CN105738998B - Polarizing film with coating layer, polarizing film with adhesive layer, and image display device - Google Patents

Abstract

The present invention relates to a polarizing film with a coating layer, a polarizing film with an adhesive layer, and an image display device. The purpose of the present invention is to provide a polarizing film with a coating layer, which, even when laminated on a transparent conductive layer via an adhesive layer, can suppress deterioration of the transparent conductive layer and increase in the surface resistance value of the transparent conductive layer, and which, even when the adhesive layer is formed, has excellent adhesion to the polarizing film. The polarizing film with a coating layer of the present invention comprises a transparent protective film, an iodine-based polarizing plate containing iodine and/or iodide ions, and a coating layer in this order, and is characterized in that the iodine-based polarizing plate and/or the coating layer contains a phosphorus-based compound.

Description

Polarizing film with coating layer, polarizing film with adhesive layer, and image display device

Technical Field

The present invention relates to a polarizing film with a coating layer, which comprises a transparent protective film, an iodine-based polarizing plate, and a coating layer in this order, and a polarizing film with an adhesive layer, which comprises the polarizing film with the coating layer and an adhesive layer. The present invention also relates to an image display device such as a Liquid Crystal Display (LCD) or an organic EL display device, which has the polarizing film with the pressure-sensitive adhesive layer.

Background

In recent years, transparent conductive films such as Indium Tin Oxide (ITO) thin films have been widely used in various applications. For example, it is known that the transparent conductive film is formed on the opposite side of the liquid crystal layer contact side of the transparent substrate constituting the liquid crystal cell in a liquid crystal display device using the liquid crystal cell such as an in-plane switching (IPS) system, as an antistatic layer. In addition, a transparent conductive film in which the transparent conductive film is formed on a transparent resin film is used for an electrode substrate of a touch panel, and for example, an input device in which a liquid crystal display device or an image display device used in a mobile phone, a portable music player, or the like is used in combination with the touch panel has been widely used.

As an input device used by combining a touch panel with an image display device, an Out-Cell type In which a transparent conductive film having a transparent conductive layer formed On a transparent base material including a glass plate or a transparent resin film is provided On a liquid crystal display device (On the upper side of a polarizing film On the observation side of the liquid crystal display device) has been widely used. In addition, it is also known that a touch panel function is realized by patterning an ITO layer, which is an antistatic layer of an image display device, as a touch sensor.

An optical member such as a polarizing film may be bonded to such an ITO layer through a pressure-sensitive adhesive layer, but it is known that when the pressure-sensitive adhesive has a carboxyl group, the ITO layer is corroded to decrease the conductivity, and as a pressure-sensitive adhesive for suppressing the decrease in conductivity, a pressure-sensitive adhesive containing a phosphorus antioxidant is known (for example, see patent document 1).

Documents of the prior art

Patent document

Patent document 1: patent specification No. 5540383

Disclosure of Invention

Problems to be solved by the invention

In recent years, weight reduction and thickness reduction have been strongly required for liquid crystal display devices, image display devices, and the like using the above transparent conductive film, and also for polarizing films used for the liquid crystal display devices and the like, weight reduction and thickness reduction have been required. As methods for making a polarizing film thinner and lighter, for example, a method for making a single-sided protective polarizing film in which a transparent protective film is provided only on one side of a polarizing plate, a method for manufacturing a thin polarizing film in which the thickness of the polarizing plate itself is made thinner, and the like are known.

For example, when a transparent conductive film is used for an antistatic layer, a polarizing film with a pressure-sensitive adhesive layer is generally stacked on a liquid crystal cell having the antistatic layer, and the antistatic layer including the transparent conductive film is bonded to the polarizing film via the pressure-sensitive adhesive layer. In the case of using a transparent conductive film for an electrode of a touch panel, depending on the configuration of the touch panel, a polarizing film with a pressure-sensitive adhesive layer may be laminated on the transparent conductive film for an electrode, and an antistatic layer including the transparent conductive film may be bonded to the polarizing film via the pressure-sensitive adhesive layer.

When the polarizing film is an iodine-based polarizing film, if the transparent conductive layer is laminated to the iodine-based polarizing film as described above and subjected to a humidification durability test (normal durability test), the resistance value of the transparent conductive layer may increase. The reason why the above-mentioned increase in the resistance value is known to be that iodine contained in the polarizing plate bleeds out to the adhesive layer, and the iodine reaches the transparent conductive layer to corrode the transparent conductive layer.

In particular, it is known that a thin iodine-based polarizing plate having a thickness of 10 μm or less requires an increase in iodine concentration in the polarizing plate in order to have polarization characteristics similar to those of conventional polarizing plates, and when a polarizing film including a polarizing plate having a high iodine concentration is laminated to a transparent conductive layer, corrosion of the transparent conductive layer by iodine is likely to occur. Further, it is known that when an iodine-based polarizing film having one surface protected is used, the transparent conductive layer is directly bonded to the iodine-based polarizing sheet via the adhesive layer, and thus corrosion of the transparent conductive layer is also likely to occur.

In addition, the pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive containing a phosphorus antioxidant described in patent document 1 cannot sufficiently secure adhesion to a polarizing film.

Accordingly, an object of the present invention is to provide a polarizing film with a coating layer, which is capable of suppressing deterioration of a transparent conductive layer and an increase in surface resistance of the transparent conductive layer even when laminated on the transparent conductive layer via an adhesive layer, and which has excellent adhesion to a polarizing film even when the adhesive layer is formed. Another object of the present invention is to provide a polarizing film with an adhesive layer, wherein the adhesive layer is provided on the polarizing film with a coating layer. Another object of the present invention is to provide an image display device including the pressure-sensitive adhesive layer of the pressure-sensitive adhesive layer-attached polarizing film and a liquid crystal panel having a transparent conductive layer.

Means for solving the problems

The present inventors have conducted extensive studies and, as a result, have found that the above problems can be solved by the following polarizing film with a coating layer, polarizing film with an adhesive layer, and the like, and have completed the present invention.

That is, the present invention relates to a polarizing film having a coating layer, comprising a transparent protective film, an iodine-based polarizing plate containing iodine and/or iodide ions, and a coating layer in this order,

the iodine-based polarizing plate and/or the coating layer contain a phosphorus-based compound.

The phosphorus-based compound preferably contains 1 or more kinds of phosphoric acid-based compounds selected from the group consisting of a polymer of a compound represented by the following general formula (1) and a compound represented by the above general formula (1), and/or 1 or more kinds of phosphonic acid-based compounds selected from the group consisting of a compound represented by the following general formula (2) and salts thereof,

[ CHEM 1 ]

(in the formula, R¹And R²Each independently represents a hydrogen atom or a hydrocarbon residue of 1 to 18 carbon atoms which may contain an oxygen atom),

[ CHEM 2 ]

(wherein R represents a hydrogen atom or a hydrocarbon residue of 1 to 18 carbon atoms which may contain an oxygen atom).

The thickness of the iodine-based polarizing plate is preferably 10 μm or less.

The iodine and/or iodide ion content in the iodine-based polarizing plate may be 3 to 12% by weight.

The coating layer may not have a transparent protective film between the iodine-based polarizing plate and the coating layer.

The coating layer is preferably formed from a resin composition containing at least 1 resin selected from the group consisting of polyurethane resins, polyvinyl alcohol resins, and acrylic resins.

The present invention also relates to a polarizing film with an adhesive layer, wherein the polarizing film with an adhesive layer is characterized by having an adhesive layer on the coating layer side of the polarizing film with a coating layer.

The pressure-sensitive adhesive layer preferably contains an ionic compound.

The pressure-sensitive adhesive layer-equipped polarizing film of the present invention can be used by laminating the pressure-sensitive adhesive layer of the pressure-sensitive adhesive layer-equipped polarizing film so as to be in contact with the transparent conductive layer of the transparent conductive member having a transparent conductive layer.

The transparent conductive layer is preferably formed of indium tin oxide. The indium tin oxide is preferably amorphous indium tin oxide.

The present invention also relates to an image display device, wherein the pressure-sensitive adhesive layer of the pressure-sensitive adhesive layer-attached polarizing film is bonded to a liquid crystal panel having a transparent conductive layer such that the pressure-sensitive adhesive layer of the pressure-sensitive adhesive layer-attached polarizing film is in contact with the transparent conductive layer of the liquid crystal panel.

Effects of the invention

The polarizing film with a coating layer of the present invention can suppress deterioration of the transparent conductive layer and increase in the surface resistance value of the transparent conductive layer even when the polarizing film is laminated on the transparent conductive layer via an adhesive layer. This is considered to be because the transfer of iodine contained in the iodine-based polarizing plate to the surface of the transparent conductive layer can be suppressed by the action of the phosphorus-based compound contained in the iodine-based polarizing plate and/or the coating layer, and as a result, corrosion of the transparent conductive layer can be prevented.

In addition, the polarizing film with an adhesive layer of the present invention can suppress deterioration of the transparent conductive layer even when the adhesive layer is bonded to the transparent conductive layer as described above. In addition, in the polarizing film with an adhesive layer of the present invention, since the polarizing film and the adhesive layer are laminated via the coating layer and the phosphorus-based compound is mixed in the iodine-based polarizing plate and/or the coating layer, the adhesiveness between the adhesive layer and the polarizing film or the coating layer is excellent. As a result, the adhesive remains during the return, peeling due to durability, insufficient adhesive during processing, and the like can be prevented. The present invention can also provide an image display device including the pressure-sensitive adhesive layer of the pressure-sensitive adhesive layer-attached polarizing film and a liquid crystal panel having a transparent conductive layer.

Drawings

FIG. 1 is a schematic cross-sectional view of a polarizing film having a coating layer according to an embodiment of the present invention.

FIG. 2 is a schematic cross-sectional view of a polarizing film with an adhesive layer according to an embodiment of the present invention.

Detailed Description

1. Polarizing film with coating layer

The polarizing film with a coating layer of the present invention comprises a transparent protective film, an iodine-based polarizing plate containing iodine and/or iodide ions, and a coating layer in this order,

the iodine-based polarizing plate and/or the coating layer contain a phosphorus-based compound.

The structure of the polarizing film with a coating layer of the present invention will be described below with reference to fig. 1, which is one embodiment of the present invention. However, the polarizing film with a coating layer of the present invention is not limited to the embodiment of fig. 1.

The polarizing film 1 with a coating layer of the present invention comprises a transparent protective film 3, an iodine-based polarizing plate 2 and a coating layer 4 in this order. Although not shown, the iodine-based polarizing plate 2 and the transparent protective film 3 are generally laminated via an adhesive layer or the like. The coating layer 4 may be directly provided on the surface of the iodine-based polarizing plate 2 not having the transparent protective film 3. As described later, the coating layer 4 may be 1 layer or 2 or more layers, and a transparent protective film may be provided between the iodine-based polarizing plate 2 and the coating layer 4, but in the present invention, the effect of the present invention is remarkable when the iodine-based polarizing plate 2 and the coating layer 4 are directly laminated. Hereinafter, the respective materials will be described.

(1) Iodine polarizing film

As the iodine-based polarizing plate 2, any polarizing plate may be used as long as it is a polarizing plate containing iodine and/or iodine ions, and examples thereof include: a polarizing plate obtained by uniaxially stretching a hydrophilic polymer film such as a polyvinyl alcohol (PVA) film, a partially formalized PVA film, or an ethylene-vinyl acetate copolymer partially saponified film, while adsorbing iodine. Among these, a polarizing plate including a PVA-based film and iodine is preferable. The thickness of these polarizing plates is not particularly limited, and is usually about 80 μm or less.

A polarizing plate obtained by dyeing a PVA-based film with iodine and uniaxially stretching the film can be produced, for example, as follows: the PVA is immersed in an aqueous iodine solution for dyeing, and then stretched to 3 to 7 times the original length. If necessary, the substrate may be immersed in an aqueous solution of boric acid, potassium iodide containing zinc sulfate, zinc chloride, or the like. If necessary, the PVA film may be immersed in water and washed with water before dyeing. The PVA film can be washed with water to wash dirt and an antiblocking agent on the surface of the PVA film, and the PVA film can be swollen to prevent unevenness such as uneven dyeing. The stretching may be performed after the dyeing with iodine, or may be performed while dyeing, or may be performed after the stretching with iodine. Stretching may also be carried out in an aqueous solution of boric acid, potassium iodide, or the like, or in a water bath.

In the present invention, a thin iodine-based polarizing plate having a thickness of 10 μm or less can be suitably used. The thickness of the iodine-based polarizing plate is preferably 1 to 7 μm from the viewpoint of thinning. Such a thin iodine-based polarizing plate is preferable because it has less thickness unevenness and excellent observation properties, and because it has less dimensional change and excellent durability, it can be thinned as the thickness of the polarizing film.

Typical examples of the thin polarizing plate include thin polarizing films described in japanese patent laid-open nos. 51-069644, 2000-338329, 2010/100917, 2010/100917, 4751481, and 2012-073563. These thin polarizing films can be obtained by a production method including a step of stretching the PVA-based resin layer and the stretching resin base material in a state of a laminate and a step of dyeing. According to this production method, even if the PVA-based resin layer is thin, it can be stretched without any trouble such as breaking due to stretching by being supported by the stretching resin base material.

As the thin polarizing film, in the production method including the step of stretching and the step of dyeing in a state of being laminated, from the viewpoint of being stretchable to a high magnification to improve the polarizing performance, a polarizing film obtained by a production method including the step of stretching in an aqueous boric acid solution as described in wo 2010/100917 pamphlet, wo 2010/100917 pamphlet, or jp 4751481 a, or jp 2012-073563 a is preferable, and a polarizing film obtained by a production method including the step of auxiliarily stretching in air before stretching in an aqueous boric acid solution as described in jp 4751481 a, or jp 2012-073563 a is particularly preferable.

By laminating a coating layer containing a phosphorus compound described later on the iodine polarizing plate 2 obtained by the above method, the phosphorus compound may be transferred from the coating layer or the like to the iodine polarizing plate 2, and the iodine polarizing plate 2 may contain the phosphorus compound. In this way, when the iodine-based polarizing plate 2 contains a phosphorus-based compound, corrosion of the transparent conductive layer can be suppressed, which is preferable. Examples of the phosphorus-based compound that can be contained in the iodine-based polarizing plate 2 include those equivalent to the phosphorus-based compound described later.

When the iodine-based polarizing plate 2 contains a phosphorus-based compound, the content thereof in the iodine-based polarizing plate 2 is preferably 3% by weight or less, more preferably 0.01 to 1% by weight, and still more preferably 0.02 to 0.6% by weight.

The content of iodine and/or iodide ions (hereinafter, also referred to as iodine content) in the iodine-based polarizing plate 2 used in the present invention may be 3 to 12 wt%, and may be 4 to 7.5 wt%. In the polarizing film 1 with a coating layer of the present invention, even if the iodine content in the iodine-based polarizing plate 2 is as high as the above range, the increase in the surface resistance of the transparent conductive layer laminated on the polarizing film 1 of the present invention can be suppressed. This is considered to be because the iodine contained in the iodine-based polarizing plate 2 and/or the phosphorus-based compound contained in the coating layer 4 described later acts to suppress the transfer of iodine contained in the iodine-based polarizing plate to the surface of the transparent conductive layer, and as a result, the corrosion of the transparent conductive layer can be prevented.

(2) Transparent protective film

The material for forming the transparent protective film 3 is preferably excellent in transparency, mechanical strength, thermal stability, moisture blocking property, isotropy, and the like. Examples thereof include: polyester polymers such AS polyethylene terephthalate and polyethylene naphthalate, cellulose polymers such AS diacetylcellulose and triacetylcellulose, acrylic polymers such AS polymethyl methacrylate, styrene polymers such AS polystyrene and acrylonitrile-styrene copolymer (AS resin), and polycarbonate polymers. Examples of the polymer forming the transparent protective film 3 include: examples of the polymer include polyolefin polymers such as polyethylene, polypropylene, polyolefins having a ring system or a norbornene structure, ethylene-propylene copolymers, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamide, imide polymers, sulfone polymers, polyether ether ketone polymers, polyphenylene sulfide polymers, vinyl alcohol polymers, vinylidene chloride polymers, vinyl butyral polymers, aryl ester polymers, polyoxymethylene polymers, epoxy polymers, and blends of the above polymers. The transparent protective film 3 may be formed as a cured layer of a heat-curable or ultraviolet-curable resin such as an acrylic, urethane, acrylic urethane, epoxy, or silicone resin.

The thickness of the transparent protective film 3 can be suitably determined, and is usually about 1 to 500 μm, preferably 1 to 300 μm, more preferably 5 to 200 μm, further preferably 5 to 150 μm, and particularly preferably 20 to 100 μm from the viewpoints of workability such as strength and workability, and thin film property.

The transparent protective film 3 may be disposed only on one side of the iodine-based polarizing plate 2 (single-sided protective polarizing film), or may be disposed on both sides of the iodine-based polarizing plate 2 (double-sided protective polarizing film). The effect of the present invention is remarkable when a single-sided protective polarizing film is used (that is, when there is no transparent protective film between the iodine-based polarizing plate 2 and the coating layer 4). In addition, even in the case of a double-sided protective polarizing film, the effect of the present invention is remarkable when the thickness of the transparent protective film (not shown) on the side in contact with the coating layer 4 is small (for example, 25 μm or less).

The iodine-based polarizing plate 2 and the transparent protective film 3 are usually adhered to each other via an aqueous adhesive or the like. Examples of the aqueous adhesive include isocyanate adhesives, polyvinyl alcohol adhesives, gelatin adhesives, vinyl adhesives, latex adhesives, aqueous polyurethanes, and aqueous polyesters. In addition to the above, examples of the adhesive for the iodine-based polarizing plate 2 and the transparent protective film 3 include an ultraviolet-curable adhesive, an electron beam-curable adhesive, and the like. The adhesive for electron beam curing type polarizing film exhibits suitable adhesiveness to the various transparent protective films 3 described above. The adhesive used in the present invention may contain a metal compound filler.

The surface of the transparent protective film 3 to which the iodine-based polarizing plate 2 is not bonded may be provided with a functional layer such as a hard coat layer, an antireflection layer, an anti-blocking layer, a diffusion layer, or an antiglare layer. The functional layer may be provided on the transparent protective film 3 itself, or may be provided as a film different from the transparent protective film 3.

(3) Coating layer

When the transparent protective film 3 is provided only on one side of the iodine-based polarizing plate 2, the coating layer 4 is provided on the other side (the side on which the transparent protective film 3 is not laminated) of the iodine-based polarizing plate 2, and when the transparent protective films 3 are provided on both sides of the iodine-based polarizing plate 2, the coating layer 4 may be provided on one transparent protective film, and when the thicknesses of the 2 transparent protective films are different, it is preferably provided on the thin transparent protective film side.

The thickness of the coating layer 4 is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, and further preferably 3 μm or less, from the viewpoint of thinning and optical reliability. The coating layer 4 may be 1 layer or 2 or more layers, but when 2 or more layers are used, the entire plurality of coating layers preferably satisfies the above thickness. When the coating layer 4 has 2 or more layers, at least 1 layer may contain a phosphorus compound.

The coating layer 4 may be formed of various materials, and may be formed by applying a coating layer forming resin composition to the iodine-based polarizing plate 2, for example. Examples of the resin material contained in the resin composition for forming a coating layer include: various polymers such as polyester resins, polyether resins, polycarbonate resins, polyurethane resins, silicone resins, polyamide resins, polyimide resins, PVA resins, and acrylic resins, metal oxide sols, and silica sols. These resins may be appropriately blended with a crosslinking agent. These resin materials may be used alone in 1 kind, or in combination with 2 or more kinds, but among them, from the viewpoint of adhesion to an iodine-based polarizing plate and optical reliability, 1 or more kinds selected from among a polyurethane-based resin, a PVA-based resin, and an acrylic resin are preferable, and a PVA-based resin is more preferable. The resin may be in the form of any of an aqueous resin and a solvent resin.

When the pressure-sensitive adhesive layer contains an acid component (for example, when a carboxyl group-containing monomer such as acrylic acid is contained as a monomer unit of the (meth) acrylic polymer), the coating layer on the pressure-sensitive adhesive layer side preferably contains a compound having a functional group (for example, oxazoline group or the like) reactive with the acid component, from the viewpoint of securing adhesion. For example, when the coating layer is 2 or more layers, the coating layer closest to the adhesive layer side preferably contains a polymer containing an oxazoline group.

(resin composition for Forming coating layer containing PVA-based resin)

The PVA-based resin may be, for example, one obtained by saponifying polyvinyl acetate, and the PVA-based resin may be a saponified product of a copolymer of vinyl acetate and a monomer copolymerizable therewith, and when the monomer copolymerizable therewith is ethylene, an ethylene-vinyl alcohol copolymer may be obtained, and the monomer copolymerizable therewith may be, for example, an unsaturated carboxylic acid such as maleic acid (anhydride), fumaric acid, crotonic acid, itaconic acid, or (meth) acrylic acid, or an ester thereof, α -olefin such as ethylene or propylene, a (meth) allylsulfonic acid (sodium), a sodium sulfonate (monoalkylmaleate), a disulfonic acid alkylsulfonate, N-methylolacrylamide, an acrylamide alkylsulfonate, an N-vinylpyrrolidone, or an N-vinylpyrrolidone derivative, and the like.

As the PVA-based resin, the PVA or a modified PVA-based resin having a hydrophilic functional group in a side chain of a copolymer thereof can be used. Examples of the hydrophilic functional group include an acetoacetyl group and a carbonyl group. Further, a modified PVA obtained by acetalizing, carbamating, etherifying, grafting, phosphorylating, etc. a PVA-based resin may be used.

The coating layer 4 used in the present invention may be formed of a resin composition for forming a coating layer containing the PVA-based resin as a main component and a phosphorus-based compound described later, and the resin composition may contain a curable component (crosslinking agent) or the like. The proportion of the PVA-based resin in the coating layer 4 or the resin composition (solid content) is preferably 80 wt% or more, more preferably 90 wt% or more, and still more preferably 95 wt% or more.

(resin composition for forming coating layer containing acrylic resin)

The acrylic resin is preferably a curable forming material containing the following curable components. The curable component can be broadly classified into an active energy ray-curable type such as an electron beam-curable type, an ultraviolet-curable type, and a visible ray-curable type, and a heat-curable type. The ultraviolet-curable type and the visible-light-curable type can be classified into a radical polymerization-curable type and a cationic polymerization-curable type. In the present invention, the active energy ray having a wavelength range of 10nm or more and less than 380nm is represented as ultraviolet ray, and the active energy ray having a wavelength range of 380nm to 800nm is represented as visible ray. The radical polymerization curing type curable component can be used as a thermosetting type curable component.

(radical polymerization curing type Forming Material)

Examples of the curable component include a radical polymerizable compound. Examples of the radical polymerizable compound include compounds having a radical polymerizable functional group having a carbon-carbon double bond such as a (meth) acryloyl group or a vinyl group. Any of monofunctional radical polymerizable compounds and difunctional or higher polyfunctional radical polymerizable compounds can be used as the curable component. These radical polymerizable compounds may be used alone in 1 kind, or in combination with 2 or more kinds. As these radical polymerizable compounds, for example, compounds having a (meth) acryloyl group are suitable. In the present invention, the (meth) acryloyl group means an acryloyl group and/or a methacryloyl group, and the following (meth) acryloyl groups have the same content.

(form of radical polymerization curing type Forming Material)

The radical polymerization curing type forming material can be used as an active energy ray curing type or a thermosetting type forming material. When an electron beam or the like is used as the active energy ray, the active energy ray-curable material does not need to contain a photopolymerization initiator, but when an ultraviolet ray or a visible ray is used as the active energy ray, a photopolymerization initiator is preferably contained. On the other hand, when the curable component is used as the thermosetting component, the forming material preferably contains a thermal polymerization initiator.

The formation of the coating layer using the curable forming material is performed by applying the curable forming material to the surface of the iodine-based polarizing plate (or the transparent protective film) and then curing the material. The iodine-based polarizing plate (or transparent protective film) may be subjected to a surface modification treatment before being coated with the curing-type forming material. Specific examples of the treatment include corona treatment, plasma treatment, and saponification treatment.

The application method of the curable forming material can be appropriately selected depending on the viscosity of the curable forming material and the target thickness. Examples of the coating method include: a reverse coater, a gravure coater (direct type, reverse type, offset type), a bar reverse coater, a roll coater, a die coater, a bar coater, and the like. In addition, a dip coating method or the like can be suitably used for coating.

The curing of the forming material may be performed in the following manner.

(active energy ray-curable type)

The active energy ray-curable forming material is formed by applying the active energy ray-curable forming material to an iodine-based polarizing plate (or a transparent protective film), and then irradiating the iodine-based polarizing plate (or the transparent protective film) with active energy rays (e.g., electron beams, ultraviolet rays, and visible rays) to cure the active energy ray-curable forming material. The irradiation direction of the active energy ray (electron beam, ultraviolet ray, visible ray, etc.) may be from any appropriate direction. The irradiation is preferably performed from the coating layer side.

(thermosetting type)

On the other hand, the thermosetting type forming material forms a cured product layer by bonding a polarizing plate and a transparent protective film and heating them, thereby initiating polymerization by a thermal polymerization initiator. The heating temperature is set according to the thermal polymerization initiator, but is about 60 to 200 ℃, preferably 80 to 150 ℃.

(resin composition for forming coating layer containing polyurethane resin)

The polyurethane resin used in the present invention is a resin obtainable by reacting a polyol with a polyisocyanate, and specifically, a polyurethane resin preferably used includes, for example, the Denatron series manufactured by gargarine corporation.

When the coating layer is formed using an aqueous material, an aqueous dispersion polymer is used. Examples of the water-dispersible polymer include: examples of the emulsifier include those obtained by emulsifying various resins such as polyurethane and polyester with an emulsifier, those obtained by introducing water-dispersible anionic groups, cationic groups, or nonionic groups into the above resins and self-emulsifying them.

(phosphorus-based Compound)

In the present invention, either one or both of the iodine-based polarizing plate and the coating layer contain a phosphorus-based compound. Examples of the phosphorus-based compound include phosphoric acid-based compounds, phosphonic acid-based compounds, and phosphorus-based antioxidants, and in the present invention, two or more of these may be used alone or in combination. Among them, a phosphoric acid-based compound or a phosphonic acid-based compound is preferable.

Examples of the phosphoric acid-based compound include a phosphoric acid-based compound selected from a polymer of a compound represented by the following general formula (1) and a compound represented by the above general formula (1),

[ CHEM 3 ]

(in the formula, R¹And R²Each independently represents a hydrogen atom or a hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom. ).

Examples of the phosphoric acid-based compound include phosphoric acid, phosphoric acid esters, and salts, dimers, and trimers thereof, as described later. These will be described in detail below.

In the general formula (1), R¹And R²Each independently represents a hydrogen atom or a hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom. Examples of the hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom include an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, and a- (CH)₂CH₂O)_nR³(R³Is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms, and n is an integer of 0 to 15. ) And the like. The alkyl group and the alkenyl group may be linear or branched. Among them, the hydrocarbon residue having 1 to 18 carbon atoms is preferably a linear or branched alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 18 carbon atoms, and more preferably a linear or branched alkyl group having 2 to 6 carbon atoms.

In the present invention, R of the general formula (1) can also be suitably used¹And R²Phosphoric acid (H) in which any one of the above is a hydrogen atom₃PO₄). In addition, salts of the above-mentioned phosphoric acids (metal salts such as sodium, potassium, and magnesium, ammonium salts, and the like) can also be suitably used.

In the present invention, the compound represented by the general formula (1) is preferably an acidic phosphate. Here, the acidic phosphate is R of the general formula (1)¹And R²All of them are cases (diester bodies) of hydrocarbon residues having 1 to 18 carbon atoms which may contain oxygen atoms; or R¹、R²Examples of the monoester compound include a phosphate compound represented by the following general formula (1'),

[ CHEM 4 ]

(in the formula, R¹R is the same as above³Is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms, and n is an integer of 0 to 15. ).

R of the formula (1¹And R of the general formula (1)¹Also, the hydrocarbon residue is a hydrocarbon residue having 1 to 18 carbon atoms which may contain a hydrogen atom or an oxygen atom. Examples of the hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom include the same ones as described above. R as formula (1')¹The alkyl group is preferably a hydrogen atom, a C1-18 linear or branched alkyl group, or a C6-18 aryl group, more preferably a hydrogen atom, a C1-10 linear or branched alkyl group, and still more preferably a hydrogen atom, or a C2-6 linear or branched alkyl group. As R³Examples thereof include an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms, preferably an alkyl group having 1 to 18 carbon atoms and an aryl group having 6 to 18 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and further preferably an alkyl group having 2 to 6 carbon atoms. In addition, n is an integer of 0 to 15, preferably 0 to 10. In the present invention, it is preferable not to contain a polyethylene oxide structure (CH) from the viewpoint of preventing deterioration₂CH₂O) (i.e., in formula (1'), n is 0).

The phosphate ester compound represented by the general formula (1') is preferably R from the viewpoint of the adsorption effect on an adherend¹Is a hydrogen atom, R³A phosphoric monoester having a C1-18 linear or branched alkyl group, more preferably R¹Is a hydrogen atom, R³A phosphoric monoester having a C1-10 linear or branched alkyl group, and more preferably R¹Is a hydrogen atom, R³Is a phosphoric monoester of a C2-6 linear chain or branched chain alkyl.

In the present invention, 2 or more compounds represented by the general formula (1 ') may be mixed and used, and a mixture of the compound represented by the general formula (1') and the phosphoric acid may be used. In addition, the phosphate ester compound represented by the general formula (1') is usually obtained as a mixture of a monoester and a diester, and it is preferable to use the mixture of a monoester and a diester after further adding the phosphoric acid.

In the present invention, salts of the compounds represented by the general formula (1') (metal salts such as sodium, potassium and magnesium, ammonium salts, etc.) can also be suitably used.

Examples of commercially available phosphoric acid ester compounds represented by the above general formula (1') include: "Phosphanol SM-172" (R of the general formula (1')) manufactured by Toho chemical industry Co., Ltd¹＝R³＝C₈H₁₇N is 0, a mono/di mixture (monoester: diester: 5 (weight ratio), acid value: 219mgKOH/g), "Phosphanol GF-185" (R of formula (1'), "Phosphoanol GF-185¹＝R³＝C₁₃H₂₇N is 0, mono/di mixture, acid number: 158mgKOH/g), "Phosphanol BH-650" (R of formula (1')¹＝R³＝C₄H₉N ═ 1, mono/di mixture, acid number: 388mgKOH/g), "Phosphanol RS-410" (R of the general formula (1')¹＝R³＝C₁₃H₂₇N is 4, a mono/di mixture (monoester: diester: 5 (weight ratio), acid value: 105mgKOH/g), "Phosphanol RS-610" (R of formula (1'), "Photophanol RS-610¹＝C₁₃H₂₇，R³＝C₁₃H₂₇N is 6, mono/di mixture, acid number: 82mgKOH/g), "PhosphanolRS-710" (R of the general formula (1')¹＝C₁₃H₂₇，R³＝C₁₃H₂₇N is 10, mono/di mixture (monoester: diester: 5 (weight ratio)), acid value: 62mgKOH/g), "Phosphanol ML-220" (R of formula (1')¹＝R³＝C₁₂H₂₅N-2, mono/di mixture), "Phosphanol ML-200" (R of general formula (1'), "Phosphanol ML-200¹＝R³＝C₁₂H₂₅N is 0, a mono/di mixture), "Phosphanol ED-200" (R of formula (1'), "Phosphanol ED-200¹＝R³＝C₈H₁₇N-1, mono/di mixture, "Phosphanol RL-210" ((1') R¹＝R³＝C₁₈H₃₇N is 2, a mono/di mixture),'.Phosphonol GF-339 (R of general formula (1'))¹＝R³＝C₆H₁₃～C₁₀H₂₁A mono/di mixture of (a), n-0, "Phosphanol GF-199" (R of general formula (1'))¹＝R³＝C₁₂H₂₅N-0, mono/di mixture), "Phosphanol RL-310" (R of formula (1')¹＝R³＝C₁₈H₃₇N-3, mono/di mixture), "Phosphanol LP-700" (R of formula (1'), "Phosphanol LP-700¹＝R³＝C₆H₅N-6, mono/di mixture), "AP-1" (R of general formula (1'), "manufactured by da octa chemical industry co¹＝R³＝CH₃N is 0, mono/di mixture, acid number: 650mgKOH/g or more), "AP-4" (R of the general formula (1')¹＝R³＝C₄H₉N is 0, mono/di mixture, acid number: 452mgKOH/g), "DP-4" (R of the general formula (1')¹＝R³＝C₄H₉N ═ 0, diester body, acid value: 292mgKOH/g), "MP-4" (R of the general formula (1')¹＝H，R³＝C₄H₉N is 0, mono/di mixture (monoester: diester: 8: 2 (weight ratio)), acid value: 670mgKOH/g), "AP-8" (R of the general formula (1')¹＝R³＝C₈H₁₇N is 0, mono/di mixture, acid number: 306mgKOH/g), "AP-10" (R of the general formula (1')¹＝R³＝C₁₀H₂₁N is 0, mono/di mixture, acid number: 263mgKOH/g), "MP-10" (R of the general formula (1')¹＝H，R³＝C₁₀H₂₁N is 0, monoester, acid value: 400mgKOH/g), "JP-508" (R of the general formula (1'), "manufactured by North China chemical Co., Ltd¹＝R³＝C₈H₁₇N is 0, mono/di mixture, acid number: 288mgKOH/g), "JP-513" (R of the general formula (1')¹＝R³＝C₁₃H₂₇N is 0, a mono/di mixture), "JP-524R" (R of general formula (1'), "JP-524R¹＝R³＝C₂₄H₄₉N is 0, a mono/di mixture), "DBP" (R of formula (1'), "c¹＝R³＝C₄H₉N is 0, mono/di mixture (monoester: diester: 1: 9 (weight ratio)), acid value: 266mgKOH/g), "LB-58" (R of the general formula (1')¹＝R³＝C₈H₁₇N ═ 0, diester body, acid value: 173mgKOH/g), "Nikkol DDP-2" (R of the general formula (1')¹＝R³＝C₁₂H₂₅～C₁₅H₃₁And n ═ 2), and the like, and salts thereof. Furthermore, the above-mentioned "mono/di-mixture" means a monoester (R)¹H) and diesters (R)¹A hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom), for example, Phosphonol SM-172, a monoester (R of the general formula (1')¹＝H，R³＝C₈H₁₇N ═ 0) and diesters (R of the formula (1')¹＝R³＝C₈H₁₇And n ═ 0).

The phosphoric acid-based compound used in the present invention may be a mixture of 1 or more compounds selected from the group consisting of the compounds represented by the general formula (1) (or the compounds represented by the general formula (1')), salts thereof, and polymers thereof, or a mixture of 2 or more compounds selected from the group consisting of phosphoric acid, phosphoric monoester, and phosphoric diester, and more preferably a mixture containing phosphoric monoester and phosphoric acid. Here, the phosphoric monoester means R of the general formula (1)¹And R²One of the hydrogen atoms and the other being a C1-18 hydrocarbon residue which may contain an oxygen atom (in the case of the general formula (1'), R is¹A compound which is a hydrogen atom), phosphoric acid diester means R of the general formula (1)¹And R²A hydrocarbon residue of 1 to 18 carbon atoms which may contain an oxygen atom (in the case of the compound represented by the general formula (1'), R¹A hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom).

The acid value of the phosphoric acid compound used in the present invention is preferably 900mgKOH/g or less, more preferably 50 to 800mgKOH/g, and most preferably 10 to 700 mgKOH/g. From the viewpoint of the treatment in production, the acid value of the phosphoric acid compound is preferably 400mgKOH/g or less, more preferably 50 to 400mgKOH/g, still more preferably 50 to 350mgKOH/g, and particularly preferably 100 to 300 mgKOH/g. When the composition for forming the coating layer 4 contains a crosslinking agent, the phosphoric acid compound may act as a reaction catalyst for the crosslinking reaction depending on the kind of the crosslinking agent (for example, an isocyanate-based crosslinking agent), and in this case, the pot life of the composition for forming the coating layer 4 may be shortened, and the handleability may be deteriorated. When the acid value of the phosphoric acid compound is in the above range, the action as a catalyst can be suppressed, and therefore, the acid value is preferable from the viewpoint of the pot life of the composition for forming the coating layer 4. From the viewpoint of effectively exerting the effect, it is preferable to add the phosphoric acid compound having an acid value within the above range in an amount to be added as described later.

Examples of the polymer of the compound represented by the general formula (1) include dimers and trimers of the compound represented by the general formula (1).

Further, the phosphorus-based compound may be a phosphonic acid-based compound. Examples of the phosphonic acid-based compound include a phosphonic acid-based compound selected from the group consisting of compounds represented by the following general formula (2) and salts thereof,

[ CHEM 5 ]

(wherein R represents a hydrogen atom or a hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom).

In the general formula (2), R is a hydrogen atom or a hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom. Examples of the hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom include an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, and the like. The alkyl group and the alkenyl group may be linear or branched.

Phosphonic acid (HP (═ O) (OH) in which R is a hydrogen atom, which may be of general formula (2)₂). In addition, salts of the above phosphonic acids (metal salts such as sodium, potassium, and magnesium, ammonium salts, and the like) can also be suitably used.

Specific examples of the phosphonic acid-based compound represented by the general formula (2) include: phosphonic acid, methylphosphonic acid, ethylphosphonic acid, n-propylphosphonic acid, isopropylphosphonic acid, n-butylphosphonic acid, tert-butylphosphonic acid, sec-butylphosphonic acid, isobutylphosphonic acid, n-pentylphosphonic acid, n-hexylphosphonic acid, isohexylphosphonic acid, n-heptylphosphonic acid, n-octylphosphonic acid, isooctylphosphonic acid, tert-octylphosphonic acid, n-nonylphenic acid, n-decylphosphonic acid, isodecylphosphonic acid, n-dodecylphosphonic acid, n-tetradecylphosphonic acid, n-hexadecylphosphonic acid, n-octadecylphosphonic acid, n-eicosylphosphonic acid, cyclobutylphosphonic acid, cyclopentylphosphonic acid, cyclohexylphosphonic acid, norbornylphosphonic acid, phenylphosphonic acid, naphthylphosphonic acid, biphenylphosphonic acid, methoxyphenylphosphonic acid, ethoxyphenylphosphon. In the present invention, these may be used alone or in combination of two or more.

Further, as the phosphorus-based compound, a phosphorus-based antioxidant can be mentioned. Specific examples of the phosphorus-based antioxidant include: trioctyl phosphite, trilauryl phosphite, tris (tridecyl) phosphite, triisodecyl phosphite, phenyl diisooctyl phosphite, phenyl diisodecyl phosphite, phenyl ditridecyl phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl phosphite, diphenyl tridecyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2, 4-di-tert-butylphenyl) phosphite, tris (butoxyethyl) phosphite, tetrakis (tridecyl) -4, 4 ' -butylidebis (3-methyl-6-tert-butylphenol) -diphosphite, 4 ' -isopropylidenediphenol alkyl phosphite (wherein the alkyl group is about 12 to 15 carbon atoms), 4 ' -isopropylidebis (2-tert-butylphenol)/bis (nonylphenyl) phosphite, Tris (biphenyl) phosphite, tetrakis (tridecyl) -1, 1, 3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butane bisphosphite, tris (3, 5-di-tert-butyl-4-hydroxyphenyl) phosphite, hydrogenated-4, 4 '-isopropylidenediphenol polyphosphite, bis (octylphenyl)/bis [4, 4' -butylidebis (3-methyl-6-tert-butylphenol) ]/1, 6-hexanediol bisphosphite, hexa (tridecyl) -1, 1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenol) bisphosphite, tris [4, 4 '-isopropylidenebis (2-tert-butylphenol) ] phosphite, tris (4, 4' -isopropylidenebis (2-tert-butylphenol) ] phosphite, Tris (1, 3-distearoyloxyisopropyl) phosphite, 9, 10-dihydro-9-phosphaphenanthrene-10-oxide, tetrakis (2, 4-di-tert-butylphenyl) -4, 4 '-biphenylene diphosphonite, distearyl pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, phenyl/4, 4' -isopropylidenediphenol/pentaerythritol diphosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, phenyl bisphenol-A-pentaerythritol diphosphite and the like.

The amount of the phosphorus-based compound added is preferably 0.01 to 10 parts by weight, more preferably 0.01 to 5 parts by weight, and still more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the resin component contained in the resin composition for forming a coating layer. When the amount of the phosphorus compound is in the above range, the surface resistance of the transparent conductive layer can be suppressed from increasing, which is preferable. In the present invention, as described above, 2 or more phosphorus-based compounds may be used in combination, and in this case, the total amount may be added so as to fall within the above range.

The coating layer forming material may contain an antistatic agent. The antistatic agent is not particularly limited as long as it is a material capable of imparting conductivity, and examples thereof include an ionic surfactant, a conductive polymer, a metal oxide, carbon black, a carbon nanomaterial, and the like, and among these, a conductive polymer is preferable, and a water-dispersible conductive polymer is more preferable.

Examples of the water-soluble conductive polymer include polyaniline sulfonic acid (weight average molecular weight 150000 in terms of polystyrene, manufactured by mitsubishi yang corporation) and the like, and examples of the water-dispersible conductive polymer include polythiophene-based conductive polymer (tradename, dentron series, manufactured by gargle chemical company) and the like.

The amount of the antistatic agent is, for example, 70 parts by weight or less, preferably 50 parts by weight or less, based on 100 parts by weight of the polymer used as the material for forming the coating layer. In terms of antistatic effect, it is preferably 10 parts by weight or more, and more preferably 20 parts by weight or more.

In addition, various additives may be added to the material for forming the coating layer in order to suppress deterioration of the adhesive layer and the iodine-based polarizing plate, which occurs when the coating layer comes into contact with the adhesive layer, and various additives may be added to impart a function to the coating layer. For example, an antioxidant (other than phosphorus), an anti-deterioration agent, an ultraviolet absorber, a fluorescent whitening agent, and the like may be added.

The method for forming the coating layer is not particularly limited, and can be carried out by a generally known method. In addition, when the coating layer is formed, the polarizing film 1 may be subjected to an activation treatment. The activation treatment may be carried out by various methods, for example, corona treatment, low-pressure UV treatment, plasma treatment, or the like may be used.

In the present invention, by forming the coating layer-provided polarizing film having the coating layer 4 formed of the resin composition containing the phosphoric acid-based compound, even when the coating layer-provided polarizing film is laminated on the transparent conductive layer via the adhesive layer, the surface resistance of the transparent conductive layer can be prevented from increasing.

2. Polarizing film with adhesive layer

The polarizing film with an adhesive layer of the present invention is characterized by having an adhesive layer on the coating layer side of the above polarizing film with a coating layer.

The structure of the polarizing film with an adhesive layer of the present invention will be described below with reference to fig. 2, which is one embodiment of the present invention. The polarizing film with an adhesive layer according to the present invention is not limited to the embodiment of fig. 2.

As shown in fig. 2, the polarizing film with an adhesive layer 6 of the present invention has an adhesive layer 5 on the coating layer 4 side of the above-described polarizing film with a coating layer 1. A separator (not shown) may be provided on the adhesive layer 5 of the adhesive layer-attached polarizing film 6 of the present invention to protect the adhesive layer 5 before it is put to practical use. Further, a surface protective film (not shown) may be provided on the transparent protective film 3 side of the polarizing film 6 with the pressure-sensitive adhesive layer. Hereinafter, the respective materials will be described.

The adhesive layer 5 may be formed using any suitable adhesive, and the type thereof is not particularly limited. Examples of the binder include: among these, acrylic adhesives are preferably used from the viewpoint of excellent optical transparency, adhesion properties exhibiting suitable adhesiveness, cohesiveness and adhesiveness, and excellent weather resistance and heat resistance.

Examples of the acrylic adhesive include adhesives containing a (meth) acrylic polymer. The (meth) acrylic polymer is not particularly limited, and is preferably a polymer obtained by polymerizing a monomer component containing an alkyl (meth) acrylate and a hydroxyl group-containing monomer. The alkyl (meth) acrylate means an alkyl acrylate and/or an alkyl methacrylate, and has the same meaning as (meth) in the present invention.

As the alkyl group of the alkyl (meth) acrylate, various linear or branched alkyl groups can be used. Specific examples of the alkyl (meth) acrylate include: propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, isoprene (イソペンチル) ester (meth) acrylate, isoprene (イソアミル) ester (meth) acrylate, n-hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, isomyristyl (meth) acrylate, n-tridecyl (meth) acrylate, tetradecyl (meth) acrylate, stearyl (meth) acrylate, and, Octadecyl (meth) acrylate, dodecyl (meth) acrylate, or the like. These may be used alone or in combination. Among these, alkyl (meth) acrylates having an alkyl group having 4 to 18 carbon atoms are preferable, (meth) acrylates having an alkyl group having 4 to 10 carbon atoms are more preferable, n-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are even more preferable, and n-butyl (meth) acrylate is particularly preferable.

The hydroxyl group-containing monomer is not particularly limited, and a monomer having a hydroxyl group and having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group can be used. Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, and (4-hydroxymethylcyclohexyl) methyl (meth) acrylate, and 1 kind or 2 or more kinds of these monomers may be used alone or in combination. Among these, 4-hydroxybutyl acrylate is preferred. When an isocyanate-based crosslinking agent is used as a crosslinking agent described later, it is preferable to use 4-hydroxybutyl acrylate as a hydroxyl group-containing monomer because the crosslinking point with the isocyanate group of the isocyanate-based crosslinking agent can be efficiently secured.

The monomer component forming the (meth) acrylic polymer used in the present invention may contain the alkyl (meth) acrylate having an alkyl group having 4 to 18 carbon atoms, and optionally the hydroxyl group-containing monomer, and in addition to these monomers, a carboxyl group-containing monomer, an aryl group-containing monomer, and other comonomers may be used as the monomer component.

As the carboxyl group-containing monomer, a monomer having a carboxyl group and having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group can be used without particular limitation. Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and the like, and these may be used alone or in combination.

As the aryl group-containing monomer, a monomer having an aryl group and having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group can be used without particular limitation. Examples of the aryl group-containing monomer include aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate.

The other comonomer is not particularly limited as long as it is a monomer having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group, and examples thereof include: alicyclic hydrocarbon esters of (meth) acrylic acid such as cyclohexyl (meth) acrylate, bornyl (meth) acrylate, and isobornyl (meth) acrylate; vinyl esters such as vinyl acetate and vinyl propionate; styrenic monomers such as styrene; epoxy group-containing monomers such as glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate; alkoxy group-containing monomers such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate; cyano group-containing monomers such as acrylonitrile and methacrylonitrile; functional monomers such as 2-methacryloyloxyethyl isocyanate; olefin monomers such as ethylene, propylene, isoprene, butadiene, and isobutylene; vinyl ether monomers such as vinyl ether monomers; for example, halogen atom-containing monomers such as vinyl chloride.

Further, as the copolymerizable monomer, there may be mentioned: maleimide monomers such as N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide and N-phenylmaleimide; an itaconimide-based monomer such as N-methylitaconimide, N-ethylitaconimide, N-butylitaconimide, N-octylitaconimide, N-2-ethylhexylitaconimide, N-cyclohexylitaconimide, N-laurylitaconimide, etc.; succinimide monomers such as N- (meth) acryloyloxymethylene succinimide, N- (meth) acryloyl-6-oxyhexamethylene succinimide, and N- (meth) acryloyl-8-oxyoctamethylene succinimide; examples of the sulfonic acid group-containing monomers include styrenesulfonic acid, allylsulfonic acid, 2- (meth) acrylamido-2-methylpropanesulfonic acid, (meth) acrylamidopropanesulfonic acid, sulfopropyl (meth) acrylate, and (meth) acryloyloxynaphthalenesulfonic acid.

Further, as the copolymerizable monomer, an amide group-containing monomer may be mentioned. The amide group-containing monomer is a compound having an amide group in its structure and containing a polymerizable unsaturated double bond such as a (meth) acryloyl group or a vinyl group. Specific examples of the amide group-containing monomer include: acrylamide monomers such as (meth) acrylamide, N-dimethyl (meth) acrylamide, N-diethyl (meth) acrylamide, N-isopropylacrylamide, N-methyl (meth) acrylamide, N-butyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-methylol-N-propane (meth) acrylamide, aminomethyl (meth) acrylamide, aminoethyl (meth) acrylamide, mercaptomethyl (meth) acrylamide, and mercaptoethyl (meth) acrylamide; n-acryloyl heterocyclic monomers such as N- (meth) acryloyl morpholine, N- (meth) acryloyl piperidine, and N- (meth) acryloyl tetrahydropyrrole; and N-vinyl group-containing lactam monomers such as N-vinylpyrrolidone and N-vinyl-epsilon-caprolactam. The amide group-containing monomer is preferable from the viewpoint of satisfying durability, and among the amide group-containing monomers, particularly, the lactam-based monomer containing an N-vinyl group is preferable from the viewpoint of satisfying durability against the transparent conductive layer.

Further, as the copolymerizable monomer, there may be mentioned: glycol-based acrylate monomers such as polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxyethylene glycol (meth) acrylate, and methoxypolypropylene glycol (meth) acrylate; and acrylate monomers containing a heterocyclic ring or a halogen atom such as tetrahydrofurfuryl (meth) acrylate and fluoro (meth) acrylate.

In addition, as the copolymerizable monomer, a polyfunctional monomer can be used. Examples of the polyfunctional monomer include compounds having 2 or more unsaturated double bonds such as a (meth) acryloyl group and a vinyl group. Examples thereof include: (mono or poly) ethylene glycol di (meth) acrylates such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetraethylene glycol di (meth) acrylate, etc.; (mono or poly) alkylene glycol di (meth) acrylates such as (mono or poly) propylene glycol di (meth) acrylates such as propylene glycol di (meth) acrylate; further, there may be mentioned esterified products of (meth) acrylic acid and polyhydric alcohols such as neopentyl glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like; polyfunctional vinyl compounds such as divinylbenzene; and compounds having a reactive unsaturated double bond such as allyl (meth) acrylate and vinyl (meth) acrylate. In addition, as the polyfunctional monomer, polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, or the like obtained by adding 2 or more unsaturated double bonds such as a (meth) acryloyl group, a vinyl group, or the like, which are the same functional groups as the monomer components, to a skeleton such as polyester, epoxy compound, urethane, or the like, may be used.

The production of such a (meth) acrylic polymer is not particularly limited, and known production methods such as solution polymerization, bulk polymerization, emulsion polymerization, and various radical polymerizations can be appropriately selected. The obtained (meth) acrylic polymer may be any of a random copolymer, a block copolymer, a graft copolymer, and the like.

In the solution polymerization, for example, ethyl acetate, toluene, or the like is used as a polymerization solvent. As a specific example of the solution polymerization, the reaction is carried out under reaction conditions of about 50 to 70 ℃ and about 5 to 30 hours, in which a polymerization initiator is added under a stream of an inert gas such as nitrogen.

The polymerization initiator, chain transfer agent, emulsifier, and the like used in the radical polymerization are not particularly limited and may be appropriately selected and used. The weight average molecular weight of the (meth) acrylic polymer can be controlled by the amount of the polymerization initiator, the amount of the chain transfer agent used, and the reaction conditions, and the amount of the polymerization initiator, the amount of the chain transfer agent used can be appropriately adjusted according to the kind of the polymerization initiator, the amount of the chain transfer agent used, and the reaction conditions.

The acrylic pressure-sensitive adhesive composition used in the present invention may contain various silane coupling agents for improving the adhesion under high-temperature and high-humidity conditions, and the silane coupling agents may include any suitable functional group, examples of the functional group include vinyl-containing silane coupling agents such as vinyl, epoxy, amino, mercapto, (meth) acryloxy, acetoacetyl, isocyanate, styryl, and polythioether, specific examples include epoxy-containing silane coupling agents such as vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, and vinyltributoxysilane, epoxy-containing silane coupling agents such as γ -glycidoxypropyltrimethoxysilane, γ -glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, epoxy-containing silane coupling agents such as γ -aminopropyltrimethoxysilane, N- β - (aminoethyl) - γ -aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, γ -aminopropyltrimethoxysilane, γ -containing silane coupling agents such as γ -glycidyloxypropyltrimethoxysilane, γ -containing silane coupling agents such as N-glycidyloxypropyltrimethoxysilane, γ -glycidyloxysilane coupling agents, γ -glycidyl-containing isocyanate, and γ -containing aminosilane coupling agents such as N- (1, 3-dimethylbutyloxy) dimethoxysilane, N-phenyltrimethoxysilane, N-aminopropyltrimethoxysilane, and γ -aminopropyltrimethoxysilane.

In addition, the addition of a crosslinking agent to the acrylic pressure-sensitive adhesive composition used in the present invention is preferable because cohesive force relating to the durability of the pressure-sensitive adhesive can be imparted.

As the crosslinking agent, a polyfunctional compound can be used, and examples thereof include an organic crosslinking agent and a polyfunctional metal chelate. Examples of the organic crosslinking agent include: epoxy-based crosslinking agents, isocyanate-based crosslinking agents, carbodiimide-based crosslinking agents, imine-based crosslinking agents, oxazoline-based crosslinking agents, aziridine-based crosslinking agents, peroxide-based crosslinking agents, and the like. The polyfunctional metal chelate compound is a substance in which a polyvalent metal atom is covalently or coordinately bonded to an organic compound. Examples of the polyvalent metal atom include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, Ti and the like. Examples of the atom in the covalently or coordinately bonded organic compound include an oxygen atom, and examples of the organic compound include an alkyl ester, an alcohol compound, a carboxylic acid compound, an ether compound, and a ketone compound. These crosslinking agents may be used alone in 1 kind or in combination of 2 or more kinds. Among these, peroxide-based crosslinking agents and isocyanate-based crosslinking agents are preferable, and a combination of these is more preferable.

The isocyanate-based crosslinking agent is a compound having 2 or more isocyanate groups (including an isocyanate-regenerating functional group in which an isocyanate group is temporarily protected by a blocking agent, polymerization, or the like) in 1 molecule.

Examples of the isocyanate-based crosslinking agent include: aromatic isocyanates such as toluene diisocyanate and xylene diisocyanate, alicyclic isocyanates such as isophorone diisocyanate, and aliphatic isocyanates such as hexamethylene diisocyanate.

Various peroxides are used as the peroxide-based crosslinking agent. Examples of the peroxide include: di (2-ethylhexyl) peroxydicarbonate, di (4-tert-butylcyclohexyl) peroxydicarbonate, di-sec-butyl peroxydicarbonate, tert-butyl peroxyneodecanoate, tert-hexyl peroxypivalate, tert-butyl peroxypivalate, dilauroyl peroxide, di-n-octanoyl peroxide, 1, 3, 3-tetramethylbutyl peroxyisobutyrate, 1, 3, 3-tetramethylbutyl peroxy2-ethylhexanoate, di (4-methylbenzoyl) peroxide, dibenzoyl peroxide, tert-butyl peroxyisobutyrate, and the like. Among these, bis (4-t-butylcyclohexyl) peroxydicarbonate, dilauroyl peroxide, and dibenzoyl peroxide, which are excellent in crosslinking reaction efficiency, are particularly preferably used.

In addition, it is preferable to add an ionic compound to the acrylic pressure-sensitive adhesive composition used in the present invention, from the viewpoint of not only imparting an antistatic function but also suppressing an increase in the surface resistance of the transparent conductive layer.

As the ionic compound, an alkali metal salt and/or an organic cation-anion salt can be preferably used. The alkali metal salt can be an organic salt or an inorganic salt of an alkali metal. The term "organic cation-anion salt" as used herein refers to a compound which is an organic salt and in which the cation portion is composed of an organic substance, and the anion portion may be either an organic substance or an inorganic substance. The "organic cation-anion salt" is also referred to as an ionic liquid or an ionic solid.

In addition, the ionic compound may include, in addition to the alkali metal salt and the organic cation-anion salt: inorganic salts such as ammonium chloride, aluminum chloride, copper chloride, ferrous chloride, ferric chloride, ammonium sulfate, etc. These ionic compounds may be used alone or in combination of two or more.

In the acrylic pressure-sensitive adhesive composition used in the present invention, various additives such as a viscosity modifier, a release modifier, a tackifier, a plasticizer, a softener, a filler containing glass fibers, glass beads, metal powder, other inorganic powder, etc., a pigment, a colorant (such as a pigment and a dye), a pH adjuster (such as an acid or an alkali), an antioxidant, and an ultraviolet absorber may be used as needed within a range not departing from the object of the present invention. These additives can also be compounded in the form of an emulsion.

The acrylic pressure-sensitive adhesive composition used in the present invention may contain the phosphorus-based compound described in the present specification, but is preferably not contained from the viewpoint of adhesion to a polarizing film or a coating layer.

The method for forming the pressure-sensitive adhesive layer 5 is not particularly limited, and may be a method in which the acrylic pressure-sensitive adhesive composition is applied to various substrates, dried by a dryer such as a heat oven, and the solvent or the like is volatilized to form a pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer is transferred to the coating layer side of the polarizing film 1 with the coating layer, or the pressure-sensitive adhesive layer 5 may be formed by directly applying the acrylic pressure-sensitive adhesive composition to the coating layer of the polarizing film 1 with the coating layer.

The substrate is not particularly limited, and examples thereof include various substrates such as a release film and a transparent resin film substrate.

As a method for coating the substrate or the polarizing film, various methods can be used. Specifically, examples thereof include: a spray coater, roll coating, contact roll coating, gravure coating, reverse coating, roll brushing, spray coating, dip roll coating, bar coating, blade coating, air knife coating, curtain coating, lip coating, extrusion coating using a die coater, and the like.

The drying conditions (temperature and time) are not particularly limited, and may be suitably set according to the composition, concentration, etc. of the acrylic pressure-sensitive adhesive composition, and are, for example, about 80 to 170 ℃, preferably 90 to 200 ℃, and 1 to 60 minutes, preferably 2 to 30 minutes.

The thickness (after drying) of the adhesive layer 5 is, for example, preferably 5 to 100 μm, more preferably 10 to 60 μm, and still more preferably 12 to 40 μm. If the thickness of the pressure-sensitive adhesive layer 5 is less than 10 μm, the adhesiveness to the adherend tends to be poor, and the durability under high temperature and high humidity tends to be insufficient. On the other hand, when the thickness of the pressure-sensitive adhesive layer 5 exceeds 100 μm, the acrylic pressure-sensitive adhesive composition is not sufficiently dried at the time of application and drying of the pressure-sensitive adhesive layer 5 to leave air bubbles, or unevenness in thickness occurs on the surface of the pressure-sensitive adhesive layer, or a problem in appearance tends to become conspicuous.

Examples of the material constituting the release film include resin films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films, porous materials such as paper, cloth, and nonwoven fabric, meshes, foamed sheets, metal foils, and suitable sheets such as laminates thereof, and the resin films are preferably used from the viewpoint of excellent surface smoothness.

Examples of the resin film include: polyethylene films, polypropylene films, polybutylene films, polybutadiene films, polymethylpentene films, polyvinyl chloride films, vinyl chloride copolymer films, polyethylene terephthalate films, polybutylene terephthalate films, polyurethane films, ethylene-vinyl acetate copolymer films, and the like.

The thickness of the release film is usually 5 to 200 μm, preferably about 5 to 100 μm. The release film may be subjected to release and anti-fouling treatment using a silicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based release agent, silica powder or the like, or antistatic treatment such as coating type, kneading type, vapor deposition type or the like, as necessary. In particular, by appropriately subjecting the surface of the release film to a release treatment such as a silicone treatment, a long-chain alkyl treatment, or a fluorine treatment, the releasability from the pressure-sensitive adhesive layer can be further improved.

The transparent resin film substrate is not particularly limited, and various transparent resin films can be used. The resin film can be formed by 1-layer film. Examples of the material include: polyester resins such as polyethylene terephthalate and polyethylene naphthalate, acetate resins, polyether sulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth) acrylic resins, polyvinyl chloride resins, polyvinylidene chloride resins, polystyrene resins, polyvinyl alcohol resins, polyarylate resins, polyphenylene sulfide resins, and the like. Among these, polyester-based resins, polyimide-based resins, and polyether sulfone-based resins are particularly preferable.

The thickness of the film substrate is preferably 15 to 200 μm.

The method of forming the adhesive layer on the coating layer of the above-mentioned coating layer-attached polarizing film 1 is as described above.

In addition, when the pressure-sensitive adhesive layer of the pressure-sensitive adhesive layer-attached polarizing film of the present invention is exposed, the pressure-sensitive adhesive layer may be protected with a release film (separator) before being put to practical use. Examples of the release film include those described above. When a release film is used as a substrate in the production of the pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer on the release film is bonded to the iodine-based polarizing film, whereby the release film can be used as a release film for a pressure-sensitive adhesive layer of a pressure-sensitive adhesive layer-attached polarizing film, and the process can be simplified.

The pressure-sensitive adhesive layer-attached polarizing film of the present invention may be used by laminating the pressure-sensitive adhesive layer of the pressure-sensitive adhesive layer-attached polarizing film and the transparent conductive layer of the transparent conductive layer-equipped member in such a manner that the pressure-sensitive adhesive layer is in contact with each other.

The member having a transparent conductive layer is not particularly limited, and known members can be used, and examples thereof include a member having a transparent conductive layer on a transparent substrate such as a transparent film, and a member having a transparent conductive layer and a liquid crystal cell.

The transparent substrate may be a substrate having transparency, and examples thereof include substrates (e.g., sheet-shaped, film-shaped, plate-shaped substrates) including a resin film, glass, and the like, and particularly a resin film is preferable. The thickness of the transparent substrate is not particularly limited, but is preferably about 10 to 200. mu.m, and more preferably about 15 to 150. mu.m.

The material of the resin film is not particularly limited, and various plastic materials having transparency can be used. Examples of the material include: polyester resins such as polyethylene terephthalate and polyethylene naphthalate, acetate resins, polyether sulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth) acrylic resins, polyvinyl chloride resins, polyvinylidene chloride resins, polystyrene resins, polyvinyl alcohol resins, polyarylate resins, polyphenylene sulfide resins, and the like. Among these, polyester-based resins, polyimide-based resins, and polyether sulfone-based resins are particularly preferable.

In addition, the surface of the transparent base material may be subjected to an etching treatment or an undercoating treatment such as sputtering, corona discharge, flame, ultraviolet irradiation, electron beam irradiation, chemical conversion, or oxidation in advance to improve the adhesion of the transparent conductive layer provided thereon to the transparent base material. Before the transparent conductive layer is provided, dust removal and cleaning may be performed by solvent cleaning, ultrasonic cleaning, or the like, as necessary.

The material constituting the transparent conductive layer is not particularly limited, and a metal oxide of at least 1 metal selected from the group consisting of indium, tin, zinc, gallium, antimony, titanium, silicon, zirconium, magnesium, aluminum, gold, silver, copper, palladium, and tungsten is used. The metal oxide may further contain a metal atom shown in the above group as needed. For example, indium oxide (ITO) containing tin oxide, tin oxide containing antimony, or the like can be preferably used, and ITO can be particularly preferably used. The ITO preferably contains 80 to 99 wt% of indium oxide and 1 to 20 wt% of tin oxide.

Examples of the ITO include crystalline ITO and amorphous (amorphous) ITO. Crystalline ITO can be obtained by applying high temperature at the time of sputtering, or further heating amorphous ITO. The above-described deterioration by iodine is remarkably generated on the amorphous ITO, so that the polarizing film with an adhesive layer of the present invention is particularly effective for the amorphous ITO.

The thickness of the transparent conductive layer is not particularly limited, but is preferably 7nm or more, more preferably 10nm or more, further preferably 12 to 60nm, further preferably 15 to 45nm, further preferably 18 to 45nm, and particularly preferably 20 to 30 nm. When the thickness of the transparent conductive layer is less than 7nm, deterioration of the transparent conductive layer due to iodine tends to occur, and a change in resistance value of the transparent conductive layer tends to increase. On the other hand, when the thickness exceeds 60nm, the productivity of the transparent conductive layer tends to be low, the cost tends to be high, and the optical characteristics tend to be low.

The method for forming the transparent conductive layer is not particularly limited, and a conventionally known method can be used. Specifically, for example, vacuum deposition, sputtering, and ion plating can be exemplified. In addition, an appropriate method may be adopted according to the desired film thickness.

The thickness of the substrate having the transparent conductive layer is 15 to 200 μm. Further, from the viewpoint of making the film thinner, it is preferably 15 to 150 μm, and more preferably 15 to 50 μm. When the substrate having the transparent conductive layer is used as a resistive film, the thickness is, for example, 100 to 200 μm. When used in a capacitance system, the thickness is preferably 15 to 100 μm, for example, and particularly, in accordance with the recent demand for further thin films, the thickness is more preferably 15 to 50 μm, and still more preferably 20 to 50 μm.

Further, an undercoat layer, an oligomer-preventing layer, and the like may be provided between the transparent conductive layer and the transparent substrate as necessary.

Examples of the member having a transparent conductive layer and a liquid crystal cell include a member having a transparent conductive layer on the side of a substrate (e.g., glass substrate) of a liquid crystal cell including the substrate/liquid crystal layer/substrate, which is not in contact with the liquid crystal layer, used in an image display device such as a liquid crystal display device. In addition, when a color filter substrate is provided on the liquid crystal cell, a transparent conductive layer may be provided on the color filter. The method of forming the transparent conductive layer on the substrate of the liquid crystal cell is the same as described above.

3. Image display device

As described above, in the polarizing film with an adhesive layer of the present invention, even when the transparent conductive layer is laminated on the adhesive layer of the polarizing film with an adhesive layer, corrosion of the transparent conductive layer can be suppressed, and an increase in surface resistance of the transparent conductive layer can be suppressed. Therefore, the polarizing film with an adhesive layer of the present invention can be suitably used as long as it is an image display device having a configuration in which the adhesive layer of the polarizing film with an adhesive layer is in contact with the transparent conductive layer. For example, the polarizing film with an adhesive layer of the present invention and a liquid crystal panel having a transparent conductive layer may be bonded to each other so that the adhesive layer of the polarizing film with an adhesive layer is in contact with the transparent conductive layer of the liquid crystal panel, thereby producing an image display device.

More specifically, the image display device uses the transparent conductive layer as an antistatic layer, or the image display device uses the transparent conductive layer as an electrode of a touch panel. Specific examples of the image display device using the transparent conductive layer as an antistatic layer include: an image display device comprising a polarizing film, an adhesive layer, an antistatic layer, a glass substrate, a liquid crystal layer, a driving electrode, a glass substrate, an adhesive layer, and a polarizing film, wherein the antistatic layer and the driving electrode are formed of transparent conductive layers. As the polarizing film with an adhesive layer on the upper side (viewing side) of the image display device, the polarizing film with an adhesive layer of the present invention can be used. Further, as an image display device for use in which a transparent conductive layer is used as an electrode of a touch panel, for example, there are: an image display device having a constitution of a polarizing film/an adhesive layer/a sensor layer doubling as an antistatic layer/a glass substrate/a liquid crystal layer/a sensor layer doubling as a drive electrode/a glass substrate/an adhesive layer/a polarizing film (In-Cell type touch panel), or a constitution of a polarizing film/an adhesive layer/a sensor layer doubling as an antistatic layer/a glass substrate/a liquid crystal layer/a drive electrode/a glass substrate/an adhesive layer/a polarizing film (On-Cell type touch panel), wherein the sensor layer, the sensor layer and the drive electrode are formed of a transparent conductive layer. As the polarizing film with an adhesive layer on the upper side (viewing side) of the image display device, the polarizing film with an adhesive layer of the present invention can be used.

Examples

The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples as long as the gist of the invention is not exceeded.

< iodine content in polarizing plate >

The iodine content (iodine and/or iodine ion content) in the polarizing plate was measured by the following procedure.

1) The fluorescence X-ray intensity was measured for a plurality of polarizing plates containing a predetermined amount of potassium iodide, and a relational expression between the iodine content and the fluorescence X-ray intensity was derived.

2) The amount of iodine was calculated from the value of the fluorescence X-ray measured for the iodine-based polarizing plate having an unknown iodine content by using the above-mentioned relational expression.

< measurement of weight average molecular weight (Mw) of acrylic Polymer >

The weight average molecular weight of the acrylic polymer prepared was measured by GPC (gel permeation chromatography).

The device comprises the following steps: HLC-8220GPC, manufactured by Tosoh corporation

Column:

sample column: TSKguardcolumn Super HZ-H manufactured by Tosoh corporation

(1 root) + TSKgel Super HZM-H (2 root)

Reference column: TSKgel Super H-RC (1 root)

Flow rate: 0.6mL/min

Injection amount: 10 μ L

Column temperature: 40 deg.C

Eluent: THF (tetrahydrofuran)

Concentration of injected sample: 0.2% by weight

A detector: differential refractometer

The weight average molecular weight is calculated by polystyrene conversion.

Production example 1 (production of Single-sided protective polarizing film)

A laminate comprising a PVA layer having a thickness of 9 μm formed on an amorphous PET substrate was subjected to in-air auxiliary stretching at a stretching temperature of 130 ℃ to produce a stretched laminate. Then, the stretched laminate was immersed in a dyeing solution containing 0.1 parts by weight of iodine and 0.7 parts by weight of potassium iodide with respect to 100 parts by weight of water for 60 seconds to produce a colored laminate. Further, the colored laminate was integrally stretched with the amorphous PET substrate by boric acid underwater stretching at a stretching temperature of 65 ℃ so that the total stretching ratio became 5.94 times, to produce an optical film laminate including a PVA layer having a thickness of 4 μm. By the above 2-step stretching, an optical film laminate comprising a PVA layer having a thickness of 4 μm constituting a high-functional polarizing layer highly orienting the PVA molecules of the PVA layer of the film produced on the amorphous PET substrate and highly orienting iodine adsorbed by dyeing in one direction in the form of a polyiodide ion complex can be produced. Further, a PVA-based adhesive was applied to the surface of the polarizing layer of the optical film laminate, and a saponified 40 μm thick acrylic resin film (transparent protective film) was bonded thereto, and then the amorphous PET substrate was peeled off to prepare a single-sided protective polarizing film having a transparent protective film only on one side using a thin iodine-based polarizing plate. Hereinafter, this is referred to as a single-sided protective polarizing film (1). The iodine content of the single-sided protective polarizing film (1) was 5.1% by weight.

Production example 2 (preparation of resin composition (A1) for Forming coating layer)

A PVA resin having a polymerization degree of 2500 and a saponification degree of 99.0 mol% was dissolved in pure water to prepare an aqueous solution having a solid content concentration of 4 wt%, and 2 parts by weight of monobutyl phosphate (trade name: MP-4, manufactured by Daihuaiki chemical industries, Ltd.) as a phosphorus-based compound was added to 100 parts by weight of the solid content of the polyvinyl alcohol resin in the aqueous solution to obtain a resin composition (A1) for forming a coating layer.

Production example 3 (preparation of resin composition (A2) for Forming coating layer)

A PVA resin having a polymerization degree of 2500 and a saponification degree of 99.0 mol% was dissolved in pure water to prepare an aqueous solution having a solid content concentration of 4 wt%, which was used as a resin composition for forming a coating layer (a 2).

Production example 4 (preparation of resin composition (A3) for Forming coating layer)

12.5 parts of N-hydroxyethyl acrylamide (trade name: HEAA, manufactured by KANGREN corporation), 25 parts of acryloylmorpholine (trade name: ACMO (registered trade name)), 62.5 parts of dimethylol tricyclodecane diacrylate (trade name: lightacrylate DCP-A, manufactured by KANGNIGHOSE corporation), 2 parts of ｃA photo-radical polymerization initiator (2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, trade name: IRGACURE 907, manufactured by BASF corporation), and 2 parts of ｃA photosensitizing agent (diethylthioxanthone, trade name: KAYACURE DETX-S, manufactured by KANGUIYAKU corporation) were mixed and stirred at 50 ℃ for 1 hour to obtain ｃA mixture. Further, 2 parts by weight of monobutyl phosphate (trade name: MP-4, manufactured by Dai chemical industries, Ltd.) as a phosphorus compound was added to 100 parts by weight of the solid content of the mixture to obtain a resin composition (A3) for forming a coating layer.

Production example 5 (preparation of resin composition (A4) for Forming coating layer)

A resin composition for forming a coating layer (a4) was obtained in the same manner as in production example 4, except that the phosphorus-based compound was not added.

Production example 6 (preparation of resin composition for Forming coating layer (A5))

After a PVA resin having a polymerization degree of 2500 and a saponification degree of 99.0 mol% was dissolved in pure water to prepare an aqueous solution having a solid content concentration of 4 wt%, 5 parts by weight of phenylphosphonic acid (manufactured by wako pure chemical industries, ltd.) as a phosphorus-based compound was added to 100 parts by weight of the solid content of the polyvinyl alcohol resin in the aqueous solution, to obtain a coating layer-forming resin composition (a 5).

Production example 7 (preparation of resin composition for Forming coating layer (B1))

A solution (trade name: Dentron P-580W, manufactured by Kazakusho Co., Ltd.) containing 30 to 90 wt% of a urethane polymer and 10 to 50 wt% of a polythiophene polymer (conductive material) in terms of solid content and a solution (trade name: Epocros WS-700, manufactured by Nippon catalyst Co., Ltd.) containing 10 to 70 wt% of an oxazoline group-containing acrylic polymer in terms of solid content were added to a (mixed) solution containing 100 wt% of water, and the solid content concentration (base concentration) was 0.4 wt%, thereby obtaining a coating layer-forming resin composition (B1).

Production example 8 (preparation of resin composition for Forming coating layer (B2))

A resin composition for forming a coating layer (B2) was obtained in the same manner as in production example 7, except that a urethane polymer solution (trade name: Dentron B-510C, tradename: tradename, tradename of tradename, etc.) not containing a polythiophene polymer was used instead of Den.

Production example 9 (production of acrylic pressure-sensitive adhesive layer (C1))

In a reaction vessel equipped with a condenser, a nitrogen inlet tube, a thermometer, and a stirrer, 99 parts of butyl acrylate, 1 part of 4-hydroxybutyl acrylate, and 0.3 part of 2, 2' -azobisisobutyronitrile per 100 parts of the total amount (solid content) of the monomers were added together with ethyl acetate, and reacted at 60 ℃ for 4 hours under a nitrogen stream, and then ethyl acetate was added to the reaction solution to obtain a polymer solution (solid content concentration 30 wt%) containing an acrylic polymer (a1) having a weight average molecular weight of 165 million. An acrylic pressure-sensitive adhesive solution was obtained by mixing 0.3 parts of dibenzoyl peroxide (trade name: NYPER BMT, manufactured by Nippon fat and oil Co., Ltd.) as a crosslinking agent, 0.1 parts of trimethylolpropane dimethyldiisocyanate (trade name: Takenate D110N, manufactured by Mitsui Wutian chemical Co., Ltd.), 0.2 parts of an acetoacetyl group-containing silane coupling agent (trade name: A-100, manufactured by Sudoku Co., Ltd.) and 0.1 parts of monobutyl phosphate (trade name: MP-4, manufactured by Dai chemical industry Co., Ltd.) as a phosphorus compound with 100 parts of the solid content of the acrylic polymer solution. The acrylic pressure-sensitive adhesive solution (C1) was applied to the surface of a release sheet (separator) made of a polyethylene terephthalate film (thickness: 38 μm) after release treatment so that the thickness after drying was 25 μm, and dried to form a pressure-sensitive adhesive layer (C1).

Production example 10 (production of acrylic pressure-sensitive adhesive layer (C2))

An acrylic pressure-sensitive adhesive layer was formed in the same manner as in production example 9 except that no phosphorus-based compound was added during the preparation of the pressure-sensitive adhesive solution (C2).

Production example 11 (production of acrylic pressure-sensitive adhesive layer (C3))

An acrylic pressure-sensitive adhesive layer (C3) was formed in the same manner as in production example 9, except that 0.5 parts of 1-methyl-1-ethylpyrrolidinium bis (trifluoromethanesulfonyl) imide (manufactured by shoitan chemical) as a conductive material was further added at the time of production of the pressure-sensitive adhesive solution.

Production example 12 (production of acrylic pressure-sensitive adhesive layer (C4))

An acrylic pressure-sensitive adhesive layer (C4) was formed in the same manner as in production example 11, except that no phosphorus compound was added during the preparation of the pressure-sensitive adhesive solution.

Production example 13 (production of acrylic pressure-sensitive adhesive layer (C5))

In a reaction vessel equipped with a condenser, a nitrogen inlet tube, a thermometer and a stirrer, 95 parts of butyl acrylate, 1 part of 4-hydroxybutyl acrylate, 4 parts of acrylic acid and 1 part of 2, 2' -azobisisobutyronitrile as an initiator per 100 parts of the total amount (solid content) of the monomers were added together with ethyl acetate, and the mixture was reacted at 60 ℃ for 7 hours under a nitrogen stream. Then, ethyl acetate was added to the reaction solution to obtain a solution (solid content concentration 30% by weight) containing 155 ten thousand of the acrylic polymer (a 2).

An acrylic pressure-sensitive adhesive solution was obtained in the same manner as in production example 9, except that the acrylic polymer (a2) -containing solution was used in production example 9 instead of the acrylic polymer (a1) -containing solution, and a crosslinking agent, a silane coupling agent, and a phosphorus compound were added thereto. Further, a pressure-sensitive adhesive layer was formed using the acrylic pressure-sensitive adhesive solution in the same manner as in production example 9 (C5).

Production example 14 (production of acrylic pressure-sensitive adhesive layer (C6))

An acrylic pressure-sensitive adhesive layer (C6) was formed in the same manner as in production example 13, except that no phosphorus compound was added during the preparation of the pressure-sensitive adhesive solution.

Production example 15 (production of acrylic pressure-sensitive adhesive layer (C7))

An acrylic pressure-sensitive adhesive layer (C7) was formed in the same manner as in production example 9, except that 0.5 parts of 1-methyl-1-ethylpyrrolidinium bis (trifluoromethanesulfonyl) imide (manufactured by shoitan chemical) as a conductive material was further added at the time of production of the pressure-sensitive adhesive solution.

Production example 16 (production of acrylic pressure-sensitive adhesive layer (C8))

An acrylic pressure-sensitive adhesive layer (C8) was formed in the same manner as in production example 15, except that no phosphorus compound was added during the preparation of the pressure-sensitive adhesive solution.

Example 1

The surface of the polarizing plate (the surface of the polarizing plate not provided with the transparent protective film) of the single-sided protective polarizing film (1) obtained in production example 1 was coated with a coating layer forming resin composition (a1) adjusted to 25 ℃ using a wire bar coater so that the thickness after drying was 1 μm, and then dried with hot air at 60 ℃ for 1 minute to form a coating layer 1, thereby producing a single-sided protective polarizing film with 1 coating layer.

Then, the coating layer composition (B1) adjusted to 25 ℃ was further applied to the coating layer 1 of the single-sided protective polarizing film with 1 coating layer obtained above using a wire bar coater so that the dried thickness was 1 μm, and then dried with hot air at 60 ℃ for 1 minute to form a coating layer 2, thereby producing a polarizing film with 2 coating layers.

Then, an adhesive layer (C2) formed on the release-treated surface of the release sheet (separator) was laminated on the coating layer 2 of the polarizing film with 2 coating layers obtained above, to prepare a polarizing film with an adhesive layer.

Examples 2 to 11 and comparative examples 1 to 12

A polarizing film with an adhesive layer was formed in the same manner as in example 1, except that the resin composition for forming a coating layer and the adhesive layer in example 1 were changed as shown in tables 1 and 2.

The polarizing films with adhesive layers obtained in the above examples and comparative examples were evaluated as follows. The results are shown in tables 1 and 2.

< Rate of resistance Change >

The conductive film having an ITO layer formed on the surface thereof (trade name: Elecrysta (P400L), manufactured by ritonan corporation) was cut into 15mm × 15mm, the polarizing films with adhesive layers obtained in examples and comparative examples were cut into 8mm × 8mm, the separator film was peeled off and then bonded to the center portion of the conductive film, and then, autoclave treatment was performed at 50 ℃ and 5atm for 15 minutes, and the obtained sample was used as a corrosion resistance measurement sample. The resistance value of the obtained measurement sample was measured using the following measurement apparatus, and was set as an "initial resistance value".

Then, the sample for measurement was put under an environment of 60 ℃ and 95% humidity for 500 hours, and the resistance value was measured to obtain "resistance value after wet heat". The resistance value was measured using HL5500PC manufactured by Accent Optical Technologies. From the "initial resistance value" and the "resistance value after moist heat" measured in the above manner, the rate of change (%) in the resistance value in each moist heat state was calculated from the following equation.

If the resistance value change rate is less than 150%, the resistance value increases little due to heat and humidity, and the corrosion resistance is good.

< adhesion force >

The polarizing films with adhesive layers obtained in examples and comparative examples were cut into a size of 25mm × 150mm, and bonded so that the adhesive layer side was in contact with the deposition surface of the indium-tin oxide vapor-deposited film deposited on the surface of the 50 μm-thick polyethylene terephthalate film. Then, the edge of the polyethylene terephthalate film was peeled off by hand, and the adhesion of the pressure-sensitive adhesive layer to the side of the polyethylene terephthalate film was confirmed, and then the stress (N/25mm) at the time of peeling was measured (25 ℃) at a speed of 300 mm/min in a direction of 180 ℃ by using a tensile tester AG-1 manufactured by Shimadzu corporation.

When the adhesive strength is 15N/25mm or more, the adhesive is excellent in that no adhesive remains during the return and insufficient adhesive during the processing.

[ TABLE 1 ]

[ TABLE 2 ]

The abbreviations in the tables are as follows.

(A1) To (A4): resin compositions for forming coating layer (A1) - (A4)

(B1) (B2): composition for anchor layer (B1), (B2)

(C1) (C8): adhesive layer (C1) - (C8)

In the items described as "presence or absence", "○" indicates "containing" and "-" indicates "not containing".

Description of the symbols

Polarizing film with coating layer

2 iodine polarizing film

3 transparent protective film

4 coating layer

5 adhesive layer

6 polarizing film with adhesive layer

Claims (11)

1. A polarizing film having a coating layer, comprising a transparent protective film, an iodine-based polarizing plate containing iodine and/or iodide ions, and a coating layer in this order,

the iodine-based polarizing plate and/or the coating layer contain a phosphorus-based compound,

the phosphorus-based compound contains 1 or more kinds of phosphorus-based compounds selected from a polymer of a compound represented by the following general formula (1) and a compound represented by the general formula (1), and/or 1 or more kinds of phosphonic acid-based compounds selected from a compound represented by the following general formula (2) and salts thereof,

in the formula, R¹And R²Each independently represents a hydrogen atom or a hydrocarbon residue of 1 to 18 carbon atoms which may contain an oxygen atom,

wherein R is a hydrogen atom or a hydrocarbon residue of 1 to 18 carbon atoms which may contain an oxygen atom.

2. The coated polarizing film according to claim 1,

the iodine-based polarizing plate has a thickness of 10 [ mu ] m or less.

3. The coating-layer-bearing polarizing film according to claim 1 or 2,

the iodine and/or iodide ion content in the iodine-based polarizing plate is 3 to 12 wt%.

4. The coating-layer-bearing polarizing film according to claim 1 or 2,

the coating layer is formed on the substrate and has no transparent protective film between the iodine-based polarizing plate and the coating layer.

5. The coating-layer-bearing polarizing film according to claim 1 or 2,

the coating layer is formed from a resin composition containing at least 1 resin selected from the group consisting of polyurethane resins, polyvinyl alcohol resins, and acrylic resins.

6. A polarizing film with an adhesive layer, characterized in that,

the polarizing film with a coating layer according to any one of claims 1 to 5, which has an adhesive layer on the coating layer side.

7. The adhesive layer-bearing polarizing film according to claim 6,

the adhesive layer contains an ionic compound.

8. The adhesive layer-bearing polarizing film according to claim 6 or 7,

the pressure-sensitive adhesive layer of the pressure-sensitive adhesive layer-attached polarizing film according to claim 6 or 7 is bonded so as to be in contact with the transparent conductive layer of the transparent conductive member having a transparent conductive layer.

9. The adhesive layer-bearing polarizing film according to claim 8,

the transparent conductive layer is formed of indium tin oxide.

10. The adhesive layer-bearing polarizing film according to claim 9,

the indium tin oxide is amorphous indium tin oxide.

11. An image display device is characterized in that,

bonding the adhesive layer of the adhesive layer-attached polarizing film according to any one of claims 6 to 10 to a liquid crystal panel having a transparent conductive layer such that the adhesive layer of the adhesive layer-attached polarizing film is in contact with the transparent conductive layer of the liquid crystal panel.

Images