxy group, i.e., specific examples of the (meth) acrylic acid ester represented by formula (I) when R ² is an alkoxyalkyl group are acrylic acid 2- Including methoxyethyl, ethoxymethyl acrylate, 2-methoxyethyl methacrylate, ethoxymethyl methacrylate and the like. Carbon number of the alkyl group in the said alkoxyalkyl group becomes like this. Preferably it is 1-8, More preferably, it is 1-6. Carbon number of the alkoxy group in the said alkoxyalkyl group becomes like this. Preferably it is 1-8, More preferably, it is 1-4. Specific examples of the (meth) acrylic acid ester represented by the formula (I) when R ² is an aralkyl group having 7 to 21 carbon atoms include benzyl acrylate, benzyl methacrylate and the like. Carbon number of the aralkyl group is preferably 7-11.

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

  The (meth) acrylic resin (A-1) is usually composed of (meth) acrylic acid ester of the above formula (I) and at least one other monomer represented by a monomer having a polar functional group. It is a copolymer. The monomer having a polar functional group is preferably a (meth) acrylic acid compound having a polar functional group. Examples of polar functional groups include free carboxyl groups, hydroxyl groups, amino groups, and heterocyclic groups including epoxy groups.

  Specific examples of the monomer having a polar functional group include (meth) acrylic acid, a monomer having a free carboxyl group such as β-carboxyethyl (meth) acrylate; (meth) acrylic acid 2-hydroxyethyl, ( 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2- (2-hydroxyethoxy) ethyl (meth) acrylate, 2- or 3-chloro-2-hydroxypropyl (meth) acrylate (Meth) acrylic acid hydroxyl group-containing alkyl esters and dihydroxy glycol mono (meth) acrylates and other incomplete esterification products of polyfunctional alcohols such as (meth) acrylic acid; monomers having a hydroxyl group; acryloylmorpholine , Vinyl caprolactam, N-vinyl-2-pyrrolidone, vinyl pyridine, tetra Monomers having a heterocyclic group such as drofurfuryl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, glycidyl (meth) acrylate, 2,5-dihydrofuran; amino It includes a monomer having an amino group different from a heterocyclic ring, such as ethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, and dimethylaminopropyl (meth) acrylate. The monomer which has a polar functional group may be used individually by 1 type, and may use 2 or more types together.

  Among the above, from the viewpoint of the reactivity of the (meth) acrylic resin (A-1), as one of the polar functional group-containing monomers constituting the (meth) acrylic resin (A-1), a hydroxyl group is used. It is preferable to use the monomer which has. In addition to the monomer having a hydroxyl group, it is also effective to use a monomer having another polar functional group, for example, a monomer having a free carboxyl group. From the viewpoint of adhesion between the pressure-sensitive adhesive layer 40 and the antistatic polarizing plate 100 and durability of the pressure-sensitive adhesive layer 40, the monomer having a hydroxyl group is preferably a (meth) acrylic acid ester having a hydroxyl group, More preferred is a hydroxyl group-containing alkyl ester of (meth) acrylic acid. The carbon number of the alkyl moiety in the hydroxyl group-containing alkyl ester of (meth) acrylic acid is preferably 1-8, more preferably 1-6.

  The (meth) acrylic resin (A-1) is a monomer having one olefinic double bond and at least one aromatic ring in the molecule (however, a single monomer represented by the above formula (I)). A constituent unit derived from a monomer and a monomer having a polar functional group is excluded. Preferable examples include (meth) acrylic acid compounds having an aromatic ring. Suitable examples of the (meth) acrylic acid compound having an aromatic ring include the following formula (II):

A (meth) acrylic acid ester having an aryloxyalkyl group such as a phenoxyethyl group-containing (meth) acrylic acid ester represented by the formula: A monomer having one olefinic double bond and at least one aromatic ring in the molecule, such as a phenoxyethyl group-containing (meth) acrylic acid ester, may be used alone or 2 More than one species may be used in combination.

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 can be about 1 to 9, and when it is an aralkyl group, the carbon number is about 7 to 11, and when it is an aryl group, the carbon number is 6 Can be on the order of -10.

Examples of the alkyl group having 1 to 9 carbon atoms constituting R ⁴ in the formula (II) include methyl, butyl and nonyl, and examples of the aralkyl group having 7 to 11 carbon atoms include benzyl, phenethyl and naphthylmethyl. Examples of the aryl group having 6 to 10 carbon atoms include phenyl, tolyl, naphthyl and the like.

  Specific examples of the phenoxyethyl group-containing (meth) acrylic acid ester represented by the formula (II) are: (meth) acrylic acid 2-phenoxyethyl, (meth) acrylic acid 2- (2-phenoxyethoxy) ethyl, ethylene oxide (Meth) acrylic acid ester of modified nonylphenol, 2- (o-phenylphenoxy) ethyl (meth) acrylate, and the like. Among them, phenoxyethyl group-containing (meth) acrylic acid esters include 2-methoxyethyl (meth) acrylate, 2- (o-phenylphenoxy) ethyl (meth) acrylate and / or 2- (2) (meth) acrylic acid. -Phenoxyethoxy) ethyl is preferably included.

  The (meth) acrylic resin (A-1) is a structural unit derived from the (meth) acrylic acid ester represented by the above formula (I), preferably 60 to 99. It is contained in a proportion of 9% by weight, more preferably 80 to 99.6% by weight, and the structural unit derived from the monomer having a polar functional group is preferably 0.1 to 20% by weight, more preferably 0.8. 4 to 10% by weight of a constituent unit derived from a monomer having one olefinic double bond and at least one aromatic ring in the molecule, preferably 0 to 40% by weight, More preferably, it can contain in the ratio of 6-12 weight%.

  The (meth) acrylic resin (A-1) includes a (meth) acrylic acid ester represented by the formula (I), a monomer having a polar functional group, and one olefinic double bond in the molecule. A structural unit derived from a monomer other than the monomer having at least one aromatic ring (hereinafter also referred to as “other monomer”) may be included. Specific examples of other monomers are derived from structural units derived from (meth) acrylic acid esters having an alicyclic structure in the molecule, structural units derived from styrene monomers, and vinyl monomers. The structural unit includes a structural unit derived from a monomer having a plurality of (meth) acryloyl groups in the molecule, a structural unit derived from a (meth) acrylamide monomer, and the like. Other monomers may be used alone or in combination of two or more.

  The alicyclic structure usually has 5 or more carbon atoms, preferably about 5 to 7 carbon atoms. Specific examples of the (meth) acrylic acid ester having an alicyclic structure include isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, cyclododecyl (meth) acrylate, ( (Meth) acrylic acid methyl cyclohexyl, (meth) acrylic acid trimethyl cyclohexyl, (meth) acrylic acid tert-butyl cyclohexyl, (meth) acrylic acid cyclohexyl phenyl, α-ethoxyacrylic acid cyclohexyl and the like.

  Specific examples of the styrenic monomer include styrene; alkyl styrene such as methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene, octyl styrene; Halogenated styrene such as fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, iodostyrene; nitrostyrene, acetylstyrene, methoxystyrene, divinylbenzene and the like.

  Specific examples of vinyl monomers include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, and other fatty acid vinyl esters; vinyl chloride, vinyl halides such as vinyl bromide; Examples include vinylidene halides such as vinylidene chloride; nitrogen-containing aromatic vinyls such as vinylpyridine, vinylpyrrolidone and vinylcarbazole; conjugated diene monomers such as butadiene, isoprene and chloroprene; acrylonitrile, methacrylonitrile and the like.

  Specific examples of monomers having a plurality of (meth) acryloyl groups in the molecule include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1,9-nonanediol. 2 (meth) in the molecule such as di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate A monomer having an acryloyl group; a monomer having three (meth) acryloyl groups in the molecule such as trimethylolpropane tri (meth) acrylate.

  Specific examples of the (meth) acrylamide compound include N-methylol (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N- (3-hydroxypropyl) (meth) acrylamide, and N- (4-hydroxy). Butyl) (meth) acrylamide, N- (5-hydroxypentyl) (meth) acrylamide, N- (6-hydroxyhexyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meta) ) Acrylamide, N-isopropyl (meth) acrylamide, N- (3-dimethylaminopropyl) (meth) acrylamide, N- (1,1-dimethyl-3-oxobutyl) (meth) acrylamide, N- [2- (2 -Oxo-1-imidazolidinyl) ethyl] (meth) acrylamide, -Acryloylamino-2-methyl-1-propanesulfonic acid, N- (methoxymethyl) acrylamide, N- (ethoxymethyl) (meth) acrylamide, N- (propoxymethyl) (meth) acrylamide, N- (1-methyl) Ethoxymethyl) (meth) acrylamide, N- (1-methylpropoxymethyl) (meth) acrylamide, N- (2-methylpropoxymethyl) (meth) acrylamide [also known as N- (isobutoxymethyl) (meth) acrylamide] N- (butoxymethyl) (meth) acrylamide, N- (1,1-dimethylethoxymethyl) (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N- (2-ethoxyethyl) ( (Meth) acrylamide, N- (2-propoxyethyl) (meth) Kurylamide, N- [2- (1-methylethoxy) ethyl] (meth) acrylamide, N- [2- (1-methylpropoxy) ethyl] (meth) acrylamide, N- [2- (2-methylpropoxy) ethyl ] (Meth) acrylamide [Alternative name: N- (2-isobutoxyethyl) (meth) acrylamide], N- (2-butoxyethyl) (meth) acrylamide, N- [2- (1,1-dimethylethoxy) ethyl ] (Meth) acrylamide and the like.

  The (meth) acrylic resin (A-1) is based on the amount of the entire solid content, and is usually 0 to 20% by weight, preferably 0 to 10% by weight, of structural units derived from other monomers. Contains in proportions.

  From the viewpoint of the adhesion between the pressure-sensitive adhesive layer and the adjacent member, the (meth) acrylic resin (A-1) has a weight average molecular weight (Mw) in terms of standard polystyrene of 50 by gel permeation chromatography (GPC). It is preferably 10,000 or more, more preferably 600,000 or more. The Mw of the (meth) acrylic resin (A-1) is usually 1.7 million or less.

  The base polymer of the (meth) acrylic pressure-sensitive adhesive composition may contain two or more kinds of (meth) acrylic resins (A-1). In addition to the (meth) acrylic resin (A-1), the base polymer is a structural unit derived from a (meth) acrylic resin different from this, for example, a (meth) acrylic acid ester of the formula (I) And a structural unit derived from the (meth) acrylic resin (A-2) having no polar functional group and the (meth) acrylic acid ester represented by the above formula (I) as a main component, Mw (Meth) acrylic resin (A-3) etc. in the range of 50,000-120,000.

  The pressure-sensitive adhesive composition may further contain a crosslinking agent (B). The crosslinking agent is a compound that reacts with a structural unit derived from a polar functional group-containing monomer in the base polymer such as a (meth) acrylic resin to crosslink the base polymer. Specific examples include isocyanate compounds, epoxy compounds, aziridine compounds, metal chelate compounds, and the like. Among these, the isocyanate compound, the epoxy compound, and the aziridine compound have at least two functional groups that can react with the polar functional group in the base polymer. Only 1 type may be used for a crosslinking agent (B) individually, and 2 or more types may be used together.

  An isocyanate compound is a compound having at least two isocyanato groups (—NCO) in the molecule. Specific examples of the isocyanate compound include tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate and the like. In addition, adducts obtained by reacting these isocyanate compounds with polyols such as glycerol and trimethylolpropane, and those obtained by converting isocyanate compounds into dimers, trimers, and the like can also serve as the 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, glycerin triglycidyl ether, 1,6-hexanediol diglycidyl ether, and trimethylolpropane. Including triglycidyl ether, N, N-diglycidylaniline, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N′-diglycidylaminomethyl) cyclohexane, etc. .

  An aziridine-based compound is a compound having at least two 3-membered ring skeletons composed of one nitrogen atom and two carbon atoms, also called ethyleneimine. Specific examples of the aziridine compound include diphenylmethane-4,4′-bis (1-aziridinecarboxamide), toluene-2,4-bis (1-aziridinecarboxamide), triethylenemelamine, isophthaloylbis-1- (2 -Methylaziridine), tris-1-aziridinylphosphine oxide, hexamethylene-1,6-bis (1-aziridinecarboxamide), trimethylolpropane-tris-β-aziridinylpropionate, tetramethylolmethane-tris -Β-aziridinyl propionate and the like.

  Specific examples of metal chelate compounds include compounds in which acetylacetone or ethyl acetoacetate is coordinated to a polyvalent metal such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium and zirconium. Including.

  The crosslinking agent (B) is usually in a proportion of 0.05 to 5 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the solid content of the base polymer (total of two or more if used) Contained. 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 be improved.

  The pressure-sensitive adhesive layer 40 can contain an antistatic agent. As an antistatic agent, conductive fine particles such as metal fine particles, metal oxide fine particles, or fine particles coated with metal, an ionic conductive composition composed of an electrolyte salt and an organopolysiloxane, an ionic compound, or the like is used. Can do.

  When the pressure-sensitive adhesive layer 40 contains an ionic compound, the ionic compound is preferably 0.1 to 8 parts by weight with respect to 100 parts by weight of the solid content of the base polymer (when two or more are used), More preferably, it mix | blends in the ratio of 0.2-5 weight part. The content of the ionic compound being 0.2 parts by weight or more is advantageous for improving the antistatic property, and the content of 8 parts by weight or less is advantageous for improving the durability of the pressure-sensitive adhesive layer. However, when the antistatic polarizing plate 300 with an adhesive layer is applied to an on-cell touch input type liquid crystal display device, the metal-containing layer of the touch input element resulting from the ionic compound contained in the adhesive layer 40 is used. In order to suppress corrosion, the content of the ionic compound is preferably 0.2 parts by weight or less, more preferably 0.1 parts by weight or less, and more preferably 0.1 parts by weight or less with respect to 100 parts by weight of the solid content of the base polymer. Preferably it is 0.05 weight part or less, Most preferably, it is 0.01 weight part or less.

  The pressure-sensitive adhesive composition may contain other components as necessary. Other components that can be blended include silane coupling agents, cross-linking catalysts, weathering stabilizers, tackifiers, plasticizers, softeners, dyes, pigments, inorganic fillers, resins other than base polymers, and light diffusing fine particles such as organic beads. And rust preventives. It is also useful to blend an ultraviolet curable compound into the pressure-sensitive adhesive composition and form a pressure-sensitive adhesive layer and then cure it by irradiating with ultraviolet rays to form a harder pressure-sensitive adhesive layer.

  Examples of the rust preventive include benzotriazole compounds, other triazole compounds; benzothiazole compounds, other thiazole compounds; benzimidazole compounds, other imidazole compounds; imidazoline compounds; quinoline compounds; Compound; pyrimidine compound; indole compound; amine compound; urea compound; sodium benzoate; benzyl mercapto compound; di-sec-butyl sulfide;

  The pressure-sensitive adhesive composition may contain a rust preventive agent, but its content is preferably as small as possible, and the solids of the base polymers (the total of them when two or more are used) constituting the pressure-sensitive adhesive composition The content of the rust inhibitor with respect to 100 parts by weight per minute is usually 15 parts by weight or less, preferably 0.01 parts by weight or less, and ideally 0 (zero).

  The pressure-sensitive adhesive composition is usually prepared as a pressure-sensitive adhesive liquid in which a compounding component is dissolved or dispersed by containing an organic solvent. The organic solvent is preferably selected according to the type of the base 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 acetate and butyl acetate. Including various esters. The concentration of the base polymer in the adhesive liquid is usually 3 to 40% by weight.

  As a method for forming the pressure-sensitive adhesive layer 40 on the antistatic layer 30, for example, a separate film is used as a base material, and the pressure-sensitive adhesive layer 40 is formed by applying the above pressure-sensitive adhesive composition. 40 is transferred to the surface of the antistatic layer 30, the pressure-sensitive adhesive composition is directly applied to the surface of the antistatic layer 30 to form the pressure-sensitive adhesive layer 40, and a separate film is attached to the outer surface of the pressure-sensitive adhesive 40. A method of matching is adopted. Moreover, after forming the adhesive layer 40 on one sheet of separate film, another separate film may be bonded on the adhesive layer 40 to form a double-sided separate film type adhesive sheet. Such a pressure-sensitive adhesive sheet is peeled off one side of the separate film at a necessary time and bonded to the antistatic layer 30.

  The separate film has, as a base material, a film that can be composed of various resins such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyarylate, polypropylene, or polyethylene. In addition, a release treatment such as a silicone treatment can be performed.

  The pressure-sensitive adhesive layer 40 obtained by applying the pressure-sensitive adhesive liquid 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%, for example, and the reaction of the crosslinking agent proceeds sufficiently. After that, it is used for sticking to a liquid crystal cell, a touch input element or the like.

  The thickness of the pressure-sensitive adhesive layer 40 is preferably 10 to 45 μm, and more preferably 15 to 35 μm. That the thickness of the pressure-sensitive adhesive layer 40 is 45 μm or less is advantageous for adhesion with an adjacent member. Moreover, the followability of the adhesive layer 40 with respect to the dimensional change of an adjacent member becomes favorable as the thickness is 10 micrometers or more.

(5) Metal-containing layer As the metal-containing layer 60, thin films such as ITO (indium / tin oxide), tin / antimony oxide, aluminum, gold, silver, copper, titanium, palladium, chromium, nickel, A metal-containing layer formed of a thin film of metal such as tungsten, platinum, iron, indium, tin, iridium, rhodium, neodymium, molybdenum, or an alloy thereof can be used. Among these, from the viewpoint of excellent conductivity and low cost, aluminum, gold, silver, copper, titanium, palladium, chromium, nickel, tungsten, platinum, iron, indium, tin, iridium, rhodium, neodymium, molybdenum, or these It is preferable to use a metal-containing layer made of a metal thin film such as an alloy. The metal-containing layer 60 may be a continuous film formed over the entire surface of the translucent substrate 70 or a metal wiring layer formed of a metal mesh.

  The formation method of the metal containing layer 60 is not specifically limited, It can form on the surface of the translucent board | substrate 70 using a vacuum evaporation method, an ion beam evaporation method, sputtering method, an ion plating method etc. Examples of the method for forming the metal-containing layer 60 include an inkjet printing method and a gravure printing method. The metal-containing layer 60 can also be formed by providing a metal-containing layer 60 obtained by processing a metal foil.

  The metal-containing layer 60 formed by sputtering is generally inferior in corrosion resistance as compared with the metal-containing layer 60 obtained by processing a metal foil, for example. Even a metal-containing layer formed by such a sputtering method can suppress corrosion. For this reason, the optical layered body 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 with the metal-containing layer 60 having such a thickness, corrosion of the metal-containing layer 60 can be suppressed in the optical laminate of the present invention.

  When the metal-containing layer 60 is a metal-containing wiring layer composed of a metal mesh, the line width is usually 10 μm or less, preferably 5 μm or less, more preferably 3 μm or less, and usually 0.5 μm or more. Even with 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 laminate of the present invention, the metal-containing layer 60 is, for example, a metal-containing wiring layer (metal mesh) having a thickness of 3 μm or less and a line width of 10 μm or less, or a thickness of 3 μm or less and a line width of 10 μm or less. Even a metal-containing wiring layer (metal mesh) formed by a sputtering method can suppress corrosion.

  When the optical laminates 400 and 500 are applied to an on-cell touch input type liquid crystal display device or the like, the metal-containing layer 60 is formed on the light-transmitting substrate 70 by processing a metal into a fine mesh. A metal mesh can also be used. As the metal forming the metal mesh, aluminum, gold, silver, copper, titanium, palladium, chromium, nickel, tungsten, platinum, iron, indium, tin, iridium, rhodium, neodymium, molybdenum, or an alloy thereof is used. be able to.

  Of these metals, the metal forming the metal mesh is preferably aluminum, copper, silver, or an alloy containing one or more metals selected from these from the viewpoint of excellent conductivity and cost. It is preferable that the metal component which comprises a metal mesh has aluminum, copper, and / or silver as a main component, ie, these total content is 30 weight% or more, Furthermore, it is preferable that it is 50 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 layers or three or more layers. Examples of the metal-containing layer (metal mesh) having a multilayer structure include a metal-containing layer (metal mesh) having a three-layer structure represented by molybdenum / aluminum / molybdenum.

  You may have the transparent electrode layer which consists of metal oxides, such as ITO, with the metal containing layer 60. FIG.

  In the case where the metal-containing layer 60 is a metal wiring layer (metal mesh) patterned into a predetermined shape as in the optical laminated body 600 shown in FIG. 3, an adhesive layer directly on the metal wiring layer. When laminating 40, the pressure-sensitive adhesive layer 40 may have a portion that does not contact the metal-containing layer 60 but directly contacts the light-transmitting substrate 70 below.

  When the metal-containing layer 60 includes at least one metal element selected from the group consisting of aluminum, copper, silver, iron, tin, nickel, and indium, when used with the pressure-sensitive adhesive layer 40 including an ionic compound, With the use of the optical laminate 400, 500, 600, the metal-containing layer 60 may corrode. According to the optical laminates 400, 500, and 600 according to the present invention, since the antistatic layer 30 is included, the pressure-sensitive adhesive layer 40 does not include an ionic compound, or the ionic compound is contained in the pressure-sensitive adhesive layer 40. The amount of the metal-containing layer 60 can be prevented from being corroded.

(6) Overcoat layer The overcoat layer 50 has a function of protecting the transparent electrode layer 60. As long as the overcoat layer 50 does not impair the performance of the transparent electrode layer 60, any known curable resin can be used. As resin which comprises the overcoat layer 50, resin similar to the active energy ray hardening adhesive used for the adhesive bond layer between the protective films 21 and 22 and the polarizer 11 is mentioned, for example. Specifically, it can be comprised from hardened | cured material of active energy ray curable resin, such as polyfunctional (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, and epoxy (meth) acrylate.

(7) Translucent Substrate As the translucent substrate 70, a glass substrate can be used. Examples of the material for the glass substrate include soda lime glass, low alkali glass, and non-alkali glass. The translucent substrate 70 can be a transparent substrate constituting a liquid crystal cell in the touch input type liquid crystal display device.

(8) Liquid Crystal Display Device The optical laminate according to the present invention can be used by being incorporated in a touch input type liquid crystal display device. The touch input type liquid crystal display device may be an out-cell type, an on-cell type, or an in-cell type. The operation method of touch input may be a resistive film method, or may be a capacitance method such as a surface capacitance method or a projection capacitance method. 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 the backlight side). And it may be arranged on both the back side. The driving method of the liquid crystal cell is not particularly limited, and examples thereof include a TN method, a VA method, an IPS method, a multi-domain method, and an OCD method.

  The present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. Hereinafter, “parts” and “%” representing amounts used or contents are based on weight unless otherwise specified.

[Production of optical laminate]
(Production of polarizer)
A 30 μm-thick polyvinyl alcohol film (average polymerization degree of about 2400, saponification degree of 99.9 mol% or more) is about 5 times longitudinally uniaxially stretched by dry stretching and further maintained in a 60 ° C. pure water while maintaining tension. After being immersed for 1 minute, it was immersed for 60 seconds in a 28 ° C. aqueous solution having a weight ratio of iodine / potassium iodide / water of 0.05 / 5/100. Then, it was immersed for 300 seconds in 72 degreeC aqueous solution whose weight ratio of potassium iodide / boric acid / water is 8.5 / 8.5 / 100. Subsequently, after washing with pure water at 26 ° C. for 20 seconds, drying treatment was performed at 65 ° C. to obtain a 11 μm thick polarizer in which iodine was adsorbed and oriented on the polyvinyl alcohol film.

<Preparation of protective film>
Protective film A: A cyclic polyolefin resin film (thickness: 23 μm) manufactured by Nippon Zeon Co., Ltd. was prepared.

  Protective film B: A triacetyl cellulose film (thickness 25 μm) manufactured by Konica Minolta Opto Co., Ltd., whose surface was saponified was prepared.

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

  Antistatic layer coating solution # 2: solution containing polythiophene-based conductive polymer (“VERAZOL WED-SM” manufactured by Soken Chemical Co., Ltd., solid content concentration 1.5%, solvent is water), and polyvinyl alcohol aqueous solution (Solid content concentration of 6.2%) was mixed at a ratio of 1: 3 to prepare a coating solution. The solid content concentration in the coating liquid is 2.5%.

  Antistatic layer coating solution # 3: A solution containing polythiophene-based conductive polymer (“Denatron P-502RG” manufactured by Nagase ChemteX Corporation, solid content concentration 4%, solvent is water) is diluted with water (water). And 2-propanol in a volume ratio of 2: 8) were mixed so as to be 11 times diluted to prepare a coating solution. The solid content concentration in the coating solution is 0.36%.

<Preparation of adhesive layer>
Pressure-sensitive adhesive layer # 7: A pressure-sensitive adhesive layer (produced by Lintec Co., Ltd., thickness: 25 μm) having a separate film bonded on both sides was prepared.

Adhesive layer #A: Adhesive layer #A was prepared by the following procedure.
In a reaction vessel equipped with a cooling tube, a nitrogen 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, 2-phenoxyethyl acrylate 8.0 Part of the mixture, 1.0 part of 2-hydroxyethyl acrylate, and 0.6 part of acrylic acid were charged, and the internal temperature was raised to 55 ° C. while substituting the air in the apparatus with nitrogen gas to eliminate oxygen. It was. Thereafter, a total amount of a solution obtained by dissolving 0.14 part of azobisisobutyronitrile as a polymerization initiator in 10 parts of ethyl acetate was added. One hour after the addition of the initiator, the temperature was maintained at 54 to 56 ° C. for 12 hours while ethyl acetate was continuously added into the reaction vessel at an addition rate of 17.3 parts / hr so that the concentration of the acrylic resin was 35%. Finally, ethyl acetate was added to adjust the acrylic resin concentration to 20%. The obtained acrylic resin had a polystyrene-reduced weight average molecular weight Mw by GPC of 1,420,000 and Mw / Mn of 5.2. This is designated as 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 the cross-linking agent (solid part) and 0.5 part of the silane compound are mixed in the amounts shown therein, respectively. Ethyl acetate was added so that the solid concentration was 13% to obtain a pressure-sensitive adhesive composition.

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

(Crosslinking agent)
Coronate L: Ethyl acetate solution of trimethylolpropane adduct of tolylene diisocyanate manufactured by Nippon Polyurethane Co., Ltd. (solid content concentration 75%).

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

  The obtained pressure-sensitive adhesive composition was subjected to a release treatment on a release-treated polyethylene terephthalate film ("PLR-382052" manufactured by Lintec Co., Ltd .; hereinafter also referred to as a separate film) using an applicator. It apply | coated so that the thickness after drying might be set to 20 micrometers, and it dried at 100 degreeC for 1 minute, and obtained sheet-like adhesive layer #A.

<Preparation of aqueous adhesive>
Pure water with acetoacetyl group-modified polyvinyl alcohol (“Gosefimer Z-200” manufactured by Nippon Synthetic Chemical Industry Co., Ltd., viscosity of 4% aqueous solution = 12.4 mPa · sec, degree of saponification = 99.1 mol%) And a 10% strength aqueous solution was prepared. This aqueous solution of acetoacetyl group-modified polyvinyl alcohol and sodium glyoxylate serving as a cross-linking agent are mixed so that the weight ratio of the former: latter solids is 1: 0.1, and acetoacetyl is added to 100 parts of water. A water-based adhesive was prepared by diluting with pure water so that the group-modified polyvinyl alcohol was 2.5 parts.

<Preparation of translucent substrate with metal-containing layer>
A glass substrate having a 500 nm thick aluminum layer formed thereon was prepared.

<Example 1>
The optical layered body 400 having the same layer configuration as that shown in FIG. First, the above water-based adhesive is applied to both surfaces of the polarizer 11 in an atmosphere of 23 ° C., the protective film A subjected to corona treatment is applied to one adhesive application surface, and the other adhesive application surface is applied to the other adhesive application surface. The protective film B subjected to the corona treatment was pasted using a pasting device (“LPA3301” manufactured by Fuji Plastics Co., Ltd.) so that each corona-treated surface becomes a pasting surface with the polarizer 11. This was dried at 80 ° C. for 5 minutes to produce a polarizing plate.

  Next, the exposed surface of the protective film A is subjected to corona treatment, and the coating solution for the antistatic layer is coated with a coating machine (bar coater, manufactured by Daiichi Rika Co., Ltd.) so that the thickness after drying is 180 nm. After coating using, it was bonded to glass using Kapton adhesive tape. This was put into an oven having an internal temperature of 120 ° C. for 1 minute, then removed from the oven, and allowed to stand for 24 hours under conditions of a temperature of 23 ° C. and a relative humidity of 50%. Thereby, the antistatic layer 30 was formed on the surface of the protective film A.

  Next, after peeling and removing one of the separate layers of the pressure-sensitive adhesive layer # 7 as the pressure-sensitive adhesive layer 40, the above-described antistatic layer 30 is bonded to the surface of the pressure-sensitive adhesive layer 40 exposed by peeling, and the pressure-sensitive adhesive A layered antistatic polarizing plate 300 was prepared.

Next, after the other separate film of the pressure-sensitive adhesive layer # 7 is peeled and removed, the surface of the pressure-sensitive adhesive layer 40 exposed by peeling is coated with the above-described translucent substrate with a metal-containing layer (a metal having an aluminum layer on the main surface) The translucent substrate 70) on which the containing layer 60 is formed is bonded on the metal-containing layer 60 side, and subjected to a pressure-bonding treatment at a temperature of 50 ° C. and a pressure of 5 kg / cm ² (490.3 kPa) for 20 minutes. A laminate was produced.

<Example 2>
The optical laminate was prepared in the same manner as in Example 1, except that the antistatic layer coating solution # 2 was applied so that the thickness after drying was 225 nm instead of the antistatic layer coating solution # 1. Was made.

<Example 3>
The optical laminate was prepared in the same manner as in Example 1 except that the antistatic layer coating solution # 3 was applied so that the thickness after drying was 324 nm instead of the antistatic layer coating solution # 1. Was made.

<Example 4>
The optical layered body 500 having the same layer configuration as that shown in FIG. In the same manner as in Example 1, an antistatic polarizing plate 300 with an adhesive layer was produced. An overcoat 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 with a metal-containing layer (the light-transmitting substrate 70 on which the metal-containing layer 60 that is an aluminum layer is formed on the main surface). Thus, a laminated body of the translucent substrate 70, the metal-containing layer 60, and the overcoat layer 50 was obtained.

After the other separate film of the pressure-sensitive adhesive layer # 7 is peeled and removed, the above laminate is bonded to the surface of the pressure-sensitive adhesive layer 40 exposed by peeling on the overcoat layer 50 side, and the temperature is 50 ° C. and the pressure A pressure-bonding treatment was performed at 5 kg / cm ² (490.3 kPa) for 20 minutes to produce an optical laminate.

<Comparative Example 1>
A polarizing plate was produced in the same manner as in Example 1. Next, the surface opposite to the separate film of the adhesive layer #A (adhesive surface) is bonded to the surface of the protective film A of the polarizing plate with a laminator, and then the temperature is 23 ° C. and the relative humidity is 65%. After curing for 7 days, a polarizing plate with an adhesive layer was obtained.

Next, after separating and removing the separate film of the pressure-sensitive adhesive layer #A, the above-described translucent substrate with a metal-containing layer (the metal-containing layer 60 that is an aluminum layer on the main surface is formed on the surface of the pressure-sensitive adhesive layer exposed by peeling). The formed light-transmitting substrate 70) is bonded on the metal-containing layer 60 side, and subjected to a pressure-bonding treatment at a temperature of 50 ° C. and a pressure of 5 kg / cm ² (490.3 kPa) for 20 minutes to produce an optical laminate. did.

<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.

[Evaluation]
(Surface resistance)
The surface of the polarizing plate before bonding the pressure-sensitive adhesive layer 40 (the surface of the antistatic layer 30 or the surface of the protective film 22) and the light-transmitting substrate with a metal-containing layer after the pressure-sensitive adhesive layer 40 is bonded. About the surface of the polarizing plate with the pressure-sensitive adhesive layer (the surface of the pressure-sensitive adhesive layer 40 in a state where the separate film is peeled off) before bonding the film, the surface resistance is measured using “Hirest-up MCP-HT450” manufactured by Mitsubishi Chemical Analytech Co., Ltd. The value was measured. The measurement temperature was 23 ° C. and the relative humidity was 50%. The results are shown in Table 1.

(Aluminum layer corrosion)
The optical laminates obtained in Examples 1 to 4 and Comparative Examples 1 to 2 were put into an oven having an internal temperature of 80 ° C. and a relative humidity of 90% for 72 hours. After taking out the optical laminated body, the polarizing plate with an adhesive layer was peeled and removed from the aluminum layer (metal-containing layer), and corrosion of the aluminum layer was visually confirmed. When the surface of the aluminum layer was cloudy or pitting corrosion was judged as corrosion. 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>
Example 1 except that a glass substrate (manufactured by Geomatic Co., Ltd.) in which an aluminum layer (metal-containing layer) having a thickness of about 200 nm was laminated on the surface of a non-alkali glass substrate by a sputtering method was used as the translucent substrate with a metal-containing layer. In the same manner as described above, an optical laminate was produced.

<Example 6>
Example 2 except that a glass substrate (manufactured by Geomatic Co., Ltd.) in which an aluminum layer (metal-containing layer) having a thickness of about 200 nm was laminated on the surface of a non-alkali glass substrate by a sputtering method was used as the translucent substrate with a metal-containing layer. In the same manner as described above, an optical laminate was produced.

<Example 7>
Example 3 except that a glass substrate (manufactured by Geomatic Co., Ltd.) in which an aluminum layer (metal-containing layer) having a thickness of about 200 nm was laminated on the surface of a non-alkali glass substrate by a sputtering method was used as the translucent substrate with a metal-containing layer. In the same manner as described above, an optical laminate was produced.

<Comparative Example 3>
Comparative Example 1 except that a glass substrate (manufactured by Geomat Co.) in which an aluminum layer (metal-containing layer) having a thickness of about 200 nm was laminated on the surface of a non-alkali glass substrate by a sputtering method as a translucent substrate with a metal-containing layer was used. In the same manner as described above, an optical laminate was produced.

<Example 8>
As a translucent substrate with a metal-containing layer, a silver alloy layer (metal-containing layer, which is mainly composed of silver and contains palladium and copper, APC) layer having a thickness of about 200 nm is laminated on the surface of a non-alkali glass substrate by a sputtering method. An optical laminate was prepared in the same manner as in Example 1 except that a glass substrate (manufactured by Geomat Co.) was used.

<Example 9>
As a translucent substrate with a metal-containing layer, a glass substrate (manufactured by Geomat Co., Ltd.) obtained by laminating a silver alloy (alloy containing silver as a main component) layer (metal-containing layer) with a thickness of about 200 nm on the surface of a non-alkali glass substrate. ) Was used in the same manner as in Example 2 except that an optical laminate was produced.

<Example 10>
As a translucent substrate with a metal-containing layer, a glass substrate (manufactured by Geomat Co., Ltd.) obtained by laminating a silver alloy (alloy containing silver as a main component) layer (metal-containing layer) with a thickness of about 200 nm on the surface of a non-alkali glass substrate. An optical laminate was produced in the same manner as in Example 3 except that.

(Evaluation of corrosion of metal-containing layers)
(1) The optical layered bodies obtained in Examples 5 to 7 and Comparative Example 3 were put into an oven having an internal temperature of 80 ° C. and a relative humidity of 90% for 72 hours. Then, the optical layered body is taken out into the atmosphere, allowed to cool, and visually observed (with naked eyes) while illuminating with a backlight from the back side, the state of the metal-containing layer of the optical layered body is observed, and pitting corrosion occurs in the metal-containing layer. That is, the case where no generation of a hole having a diameter of 0.1 mm or more is observed is regarded as “no corrosion”, and the case where pitting corrosion (the generation of a hole having a diameter of 0.1 mm or more) is observed is determined as “the presence of corrosion”. Each was evaluated. The results are shown in Table 2.

  (2) The optical laminates obtained in Examples 8 to 10 were put into an oven having an internal temperature of 80 ° C. and a relative humidity of 90% for 160 hours, then taken out into the atmosphere, allowed to cool, and back side The state of the metal-containing layer of the optical laminate is observed visually (with the naked eye) while illuminating with a backlight, and no pitting corrosion, that is, generation of a hole with a diameter of 0.1 mm or more is not observed in the metal-containing layer The case where pitting corrosion (occurrence of a hole having a diameter of 0.1 mm or more) was observed was evaluated as “corrosion“ present ”. The results are shown in Table 3.

  DESCRIPTION OF SYMBOLS 10 Polarizing plate, 11 Polarizer, 21, 22 Protective film, 30, 31 Antistatic layer, 40 Adhesive layer, 50 Overcoat layer, 60 Metal-containing layer, 70 Translucent substrate, 100 Antistatic polarizing plate, 300 Antistatic polarizing plate with pressure-sensitive adhesive layer, 400, 500, 600 optical laminate.

Claims (3)

  An optical laminate including a polarizing plate including a polarizer, an antistatic layer, an adhesive layer, and a metal-containing layer in the order described above.   The optical laminate 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 laminate according to claim 1 or 2, further comprising an overcoat layer between the pressure-sensitive adhesive layer and the metal-containing layer.

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