JP2015146013A - Polarizing film with pressure-sensitive adhesive layer, laminate, and image display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polarizing film with a pressure-sensitive adhesive layer having such properties that, even when the polarizing film with a pressure-sensitive adhesive layer is laminated on a transparent conductive layer, the polarizing film with a pressure-sensitive adhesive layer can suppress corrosion of the transparent conductive layer and can suppress increase in the surface resistance of the transparent conductive layer, and to provide a laminate comprising the above polarizing film with a pressure-sensitive adhesive layer laminated on a substrate having a transparent conductive layer, and an image display device using the laminate as a touch panel.SOLUTION: The polarizing film with a pressure-sensitive adhesive layer has a pressure-sensitive adhesive layer formed from the following acrylic pressure-sensitive adhesive composition on at least one surface of an iodine-based polarizing film that comprises an iodine-based polarizer containing iodine and/or an iodine ion and a transparent protective film on at least one surface of the polarizer. The acrylic pressure-sensitive adhesive composition comprises: at least one phosphoric acid-based compound selected from a group consisting of a compound represented by general formula (1) and a polymer of the compound represented by general formula (1); and a (meth)acrylic polymer. In formula (1), Rand Reach independently represent a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms which may contain an oxygen atom.

Description

  The present invention relates to a polarizing film with an adhesive layer. In addition, the present invention provides a laminate in which the polarizing film with an adhesive layer and a substrate having a transparent conductive layer are bonded together, and an image in which the polarizing film with an adhesive layer and a liquid crystal panel having a transparent conductive layer are bonded. The present invention relates to a display device and an image display device using the laminate as a touch panel.

  In recent years, transparent conductive films such as indium tin oxide (ITO) thin films have been widely used in various applications. For example, the transparent conductive film is formed on the opposite side of the liquid crystal display device using an in-plane switching (IPS) type liquid crystal cell from the side in contact with the liquid crystal layer of the transparent substrate constituting the liquid crystal cell. It is known to be a layer. The transparent conductive film having the transparent conductive film formed on the transparent resin film is used for an electrode substrate of a touch panel, for example, a liquid crystal display device or an image display device used for a mobile phone, a portable music player, and the like. Input devices using a combination of touch panels have become widespread.

  As an input device using a combination of a touch panel and an image display device, conventionally, a transparent conductive film in which a transparent conductive layer is formed on a transparent substrate made of a glass plate or a transparent resin film is used on a liquid crystal display device (visual recognition of the liquid crystal display device). The out-cell type provided on the upper side of the side polarizing film has been widely used. However, in recent years, an on-cell type in which an electrode made of a transparent conductive film is formed on an upper glass substrate of a liquid crystal cell, or an electrode made of a transparent conductive film is used Various configurations are known, such as an in-cell type with internal capture. It is also known to realize a touch panel function by using an ITO layer as an antistatic layer of an image display device as a touch sensor and patterning it.

  In liquid crystal display devices and image display devices using these transparent conductive films, in recent years, there has been a strong demand for weight reduction and thinning, and even for polarizing films used in the liquid crystal display devices and the like, There is a demand for weight reduction. As a method for reducing the thickness and weight of the polarizing film, for example, a single-sided protective polarizing film provided with a transparent protective film only on one side of the polarizer, a method for producing a thin polarizing film with a thin film thickness of the polarizer itself, etc. It has been known.

  As a method for producing a thin polarizing film, there is a method for producing an optical film laminate in which a thin polarizing film made of a polyvinyl alcohol resin in which iodine is oriented is formed on an amorphous ester thermoplastic resin substrate of a continuous web. Known (see, for example, Patent Documents 1 and 2).

Japanese Patent No. 4751481 Japanese Patent No. 4691205

  For example, when a transparent conductive film is used as an antistatic layer, a polarizing film with an adhesive layer is usually laminated on a liquid crystal cell having the antistatic layer, and the antistatic layer and the polarizing film are made of a transparent conductive film. Are bonded together via an adhesive layer. Moreover, when using a transparent conductive film as an electrode application of a touch panel, depending on the configuration of the touch panel, a polarizing film with an adhesive layer is laminated on the transparent conductive film for an electrode, and an antistatic layer and a polarizing film made of a transparent conductive film May be bonded via an adhesive layer.

  When the polarizing film is an iodine polarizing film, as described above, when the humidified durability test (normal durability test) is performed by laminating the transparent conductive layer and the iodine polarizing film, the resistance value of the transparent conductive layer is There was a case of rising. It has been found that the increase in the resistance value is due to the corrosion of the transparent conductive layer when iodine contained in the polarizer oozes out to the pressure-sensitive adhesive layer and the iodine reaches the transparent conductive layer.

  For example, in a thin iodine-based polarizer having a thickness of 10 μm or less described in Patent Documents 1 and 2, it is necessary to increase the iodine concentration in the polarizer in order to have the same polarization characteristics as a conventional polarizer. It has been found that when such a polarizing film containing a polarizer having a high iodine concentration is bonded to a transparent conductive layer, corrosion of the transparent conductive layer due to iodine is likely to occur. It was also found that when a single-side protected iodine polarizing film is used, the transparent conductive layer is easily corroded because the transparent conductive layer is bonded directly to the iodine polarizer via the adhesive layer.

  Therefore, the present invention provides a polarizing film with a pressure-sensitive adhesive layer that can suppress corrosion of the transparent conductive layer and suppress an increase in surface resistance of the transparent conductive layer even when laminated on the transparent conductive layer. The purpose is to provide. In addition, the present invention provides an image obtained by laminating the polarizing film with the pressure-sensitive adhesive layer, a laminate obtained by laminating a substrate having a transparent conductive layer, and the liquid crystal panel having the polarizing film with a pressure-sensitive adhesive layer and a transparent conductive layer. Another object is to provide a display device and an image display device using the laminate as a touch panel.

  As a result of intensive studies to solve the above problems, the present inventors have used a pressure-sensitive adhesive layer formed from an acrylic pressure-sensitive adhesive composition containing a phosphoric acid compound and a (meth) acrylic polymer. The inventors have found that the object can be achieved, and have completed the present invention.

（式中、Ｒ^１及びＲ^２は、それぞれ独立して、水素原子、又は、酸素原子を含んでいてもよい、炭素数１〜１８の炭化水素残基を表す。）
で表される化合物及び前記一般式（１）で表される化合物の多量体からなる群から選択される１種以上のリン酸系化合物、並びに（メタ）アクリル系ポリマーを含有するアクリル系粘着剤組成物から形成される粘着剤層を有することを特徴とする粘着剤層付偏光フィルムに関する。ここで、「ヨウ素及び／又はヨウ素イオンを含有するヨウ素系偏光子」とは、ヨウ素を含有するヨウ素系偏光子、ヨウ素イオンを含有するヨウ素系偏光子、ヨウ素及びヨウ素イオンの両方を含有するヨウ素系偏光子のことであり、本発明においてはいずれであっても好適に用いることができる。 That is, the present invention provides at least one surface of an iodine-based polarizing film having a transparent protective film on at least one surface of an iodine-based polarizer containing iodine and / or iodine ions.
The following general formula (1):

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom.)
And an acrylic pressure-sensitive adhesive containing one or more phosphoric acid compounds selected from the group consisting of a compound represented by formula (1) and a multimer of compounds represented by the general formula (1), and a (meth) acrylic polymer It has an adhesive layer formed from a composition, and relates to a polarizing film with an adhesive layer characterized by the above-mentioned. Here, “iodine-based polarizer containing iodine and / or iodine ions” means an iodine-based polarizer containing iodine, an iodine-based polarizer containing iodine ions, iodine containing both iodine and iodine ions It is a system polarizer, and any of them can be suitably used in the present invention.

  The iodine and / or iodine ion content in the iodine-based polarizer may be 1 to 14% by weight or 3 to 12% by weight.

The phosphoric acid compound contains phosphoric acid, and one of R ¹ and R ^{2 in} the general formula (1) is a hydrogen atom, and the other may contain an oxygen atom. Phosphoric acid monoester which is a hydrocarbon residue of ˜18, and R ¹ and R ² of the general formula (1) are hydrocarbon residues having 1 to 18 carbon atoms which may contain an oxygen atom A mixture containing one or more phosphate esters selected from the group consisting of phosphate diesters is preferred.

  The phosphoric acid compound is preferably a mixture containing phosphoric acid and phosphoric acid monoester. Moreover, it is preferable that the total amount of phosphoric acid and phosphoric acid monoester is 80 weight% or more in 100 weight% of phosphoric acid compounds.

  It is preferable that the said C1-C18 hydrocarbon residue is a C1-C10 linear or branched alkyl group.

  The iodine-based polarizing film is a single-sided protective polarizing film having a transparent protective film only on one side of the iodine-based polarizer, and the surface of the single-sided protective polarizing film that does not have a transparent protective film, and the adhesive It is preferred that the layers are in contact.

  The iodine-based polarizer preferably has a thickness of 10 μm or less.

  The total thickness of the iodine polarizing film is preferably 80 μm or less.

  Moreover, it is preferable to bond and use so that the adhesive layer of the said polarizing film with an adhesive layer and the transparent conductive layer of the base material which has a transparent conductive layer may contact.

  It is preferable that the addition amount of the phosphoric acid compound is 0.001 to 4 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer.

  The (meth) acrylic polymer preferably contains an alkyl (meth) acrylate and a hydroxyl group-containing monomer as monomer units.

  The hydroxyl group-containing monomer is preferably 4-hydroxybutyl acrylate.

  The (meth) acrylic polymer preferably has a weight average molecular weight of 1,200,000 to 3,000,000.

  The acrylic pressure-sensitive adhesive composition preferably further contains a crosslinking agent, and the crosslinking agent is at least one crosslinking agent selected from the group consisting of peroxide-based crosslinking agents and isocyanate-based crosslinking agents. More preferably.

  It is preferable that the acrylic pressure-sensitive adhesive composition further contains an ionic compound.

  Moreover, this invention makes the adhesive layer of the said polarizing film with an adhesive layer, and the transparent conductive layer of the said member contact the said polarizing film with an adhesive layer, and the transparent conductive member which has a transparent conductive layer. It is related with the laminated body characterized by having bonded together.

  The transparent conductive layer is preferably formed of indium tin oxide, and the indium tin oxide is more preferably amorphous indium tin oxide.

  Moreover, this invention is the adhesive layer of the said polarizing film with an adhesive layer, and the liquid crystal panel which has a transparent conductive layer, The adhesive layer of the said polarizing film with an adhesive layer and the transparent conductive layer of the said liquid crystal panel are The present invention relates to an image display device that is bonded so as to come into contact with each other.

  Furthermore, this invention relates to the image display apparatus characterized by using the said laminated body as a touch panel.

  Although the polarizing film with the pressure-sensitive adhesive layer of the present invention uses an iodine-based polarizer, even when a transparent conductive layer is laminated on the pressure-sensitive adhesive layer of the polarizing film with the pressure-sensitive adhesive layer, corrosion of the transparent conductive layer is suppressed. The increase in surface resistance of the transparent conductive layer can be suppressed. This is because the pressure-sensitive adhesive layer of the polarizing film with a pressure-sensitive adhesive layer of the present invention contains a phosphoric acid compound. Specifically, for example, when the phosphoric acid compound contains phosphoric acid, a passive film is formed on the surface of the transparent conductive layer with phosphoric acid and metal ions in the transparent conductive layer. This is probably because the iodine does not migrate to the surface of the transparent conductive layer, and the corrosion of the transparent conductive layer is hindered. Further, when the phosphoric acid compound contains a phosphoric acid compound (for example, phosphoric acid ester, etc.), the phosphoric acid compound is selectively adsorbed on the surface of the transparent conductive layer to form a film, and as a result, in the polarizer This is probably because the iodine does not migrate to the surface of the transparent conductive layer, and the corrosion of the transparent conductive layer is hindered.

It is sectional drawing which shows typically one Embodiment of the image display apparatus of this invention. It is sectional drawing which shows typically one Embodiment of the image display apparatus of this invention. It is sectional drawing which shows typically one Embodiment of the image display apparatus of this invention.

（式中、Ｒ^１及びＲ^２は、それぞれ独立して、水素原子、又は、酸素原子を含んでいてもよい、炭素数１〜１８の炭化水素残基を表す。）
で表される化合物及び前記一般式（１）で表される化合物の多量体からなる群から選択される１種以上のリン酸系化合物、並びに（メタ）アクリル系ポリマーを含有するアクリル系粘着剤組成物から形成される粘着剤層を有することを特徴とする。 1. Polarizing film with pressure-sensitive adhesive layer The polarizing film with a pressure-sensitive adhesive layer of the present invention is provided on at least one surface of an iodine-based polarizing film having a transparent protective film on at least one surface of an iodine-based polarizer containing iodine and / or iodine ions.
The following general formula (1):

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom.)
And an acrylic pressure-sensitive adhesive containing one or more phosphoric acid compounds selected from the group consisting of a compound represented by formula (1) and a multimer of compounds represented by the general formula (1), and a (meth) acrylic polymer It has the adhesive layer formed from a composition, It is characterized by the above-mentioned.

(1) Iodine Polarizing Film The iodine polarizing film used in the present invention has a transparent protective film on at least one side of an iodine polarizer containing iodine and / or iodine ions. In the present invention, it may be a single-sided protective polarizing film having a transparent protective film on one side of the iodine-based polarizer or a double-sided protective polarizing film having transparent protective films on both sides of the iodine-based polarizer. When the protective polarizing film is used, the effect of the present invention is remarkable. Moreover, even if it is a double-sided protection polarizing film, the effect of this invention is remarkable also when the thickness of the transparent protective film in the side which contact | connects an adhesive layer is thin (for example, 25 micrometers or less). In addition, when a polarizing film is a single-sided protective polarizing film, an adhesive layer can be directly provided on the polarizer surface of the side which does not have the said transparent protective film.

  Any iodine-based polarizer can be used as long as it contains iodine and / or iodine ions. For example, polyvinyl alcohol (PVA) film, partially formalized PVA film And a uniaxially stretched film obtained by adsorbing iodine to a hydrophilic polymer film such as an ethylene / vinyl acetate copolymer partially saponified film. Among these, a polarizer made of a PVA film and iodine is preferable. The thickness of these polarizers is not particularly limited, but is generally about 5 to 80 μm.

  A polarizer obtained by dyeing a PVA-based film with iodine and uniaxially stretching it can be produced, for example, by dyeing PVA in an aqueous iodine solution and stretching it 3 to 7 times the original length. If necessary, it can be immersed in an aqueous solution such as potassium iodide which may contain boric acid, zinc sulfate, zinc chloride or the like. Further, if necessary, the PVA film may be immersed in water and washed before dyeing. Washing the PVA film with water can clean the surface of the PVA film and the anti-blocking agent. In addition, swelling the PVA film has the effect of preventing unevenness such as uneven dyeing. Stretching may be performed after dyeing with iodine, may be performed while dyeing, or may be dyed with iodine after stretching. The film can be stretched even in an aqueous solution such as boric acid or potassium iodide or in a water bath.

  In the present invention, a thin iodine polarizer having a thickness of 10 μm or less can also be suitably used. From the viewpoint of thinning, the thickness is preferably 1 to 7 μm. Such a thin iodine-based polarizer is preferable in that the thickness unevenness is small, the visibility is excellent, the dimensional change is small, the durability is excellent, and the thickness of the polarizing film can be reduced.

  As the thin polarizer, typically, Japanese Patent Application Laid-Open No. 51-069644, Japanese Patent Application Laid-Open No. 2000-338329, International Publication No. 2010/100917, International Publication No. 2010/100917, or a patent. The thin polarizing film described in the specification of 4751481 and Unexamined-Japanese-Patent No. 2012-0753563 can be mentioned. These thin polarizing films can be obtained by a production method including a step of stretching a PVA-based resin layer and a stretching resin substrate in the state of a laminate and a step of dyeing. With this manufacturing method, even if the PVA-based resin layer is thin, it can be stretched without problems such as breakage due to stretching by being supported by the stretching resin substrate.

  The thin polarizing film can be stretched at a high magnification and can improve the polarization performance among the production methods including a step of stretching in the state of a laminate and a step of dyeing. WO2010 / 100917 Pamphlet , WO 2010/100917 pamphlet, or Patent 4751481 specification or JP 2012-073563 A, which is obtained by a production method including a step of stretching in a boric acid aqueous solution is preferable. What is obtained by the manufacturing method including the process of extending | stretching in the air auxiliary before extending | stretching in the boric-acid aqueous solution which is described in the specification of 4751481 or Unexamined-Japanese-Patent No. 2012-073563 is preferable.

  The iodine-based polarizer used in the present invention may have an iodine and / or iodine ion content (hereinafter sometimes referred to as iodine content) of 1 to 14% by weight in the polarizer. It may be ˜12% by weight or 4 to 7.5% by weight. The polarizing film with a pressure-sensitive adhesive layer of the present invention suppresses an increase in the surface resistance of the transparent conductive layer laminated on the polarizing film with a pressure-sensitive adhesive layer even if the iodine content in the iodine-based polarizer is as large as the above range. it can. This is because the iodine contained in the iodine polarizing film does not migrate to the surface of the transparent conductive layer because the phosphoric acid compound contained in the pressure-sensitive adhesive layer forms a film on the surface of the transparent conductive layer. This is probably because the corrosion of the layer is prevented. Specifically, when the phosphoric acid compound contains phosphoric acid, the phosphoric acid forms a passive film with the metal ions in the transparent conductive layer on the surface of the transparent conductive layer, and the phosphoric acid compound is phosphoric acid. When a compound (for example, phosphate ester or the like) is included, the phosphate compound can be selectively adsorbed on the surface of the transparent conductive layer to form a film.

  As a material for forming a transparent protective film provided on one side or both sides of the iodine-based polarizer, a material excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy and the like is preferable. For example, polyester polymers such as polyethylene terephthalate and polyethylene naphthalate, cellulose polymers such as diacetyl cellulose and triacetyl cellulose, acrylic polymers such as polymethyl methacrylate, styrene such as polystyrene and acrylonitrile / styrene copolymer (AS resin) And polymers based on polycarbonate and polycarbonate. In addition, polyethylene, polypropylene, polyolefins having a cyclo or norbornene structure, polyolefin polymers such as ethylene / propylene copolymers, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamide, imide polymers, sulfone polymers , Polyether sulfone polymer, polyether ether ketone polymer, polyphenylene sulfide polymer, vinyl alcohol polymer, vinylidene chloride polymer, vinyl butyral polymer, arylate polymer, polyoxymethylene polymer, epoxy polymer, or Examples of the polymer that forms the transparent protective film include blends of the polymer. The transparent protective film can also be formed as a cured layer of thermosetting or ultraviolet curable resin such as acrylic, urethane, acrylurethane, epoxy, and silicone.

  Although the thickness of a protective film can be determined suitably, generally it is about 1-500 micrometers from points, such as workability | operativity, such as intensity | strength and handleability, and thin film property.

  The iodine polarizer and the transparent protective film are usually in close contact with each other via a water-based adhesive or the like. Examples of the water-based adhesive include an isocyanate-based adhesive, a polyvinyl alcohol-based adhesive, a gelatin-based adhesive, a vinyl-based latex, a water-based polyurethane, and a water-based polyester. In addition to the above, examples of the adhesive between the polarizer and the transparent protective film include an ultraviolet curable adhesive and an electron beam curable adhesive. The electron beam curable polarizing film adhesive exhibits suitable adhesiveness to the various transparent protective films. The adhesive used in the present invention can contain a metal compound filler.

  The surface of the transparent protective film to which the iodine-based polarizer is not adhered may be subjected to a treatment for the purpose of hard coat layer, antireflection treatment, antisticking, diffusion or antiglare.

  The total thickness of the iodine-based polarizing film used in the present invention is preferably 80 μm or less, more preferably 70 μm or less, and more preferably 60 μm or less in order to meet the demand for thinning the polarizing film with the pressure-sensitive adhesive layer. More preferably. Although it does not specifically limit as a minimum of the total thickness of a polarizing film, For example, 10 micrometers is mentioned.

（式中、Ｒ^１及びＲ^２は、それぞれ独立して、水素原子、又は、酸素原子を含んでいてもよい、炭素数１〜１８の炭化水素残基を表す。）
で表される化合物、及び、前記一般式（１）で表される化合物の多量体からなる群より選ばれるリン酸系化合物、及び、（メタ）アクリル系ポリマーを含有する。 (2) Adhesive layer The adhesive layer used for the polarizing film with an adhesive layer of this invention is formed from an acrylic adhesive composition. Acrylic adhesive composition
The following general formula (1):

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom.)
And a phosphoric acid compound selected from the group consisting of multimers of the compound represented by the general formula (1), and a (meth) acrylic polymer.

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

In General Formula (1), R ¹ and R ² are each independently 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,- (CH ₂ CH ₂ O) _n R ³ (R ³ is 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 0 to 0. And an integer of 15.). The alkyl group and alkenyl group may be linear or branched. Among these, as said C1-C18 hydrocarbon residue, a C1-C10 linear or branched alkyl group and a C6-C18 aryl group are preferable, C2-C6 A linear or branched alkyl group is more preferred.

In the present invention, phosphoric acid (H ₃ PO ₄ ) in which both R ¹ and R ^{2 in} the general formula (1) are hydrogen atoms can also be suitably used. In addition, salts of the phosphoric acid (metal salts such as sodium, potassium, and magnesium, ammonium salts, etc.) can also be suitably used.

（式中、Ｒ^１は、前記同様であり、Ｒ^３は、炭素数１〜１８のアルキル基、炭素数１〜１８のアルケニル基、又は、炭素数６〜１８のアリール基であり、ｎは０〜１５の整数である。）
で表されるリン酸エステル系化合物を挙げることができる。 Moreover, in this invention, it is preferable that the compound shown by General formula (1) is acidic phosphate ester. Here, the acidic phosphoric acid ester is a hydrocarbon residue having 1 to 18 carbon atoms in which R ¹ and R ^{2 in} the general formula (1) may contain an oxygen atom ( Diester) or when ^one of R ¹ and R ² is a hydrogen atom and the other is a hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom (monoester) For example, the following general formula (2):

(Wherein R ¹ is the same as above, R ³ is 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 It is an integer from 0 to 15.)
The phosphate ester type compound represented by these can be mentioned.

R ¹ in the general formula (2) is the same as R ¹ in the general formula (1), a hydrogen atom, or may contain an oxygen atom, a hydrocarbon residue having 1 to 18 carbon atoms. 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 ^{1 in the} general formula (2) is preferably a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms, a hydrogen atom or a carbon number A linear or branched alkyl group having 1 to 10 carbon atoms is more preferable, and a hydrogen atom or a linear or branched alkyl group having 2 to 6 carbon atoms is more preferable. The R ^3, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, or, there may be mentioned aryl groups having 6 to 18 carbon atoms, an alkyl group having 1 to 18 carbon atoms, carbon atoms It is preferably 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. Moreover, n is an integer of 0-15, and it is preferable that it is an integer of 0-10. In the present invention, does not contain polyethylene oxide structure _(CH 2 CH 2 O) _(i.e., in formula (2), n = 0) it is from the viewpoint of preventing deterioration.

As the phosphate ester compound represented by the general formula (2), R ¹ is a hydrogen atom, and R ³ is a linear or branched alkyl having 1 to 18 carbon atoms from the viewpoint of the adsorption effect on the adherend. phosphoric acid monoesters preferably a group in R ¹ is a hydrogen atom, R ³ is more preferably a phosphoric acid monoester is a linear or branched alkyl group having 1 to 10 carbon atoms, R ¹ is a hydrogen atom R ³ is more preferably a phosphoric acid monoester in which R ³ is a linear or branched alkyl group having 2 to 6 carbon atoms.

  In the present invention, two or more compounds represented by the general formula (2) may be mixed and used, or a mixture of the compound represented by the general formula (2) and the phosphoric acid may be used. You can do it. In general, the phosphoric ester compound represented by the general formula (2) is often obtained as a mixture of a monoester and a diester, and the phosphoric acid is further added to the mixture of the monoester and the diester. Are preferably used.

  In the present invention, a salt of a compound represented by the general formula (2) (a metal salt such as sodium, potassium and magnesium, an ammonium salt, etc.) can also be suitably used.

As a commercial item of the phosphoric ester compound represented by the general formula (2), “Phosphanol SM-172” (R ¹ = R ³ = C of the general formula (2) manufactured by Toho Chemical Industry Co., Ltd.) ₈ H ₁₇ , n = 0, mono-di mixture, acid value: 219 mg KOH / g), “phosphanol GF-185” (R ¹ = R ³ = C ₁₃ H ₂₇ in general formula (2), n = 0 , Mono-di mixture, acid value: 158 mg KOH / g), “phosphanol BH-650” (R ¹ = R ³ = C ₄ H ₉ in general formula (2), n = 1, mono-di mixture, acid Value: 388 mg KOH / g), “Phosphanol RS-410” (R ¹ = R ³ = C ₁₃ H ₂₇ in general formula (2), n = 4, mono-di mixture, acid value: 105 mg KOH / g), R of "Phosphanol RS-610" (the general formula (2) _{^{= C 13 H 27, R 3}} = C 13 H 27, n = 6, mono-di- mixture acid ^{value: 82mgKOH / g), R 1} = C of "Phosphanol RS-710" (the general formula (2) ₁₃ H ₂₇ , R ³ = C ₁₃ H ₂₇ , n = 10, mono-di mixture, acid value: 62 mg KOH / g), “phosphanol ML-220” (R ¹ = R ^{3 in} general formula (2) = C ₁₂ H ₂₅ , n = 2, mono-di mixture), “Phosphanol ML-200” (R ¹ = R ³ = C ₁₂ H ₂₅ in general formula (2), n = 0, mono-di mixture) , “Phosphanol ED-200” (R ¹ = R ³ = C ₈ H ₁₇ , n = 1, mono-di mixture of general formula (2)), “Phosphanol RL-210” (general formula (2 _{^{R 1 = R 3 = C 18}} H 37, n = 2, mono di mixtures)), Phosphanol GF-339 (mixture of _{^{R 1 = R 3 = C 6}} H 13 ~C 10 H 21 in formula (2), n = 0, mono di mixture), "Phosphanol GF-199" ( R ¹ = R ³ = C ₁₂ H ₂₅ in general formula (2), n = 0, mono-di mixture), “phosphanol RL-310” (R ¹ = R ³ = C _{18 in} general formula (2) H ₃₇ , n = 3, mono-di mixture), “Phosphanol LP-700” (R ¹ = R ³ = C ₆ H ₅ in general formula (2), n = 6, mono-di mixture), large “AP-1” (R ¹ = R ³ = CH ₃ , n = 0, mono-di mixture, acid value: 650 mgKOH / g or more) of “AP-1” manufactured by Hachi Chemical Industry Co., Ltd. 4 _{^{"(R 1 = R 3 = C}} 4 H 9 in formula (2), n = 0, mono di mixture acid value: 452MgKO / G), "DP-4" _{^{R 1 = R 3 = C 4}} H 9 of (formula (2), n = 0, mono di mixture acid value: 292mgKOH / g), "MP-4" ( R ¹ = H in general formula (2), R ³ = C ₄ H ₉ , n = 0, mono-di mixture, acid value: 670 mgKOH / g), “AP-8” (R ^{1 in} general formula (2) = R ³ = C ₈ H ₁₇ , n = 0, mono-di mixture, acid value: 306 mg KOH / g), “AP-10” (R ¹ = R ³ = C ₁₀ H ₂₁ in general formula (2), n = 0, mono-di mixture, acid value: 263 mg KOH / g), "MP-10" (R ¹ = H in general formula (2), R ³ = C ₁₀ H ₂₁ , n = 0, mono-di mixture, acid value: 400 mg KOH / g), Johoku _{^{R 1 = R 3 = C 8}} H 17, n = 0 chemical Co., Ltd. "JP-508" (the general formula (2), Roh Di mixture acid value: 288mgKOH / g), "JP-513" _{^{R 1 = R 3 = C 13}} H 27, n = 0 in (formula (2), mono di mixture), "JP-524R (R ¹ = R ³ = C ₂₄ H ₄₉ in general formula (2), n = 0, mono-di mixture), “DBP” (R ¹ = R ³ = C ₄ H ₉ in general formula (2), n = 0, mono-di mixture, acid value: 266 mg KOH / g), “LB-58” (R ¹ = R ³ = C ₈ H ₁₇ in general formula (2), n = 0, diester, acid value: 173 mg KOH / g), “Nikkor DDP-2” manufactured by Nikko Chemicals Co., Ltd. (mixture of R ¹ = R ³ = C ₁₂ H _{25 to} C ₁₅ H ₃₁ in general formula (2), n = 2), SIGMA- ALDRICH made of mono -N- butyl phosphate _{(O = P (OH) 2} (OC 4 H 9 , ^R 1 ⁼ H in the general formula _{(2), R 3 = C} 4 H 9, n = 0, Product Nomber: CDS001281, monoester), and the like as well as salts thereof. Incidentally, the "mono-di mixture" may include R ^{1 =} an oxygen atom (R ^{1 =} H in the general formula (2)) and diesters monoester (Formula (2), 1 carbon atoms For example, in the case of phosphanol SM-172, monoesters (R ¹ = H, R ³ = C ₈ H in the general formula (2)) are shown. ₁₇ , n = 0) and a diester (R ¹ = R ³ = C ₈ H _{17 in} the general formula (2), n = 0). The mixing ratio of the monoester and diester of the “mono / di mixture” can be calculated from the measurement result of ³¹ P-NMR. The measuring method is as described in the examples.

The phosphoric acid compound used in the present invention is selected from the group represented by the compound represented by the general formula (1) (or the compound represented by the general formula (2)), or a salt or multimer thereof. The compounds may be used alone or in admixture of two or more, but adherends (particularly adherends having a layer made of metal or metal oxide or metal or metal oxide) From the viewpoint of the adsorbing effect on the phosphoric acid, it is preferably a mixture of two or more selected from the group consisting of phosphoric acid, phosphoric monoester, and phosphoric diester, and includes phosphoric acid and phosphoric monoester And a mixture containing one or more phosphate esters selected from the group consisting of phosphoric acid diesters, and particularly preferably a mixture containing phosphate monoesters and phosphoric acid. In the present invention, one kind selected from the group consisting of phosphoric acid, phosphoric acid monoester, and phosphoric acid diester can be used alone, but when phosphoric acid is used alone, the pot life of the pressure-sensitive adhesive composition May be insufficient. In addition, phosphoric acid is a very polar compound and is not sufficiently compatible with acrylic polymers, so phosphoric acid bleeds out to the surface of the adhesive layer, resulting in problems with durability. There is a case. Moreover, when phosphoric acid is not used and only phosphoric acid ester (phosphoric acid monoester and / or phosphoric acid diester) is used, there is a problem in durability under extremely severe conditions (for example, heat cycle test). There is a case. In the present invention, it is most preferable to use a phosphoric acid-based compound containing phosphoric acid and phosphoric acid monoester from the viewpoint of the balance between the suppression of the corrosion of the transparent conductive layer and the durability under extremely severe conditions. The total amount of phosphoric acid and phosphoric acid monoester is not particularly limited, but is preferably 80% by weight or more in 100% by weight of the phosphoric acid compound. Here, the phosphoric acid monoester is a carbon atom having 1 to 18 carbon atoms in which ^one of R ¹ and R ^{2 in} the general formula (1) is a hydrogen atom, and the other may contain an oxygen atom. It is a compound that is a hydrogen residue (in the case of the general formula (2), a compound in which R ¹ is a hydrogen atom), and a phosphoric acid diester is a compound in which R ¹ and R ^{2 in} the general formula (1) are oxygen atoms A compound which is a hydrocarbon residue having 1 to 18 carbon atoms which may be contained (in the case of the general formula (2), R ¹ may contain an oxygen atom, and the hydrocarbon residue having 1 to 18 carbon atoms may be contained) Compound which is a group).

  The adsorption effect on the adherend (particularly metal or metal oxide) is considered to be related to the adherence surface and the phosphate compound, which is defined by the HSAB rule, that is, the “hard and soft acid-base law”. By combining a hard base with a hard acid and a soft base with a soft acid, the adsorption effect is high, and as a result, it is considered that a high deterioration preventing effect can be obtained. That is, for example, In of ITO corresponds to a hard acid defined by the HSAB rule, and the phosphoric acid compound is changed from a hard base to a soft base in the order of phosphoric acid, phosphoric monoester, and phosphoric diester. It can be adsorbed to ITO effectively in order, and as a result, it is considered that a high deterioration preventing effect can be obtained.

  Moreover, when using the mixture of a monoester body and a diester body, it is preferable that it is a mixture containing many monoester bodies. The mixing ratio (weight ratio) of the mixture of the monoester and diester is preferably monoester: diester = 6: 4 to 9: 1, more preferably 7: 3 to 9: 1. preferable. For the above reason, it is preferable to include a large amount of monoester because the adsorbing effect on the adherend is high.

  Further, as described above, in the present invention, it is preferable to further add phosphoric acid to the phosphoric ester compound (particularly phosphoric monoester). In this case, the amount of phosphoric acid added is phosphoric ester compound 100. It is preferable that it is 10-400 weight part with respect to a weight part, It is more preferable that it is 10-100 weight part, It is preferable from a viewpoint of the adsorption effect with respect to a to-be-adhered body that it is 10-50 weight part. Further, from the viewpoint of durability under very severe conditions, the amount of phosphoric acid added is preferably 10 to 100 parts by weight, and 10 to 50 parts by weight with respect to 100 parts by weight of the phosphate ester compound. More preferably, it is a part.

  Moreover, it is preferable that the acid value of the phosphoric acid compound used in this invention is 900 mgKOH / g or less, It is more preferable that it is 50-800 mgKOH / g, It is preferable that it is 10-700 mgKOH / g. From the viewpoint of handling in production, the acid value of the phosphoric acid compound is preferably 400 mgKOH / g or less, more preferably 50 to 400 mgKOH / g, and 50 to 350 mgKOH / g. Is more preferable, and 100 to 300 mgKOH / g is particularly preferable. The phosphoric acid compound may act as a reaction catalyst for the cross-linking reaction depending on the type of cross-linking agent described below (for example, an isocyanate-based cross-linking agent), and in that case, the pot life as an adhesive is shortened. There was a case. By making the acid value of a phosphoric acid compound into the said range, since it can suppress acting as a reaction catalyst, it is preferable from a viewpoint of the pot life of an adhesive. Moreover, it is preferable to add the phosphoric acid compound which has the acid value of the said range with the addition amount mentioned later from a viewpoint which can exhibit an effect efficiently.

  Moreover, as a multimer of the compound represented by the said General formula (1), the dimer of the compound represented by the said General formula (1), a trimer, etc. can be mentioned.

  The addition amount of the phosphoric acid compound is preferably 0.001 to 4 parts by weight and more preferably 0.001 to 3 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer described later. Preferably, the amount is 0.001 to 2 parts by weight, more preferably 0.005 to 1 part by weight, still more preferably 0.01 to 1 part by weight, and 0.02 to 0. 2 parts by weight is particularly preferred. It is preferable that the addition amount of the phosphoric acid compound is within the above range because an increase in the surface resistance value of the transparent conductive layer can be suppressed and durability against heating and humidification can be improved. Moreover, in this invention, as above-mentioned, although phosphoric acid compounds, such as phosphoric acid and phosphoric acid ester, can be used together, in that case, it can add so that a total amount may become the said range.

  In the present invention, by using the pressure-sensitive adhesive layer-attached polarizing film having the pressure-sensitive adhesive layer formed from the acrylic pressure-sensitive adhesive composition containing the phosphoric acid compound, on the pressure-sensitive adhesive layer surface of the pressure-sensitive adhesive layer-attached polarizing film, Even if a transparent conductive layer is laminated, an increase in surface resistance of the transparent conductive layer can be suppressed. When phosphoric acid is contained in the phosphoric acid compound, the phosphoric acid forms a passive film with the metal ions in the transparent conductive layer on the surface of the transparent conductive layer, and the iodine in the polarizer reaches the surface of the transparent conductive layer. As a result, it is considered that corrosion of the transparent conductive layer is prevented, and when the phosphoric acid compound contains a phosphoric acid compound (for example, phosphoric acid ester, etc.), the phosphoric acid compound is selective. In order to form a film by adsorbing to the surface of the transparent conductive layer, iodine in the polarizer does not migrate to the surface of the transparent conductive layer, and as a result, corrosion of the transparent conductive layer is hindered.

  As for the corrosion referred to here, the metal oxide is corroded by a mechanism different from the generally known metal corrosion. In the case of a metal oxide such as ITO, iodine derived from a polarizer soaks into the metal oxide layer and lowers the carrier mobility of the metal oxide, so that the resistance value increases.

  In the present invention, it is possible to exhibit an excellent corrosion inhibitory effect against the corrosion of the metal oxide as described above, and in particular, to exhibit a better effect on the transparent conductive layer made of the metal oxide. It is.

  The (meth) acrylic polymer used in the present invention is not particularly limited. For example, the (meth) acrylic polymer is preferably obtained by polymerizing a monomer component containing an alkyl (meth) acrylate. It is preferably obtained by polymerizing a monomer component containing a (meth) acrylate and a hydroxyl group-containing monomer. Alkyl (meth) acrylate refers to alkyl acrylate and / or alkyl methacrylate, and (meth) in the present invention has the same meaning.

  As the alkyl group related to the alkyl (meth) acrylate, various linear or branched ones can be used. Specific examples of the alkyl (meth) acrylate include, for example, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, isopentyl (meth) acrylate, isoamyl (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-tride Le (meth) acrylate, tetradecyl (meth) acrylate, stearyl (meth) acrylate, octadecyl (meth) acrylate, or dodecyl (meth) acrylate and the like. These can be used alone or in combination. Among these, the alkyl (meth) acrylate which has a C4-C18 alkyl group is preferable, the (meth) acrylate which has a C4-C10 alkyl group is more preferable, n-butyl (meth) acrylate, 2- Ethylhexyl (meth) acrylate is more preferable, and n-butyl (meth) acrylate is particularly preferable.

  The alkyl (meth) acrylate is preferably 50 parts by weight or more, preferably 60 parts by weight or more, and 70 parts by weight or more with respect to 100 parts by weight of the monomer component forming the (meth) acrylic polymer. Is more preferably 80 parts by weight or more, and particularly preferably 90 parts by weight or more.

  Moreover, as a hydroxyl group containing monomer, what has a polymerizable functional group which has unsaturated double bonds, such as a (meth) acryloyl group or a vinyl group, and has a hydroxyl group can be especially used without a restriction | limiting. 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, (4-hydroxymethylcyclohexyl) methyl (meth) acrylate, etc. can be mentioned, and these can be used alone or in combination. Two or more kinds can be mixed and used. Among these, 4-hydroxybutyl acrylate is preferable. Moreover, when using an isocyanate type crosslinking agent as a crosslinking agent mentioned later, a crosslinking point with the isocyanate group of an isocyanate type crosslinking agent can be efficiently ensured by using 4-hydroxybutyl acrylate as a hydroxyl group-containing monomer. This is preferable because it is possible.

  The hydroxyl group-containing monomer is preferably 10 parts by weight or less, more preferably 0.1 to 10 parts by weight, with respect to 100 parts by weight of the monomer component forming the (meth) acrylic polymer. 1 to 3 parts by weight is more preferable.

  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. However, in addition to these monomers, carboxyl group-containing monomers, aryl group-containing monomers, and other copolymerization monomers can be used as monomer components.

  As the carboxyl group-containing monomer, those having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and having a carboxyl 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, and crotonic acid. These may be used alone or in combination. Can be used.

  The carboxyl group-containing monomer is preferably 10 parts by weight or less, more preferably 8 parts by weight or less with respect to 100 parts by weight of the monomer component forming the (meth) acrylic polymer, and in particular, almost influence on the transparent conductive layer. In terms of the amount not added, it is more preferably 6 parts by weight or less, further preferably 2 parts by weight or less, and particularly preferably 0.5 parts by weight or less.

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

  The proportion of the aryl group-containing monomer is preferably 30 parts by weight or less, more preferably 1 to 20 parts by weight, and further preferably 5 to 15 parts by weight with respect to 100 parts by weight of the monomer component forming the (meth) acrylic polymer. preferable.

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

Examples of copolymerizable monomers include maleimide monomers such as N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, and N-phenylmaleimide; for example, N-methylitaconimide, N-ethylitaconimide, N -Itacone imide monomers such as butyl itaconimide, N-octyl itacon imide, N-2-ethylhexyl itacon imide, N- cyclohexyl itacon imide, N- lauryl itacon imide; Succinimide monomers such as (meth) acryloyl-6-oxyhexamethylene succinimide, N- (meth) acryloyl-8-oxyoctamethylene succinimide; for example, styrene sulfonic acid, Examples include sulfonic acid group-containing monomers such as aryl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) acrylamide propane sulfonic acid, sulfopropyl (meth) acrylate, and (meth) acryloyloxynaphthalene sulfonic acid. .

  In addition, as the copolymerizable monomer, for example, glycol-based acrylic ester monomers such as polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxyethylene glycol (meth) acrylate, and methoxypolypropylene glycol (meth) acrylate Other examples include, for example, tetrahydrofurfuryl (meth) acrylate, a heterocyclic ring such as fluorine (meth) acrylate, and an acrylate monomer containing a halogen atom.

  Furthermore, a polyfunctional monomer can be used as the copolymerizable monomer. Examples of the polyfunctional monomer include compounds having two or more unsaturated double bonds such as a (meth) acryloyl group and a vinyl group. For example, 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) In addition to (mono or poly) alkylene glycol di (meth) acrylates such as ethylene glycol di (meth) acrylate and (mono or poly) propylene glycol di (meth) acrylate such as propylene glycol di (meth) acrylate, neopentyl glycol Di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pen Esterified product of (meth) acrylic acid and polyhydric alcohol such as erythritol tri (meth) acrylate and dipentaerythritol hexa (meth) acrylate; polyfunctional vinyl compound such as divinylbenzene; allyl (meth) acrylate, (meth) Examples thereof include compounds having a reactive unsaturated double bond such as vinyl acrylate. In addition, as a polyfunctional monomer, polyester (meta) having two or more unsaturated double bonds such as (meth) acryloyl group and vinyl group as functional groups similar to the monomer component is added to a skeleton such as polyester, epoxy, and urethane. ) Acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, and the like can also be used.

  The proportion of the other copolymerization monomer is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, and even more preferably 15 parts by weight or less with respect to 100 parts by weight of the monomer component forming the (meth) acrylic polymer. 10 parts by weight or less is particularly preferable. When the proportion of the copolymerization monomer is too large, adhesive properties such as reduced adhesion to various adherends such as glass and films of the adhesive layer formed from the acrylic adhesive composition, transparent conductive layer, etc. May decrease.

  The weight average molecular weight of the (meth) acrylic polymer used in the present invention is preferably in the range of 1,200,000 to 3,000,000, more preferably 1,200,000 to 2,700,000, and even more preferably 1,200,000 to 2,500,000. If the weight average molecular weight is less than 1,200,000, it may not be preferable in terms of heat resistance. Moreover, when the weight average molecular weight is less than 1,200,000, the low molecular weight component increases in the pressure-sensitive adhesive composition, and the low molecular weight component bleeds out from the pressure-sensitive adhesive layer, which may impair transparency. Moreover, the pressure-sensitive adhesive layer obtained using a (meth) acrylic polymer having a weight average molecular weight of less than 1,200,000 may have poor solvent resistance and mechanical properties. On the other hand, if the weight average molecular weight is larger than 3 million, a large amount of dilution solvent is required to adjust the viscosity for coating, which is not preferable from the viewpoint of cost. Moreover, it is preferable from a viewpoint of corrosion resistance and durability because a weight average molecular weight exists in the said range. The weight average molecular weight is a value calculated by polystyrene conversion measured by GPC (gel permeation chromatography).

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

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

  The polymerization initiator, chain transfer agent, emulsifier and the like used for radical polymerization are not particularly limited and can be appropriately selected and used. In addition, the weight average molecular weight of a (meth) acrylic-type polymer can be controlled by the usage-amount of a polymerization initiator and a chain transfer agent, and reaction conditions, The usage-amount is suitably adjusted according to these kinds.

  Examples of the polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [2- (5-methyl-2). -Imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis (2-methylpropionamidine) disulfate, 2,2'-azobis (N, N'-dimethyleneisobutylamidine), 2,2 Azo initiators such as' -azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate (trade name: VA-057, manufactured by Wako Pure Chemical Industries, Ltd.), potassium persulfate, Persulfates such as ammonium sulfate, di (2-ethylhexyl) peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate, di sec-butyl peroxydicarbonate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, dilauroyl peroxide, di-n-octanoyl peroxide, 1, 1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, di (4-methylbenzoyl) peroxide, dibenzoyl peroxide, t-butylperoxyisobutyrate, 1,1-di (t- Hexylperoxy) peroxide initiators such as cyclohexane, t-butyl hydroperoxide, hydrogen peroxide, peroxides such as a combination of persulfate and sodium bisulfite, a combination of peroxide and sodium ascorbate, And redox initiators combined with reducing agents. But it is not limited thereto.

  The polymerization initiator may be used alone, or may be used in combination of two or more, but the total content is 100 weight of monomer component forming the (meth) acrylic polymer. The amount is preferably about 0.005 to 1 part by weight with respect to parts.

  Examples of the chain transfer agent include lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolate, and 2,3-dimercapto-1-propanol. The chain transfer agent may be used alone or in combination of two or more, but the total content is 0.1 parts by weight with respect to 100 parts by weight of the total amount of monomer components. Less than or equal to

  Various silane coupling agents can be added to the acrylic pressure-sensitive adhesive composition used in the present invention in order to improve adhesion under high-temperature and high-humidity conditions. As the silane coupling agent, one having any appropriate functional group can be used. Examples of the functional group include vinyl group, epoxy group, amino group, mercapto group, (meth) acryloxy group, acetoacetyl group, isocyanate group, styryl group, polysulfide group and the like. Specifically, for example, vinyl group-containing silane coupling agents such as vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycol Epoxy group-containing silane coupling agents such as sidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, γ-triethoxysilyl-N- (1,3-dimethylbutylidene) Propylamine, N-phenyl-γ Amino group-containing silane coupling agents such as aminopropyltrimethoxysilane; γ-mercaptopropylmethyldimethoxysilane and other mercapto group-containing silane coupling agents; p-styryltrimethoxysilane and other styryl group-containing silane coupling agents; (Meth) acrylic group-containing silane coupling agents such as acryloxypropyltrimethoxysilane and γ-methacryloxypropyltriethoxysilane; isocyanate group-containing silane coupling agents such as 3-isocyanatopropyltriethoxysilane; bis (triethoxysilyl) And polysulfide group-containing silane coupling agents such as propyl) tetrasulfide.

  The silane coupling agent may be used alone or in combination of two or more, but the total content is 100% of all monomer components constituting the (meth) acrylic polymer. The amount is preferably 1 part by weight or less, more preferably 0.01 to 1 part by weight, still more preferably 0.02 to 0.8 part by weight, and more preferably 0.05 to Particularly preferred is 0.7 part by weight. When the amount of the silane coupling agent exceeds 1 part by weight, an unreacted coupling agent component is generated, which is not preferable from the viewpoint of durability.

  In addition, when the silane coupling agent can be copolymerized with the monomer component by radical polymerization, the silane coupling agent can be used as the monomer component. It is preferable that the ratio is 0.005-0.7 weight part with respect to 100 weight part of all the monomer components which comprise the said (meth) acrylic-type polymer.

  Furthermore, the acrylic pressure-sensitive adhesive composition used in the present invention is preferable because a cohesive force related to the durability of the pressure-sensitive adhesive can be imparted by adding a crosslinking agent.

  As the cross-linking agent, a polyfunctional compound is used, and an organic cross-linking agent and a polyfunctional metal chelate are exemplified. Examples of the organic crosslinking agent include an epoxy crosslinking agent, an isocyanate crosslinking agent, a carbodiimide crosslinking agent, an imine crosslinking agent, an oxazoline crosslinking agent, an aziridine crosslinking agent, and a peroxide crosslinking agent. A polyfunctional metal chelate is one in which a polyvalent metal atom is covalently or coordinately bonded to an organic compound. Examples of polyvalent metal atoms 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. Can be mentioned. Examples of the atom in the organic compound that is covalently bonded or coordinated 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 can be used alone or in combination of two or more. Among these, a peroxide type crosslinking agent and an isocyanate type crosslinking agent are preferable, and it is more preferable to use these in combination.

  The isocyanate-based crosslinking agent refers to a compound having two or more isocyanate groups in a molecule (including isocyanate-regenerating functional groups in which isocyanate groups are temporarily protected by a blocking agent or quantification).

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

  More specifically, for example, lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate, alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate, 2,4-tolylene diisocyanate, Aromatic diisocyanates such as 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, polymethylene polyphenyl isocyanate, trimethylolpropane / tolylene diisocyanate trimer adduct (trade name: Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd. ), Trimethylolpropane / hexamethylene diisocyanate trimer adduct (trade name: Coronate HL, manufactured by Nippon Polyurethane Industry Co., Ltd.), hexame Isocyanurate of diisocyanate (trade name: Coronate HX, manufactured by Nippon Polyurethane Industry Co., Ltd.) and the like, trimethylolpropane adduct of xylylene diisocyanate (trade name: D110N, manufactured by Mitsui Chemicals, Inc.), Trimethylolpropane adduct of hexamethylene diisocyanate (trade name: D160N, manufactured by Mitsui Chemicals); polyether polyisocyanate, polyester polyisocyanate, and adducts of these with various polyols, isocyanurate bond, burette bond And polyisocyanate polyfunctionalized with an allophanate bond. Among these, it is preferable to use an aliphatic isocyanate because the reaction rate is high.

  Various peroxides are used as the peroxide-based crosslinking agent. Examples of peroxides include di (2-ethylhexyl) peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate, di-sec-butylperoxydicarbonate, and t-butylperoxyneodecanoate. , T-hexylperoxypivalate, t-butylperoxypivalate, dilauroyl peroxide, di-n-octanoyl peroxide, 1,1,3,3-tetramethylbutylperoxyisobutyrate, 1 1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, di (4-methylbenzoyl) peroxide, dibenzoyl peroxide, t-butylperoxyisobutyrate, and the like. Among these, di (4-t-butylcyclohexyl) peroxydicarbonate, dilauroyl peroxide, and dibenzoyl peroxide, which are particularly excellent in crosslinking reaction efficiency, are preferably used.

The blending ratio of the crosslinking agent in the acrylic pressure-sensitive adhesive composition is not particularly limited, but is usually about 10 parts by weight or less of the crosslinking agent (solid content) with respect to 100 parts by weight of the (meth) acrylic polymer (solid content). Blended in proportions. The blending ratio of the crosslinking agent is preferably 0.01 to 10 parts by weight, more preferably about 0.01 to 5 parts by weight. Moreover, especially when using a peroxide type crosslinking agent, about 0.05-1 weight part is preferable with respect to 100 weight part of (meth) acrylic-type polymer (solid content), and 0.06-0. 5 parts by weight is more preferred.

  Further, an ionic compound is preferably added to the acrylic pressure-sensitive adhesive composition used in the present invention from the viewpoint of preventing the film from being charged during the process operation.

  As the ionic compound, an alkali metal salt and / or an organic cation-anion salt can be preferably used. As the alkali metal salt, an organic salt or inorganic salt of an alkali metal can be used. The “organic cation-anion salt” in the present invention refers to an organic salt whose cation part is composed of an organic substance, and the anion part may be an organic substance or an inorganic substance. There may be. “Organic cation-anion salt” is also called an ionic liquid or ionic solid.

<Alkali metal salt>
Examples of the alkali metal ions constituting the cation part of the alkali metal salt include lithium, sodium, and potassium ions. Of these alkali metal ions, lithium ions are preferred.

The anion part of the alkali metal salt may be composed of an organic material or an inorganic material. Examples of the anion part constituting the organic salt include CH ₃ COO ⁻ , CF ₃ COO ⁻ , CH ₃ SO ₃ ⁻ , CF ₃ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₃ C ⁻ , and C ₄ F ₉ SO _{3. ^{-, C 3 F 7 COO -}} , (CF 3 SO 2) (CF 3 CO) N -, - O 3 S (CF 2) 3 SO 3 -, PF 6 -, CO 3 2-, or the following general formula ( 4) to (7),
(4): (C _n F _{2n + 1} SO ₂ ) ₂ N ⁻ (where n is an integer of 1 to 10),
_{(5): CF 2 (C} m F 2m SO 2) 2 N - ( where, m is an integer of from 1 to 10),
^{_{(6): - O 3 S}} (CF 2) l SO 3 - ( where, l is an integer of from 1 to 10),
^{_{(7) :( C p F 2p}} + 1 SO 2) N - (C q F 2q + 1 SO 2) ( where, p, q is an integer of from 1 to 10),
The one represented by is used. In particular, an anion moiety containing a fluorine atom is preferably used because an ionic compound having good ion dissociation properties can be obtained. The anion part constituting the inorganic salt includes Cl ⁻ , Br ⁻ , I ⁻ , AlCl ₄ ⁻ , Al ₂ Cl ₇ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , ClO ₄ ⁻ , NO ₃ ⁻ , AsF ₆ ⁻ , SbF. ₆ ⁻ , NbF ₆ ⁻ , TaF ₆ ⁻ , (CN) ₂ N ⁻ , and the like are used. As the anion moiety, (perfluoroalkylsulfonyl) imide represented by the general formula (4) such as (CF ₃ SO ₂ ) ₂ N ⁻ and (C ₂ F ₅ SO ₂ ) ₂ N ⁻ is preferable, (Trifluoromethanesulfonyl) imide represented by CF ₃ SO ₂ ) ₂ N ⁻ is preferable.

Specific examples of alkali metal organic salts include sodium acetate, sodium alginate, sodium lignin sulfonate, sodium toluenesulfonate, lithium hexafluorophosphate (LiPF ₆ ), LiCF ₃ SO ₃ , Li (CF ₃ SO ₂ ) ₂ N, Li (CF ₃ SO ₂ ) ₂ N, Li (C ₂ F ₅ SO ₂ ) ₂ N, Li (C ₄ F ₉ SO ₂ ) ₂ N, Li (CF ₃ SO ₂ ) ₃ C, KO ₃ S (CF ₂ ) ₃ SO ₃ K, LiO ₃ S (CF ₂ ) ₃ SO ₃ K and the like can be mentioned. Among these, lithium hexafluorophosphate (LiPF ₆ ), LiCF ₃ SO ₃ , Li (CF ₃ SO _{2) 2 N, Li (C} 2 F 5 SO 2) 2 N, Li (C 4 F 9 SO 2) 2 N, Li (CF 3 SO 2) 3 C are preferable _{Li (CF 3 SO 2) 2} N, Li (C 2 F 5 SO 2) 2 N, Li (C 4 F 9 SO 2) fluorine-containing lithium imide salt is more preferred, such as ₂ N, lithium hexafluorophosphate ( LiPF ₆ ) and lithium bistrifluoromethanesulfonylimide (LiTFSI, Li (CF ₃ SO ₂ ) ₂ N) are particularly preferred.

  Examples of the alkali metal inorganic salt include lithium perchlorate and lithium iodide.

<Organic cation-anion salt>
The organic cation-anion salt used in the present invention is composed of a cation component and an anion component, and the cation component is composed of an organic substance. As the cation component, specifically, pyridinium cation, piperidinium cation, pyrrolidinium cation, cation having pyrroline skeleton, cation having pyrrole skeleton, imidazolium cation, tetrahydropyrimidinium cation, dihydropyrimidinium cation, Examples include pyrazolium cation, pyrazolinium cation, tetraalkylammonium cation, trialkylsulfonium cation, and tetraalkylphosphonium cation.

Examples of the anion component include Cl ⁻ , Br ⁻ , I ⁻ , AlCl ₄ ⁻ , Al ₂ Cl ₇ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , ClO ₄ ⁻ , NO ₃ ⁻ , CH ₃ COO ⁻ , and CF ₃ COO. ⁻ , CH ₃ SO ₃ ⁻ , CF ₃ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₃ C ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , NbF ₆ ⁻ , TaF ₆ ⁻ , (CN) ₂ N ⁻ , C ₄ F _{^{9 SO 3 -, C 3 F}} 7 COO -, ((CF 3 SO 2) (CF 3 CO) N -, - O 3 S (CF 2) 3 SO 3 -, or the following general formula (4) to (7 ),
(4): (C _n F _{2n + 1} SO ₂ ) ₂ N ⁻ (where n is an integer of 1 to 10),
_{(5): CF 2 (C} m F 2m SO 2) 2 N - ( where, m is an integer of from 1 to 10),
_{^{(6): - O 3 S}} (CF 2) l SO 3 - ( where, l is an integer of from 1 to 10),
^{_{(7) :( C p F 2p}} + 1 SO 2) N - (C q F 2q + 1 SO 2) ( where, p, q is an integer of from 1 to 10),
The one represented by is used. Among these, in particular, an anionic component containing a fluorine atom is preferably used because an ionic compound having good ion dissociation properties can be obtained.

  As a specific example of the organic cation-anion salt, a compound comprising a combination of the cation component and the anion component is appropriately selected and used. For example, 1-butylpyridinium tetrafluoroborate, 1-butylpyridinium hexafluorophosphate, 1-butyl-3-methylpyridinium tetrafluoroborate, 1-butyl-3-methylpyridinium trifluoromethanesulfonate, 1-butyl-3-methylpyridinium Bis (trifluoromethanesulfonyl) imide, 1-butyl-3-methylpyridinium bis (pentafluoroethanesulfonyl) imide, 1-hexylpyridinium tetrafluoroborate, 2-methyl-1-pyrroline tetrafluoroborate, 1-ethyl-2 -Phenylindole tetrafluoroborate, 1,2-dimethylindole tetrafluoroborate, 1-ethylcarbazole tetrafluoroborate, 1-ethyl-3-methylimidazo Um tetrafluoroborate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium trifluoroacetate, 1-ethyl-3-methylimidazolium heptafluorobutyrate, 1-ethyl-3-methyl Imidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium perfluorobutanesulfonate, 1-ethyl-3-methylimidazolium dicyanamide, 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1- Ethyl-3-methylimidazolium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-3-methylimidazolium tris (trifluoromethanesulfonyl) methide, 1-butyl-3-methylimidazolium 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium trifluoroacetate, 1-butyl-3-methylimidazolium heptafluorobutyrate, 1-butyl-3- Methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium perfluorobutanesulfonate, 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-hexyl-3-methylimidazolium bromide, 1 -Hexyl-3-methylimidazolium chloride, 1-hexyl-3-methylimidazolium tetrafluoroborate, 1-hexyl-3-methylimidazolium hexafluorophosphate, 1-hexyl-3 -Methylimidazolium trifluoromethanesulfonate, 1-octyl-3-methylimidazolium tetrafluoroborate, 1-octyl-3-methylimidazolium hexafluorophosphate, 1-hexyl-2,3-dimethylimidazolium tetrafluoroborate, 1,2-dimethyl-3-propylimidazolium bis (trifluoromethanesulfonyl) imide, 1-methylpyrazolium tetrafluoroborate, 3-methylpyrazolium tetrafluoroborate, tetrahexylammonium bis (trifluoromethanesulfonyl) imide, Diallyldimethylammonium tetrafluoroborate, diallyldimethylammonium trifluoromethanesulfonate, diallyldimethylammonium bis (trifluoromethanes Phonyl) imide, diallyldimethylammonium bis (pentafluoroethanesulfonyl) imide, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium tetrafluoroborate, N, N-diethyl-N-methyl-N -(2-methoxyethyl) ammonium trifluoromethanesulfonate, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl-N -(2-methoxyethyl) ammonium bis (pentafluoroethanesulfonyl) imide, glycidyltrimethylammonium trifluoromethanesulfonate, glycidyltrimethylammonium bis (trifluoromethanesulfonyl) imide, glycidyl trime Ruammonium bis (pentafluoroethanesulfonyl) imide, 1-butylpyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-butyl-3-methylpyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-ethyl-3-methylimidazolium (Trifluoromethanesulfonyl) trifluoroacetamide, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium (trifluoromethanesulfonyl) trifluoroacetamide, diallyldimethylammonium (trifluoromethanesulfonyl) trifluoroacetamide, glycidyl Trimethylammonium (trifluoromethanesulfonyl) trifluoroacetamide, N, N-dimethyl-N-ethyl-N-pro Pyrammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-butylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-pentylammonium bis (trifluoromethane Sulfonyl) imide, N, N-dimethyl-N-ethyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N , N-dimethyl-N-ethyl-N-nonylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N, N-dipropylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N- Propi -N-butylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-propyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-propyl-N-hexylammonium bis (Trifluoromethanesulfonyl) imide, N, N-dimethyl-N-propyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-butyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide N, N-dimethyl-N-butyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-pentyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, , N-dimethyl-N, N-dihexylammonium bis (trifluoromethanesulfonyl) imide, trimethylheptylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl-N-propylammonium bis (trifluoromethanesulfonyl) Imido, N, N-diethyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N, N- Diethyl-N-propyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, triethylpropylammonium bis (trifluoromethanesulfonyl) imide, triethylpentylammonium bis (Trifluoromethanesulfonyl) imide, triethylheptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-methyl-N-ethylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-methyl- N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-butyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N, N-dihexylammonium bis (trifluoro) (Romethanesulfonyl) imide, N, N-dibutyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dibutyl-N-methyl-N-hexylammonium bis (g Fluoromethanesulfonyl) imide, trioctylmethylammonium bis (trifluoromethanesulfonyl) imide, N-methyl-N-ethyl-N-propyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, 1-butyl-3-methylpyridine Examples include -1-ium trifluoromethanesulfonate. As these commercially available products, for example, “CIL-314” (manufactured by Nippon Carlit Co., Ltd.), “ILA2-1” (manufactured by Koei Chemical Industry Co., Ltd.) and the like can be used.

  Also, for example, tetramethylammonium bis (trifluoromethanesulfonyl) imide, trimethylethylammonium bis (trifluoromethanesulfonyl) imide, trimethylbutylammonium bis (trifluoromethanesulfonyl) imide, trimethylpentylammonium bis (trifluoromethanesulfonyl) imide, trimethylheptyl Ammonium bis (trifluoromethanesulfonyl) imide, trimethyloctylammonium bis (trifluoromethanesulfonyl) imide, tetraethylammonium bis (trifluoromethanesulfonyl) imide, triethylbutylammonium bis (trifluoromethanesulfonyl) imide, tetrabutylammonium bis (trifluoromethanesulfonyl) Imide, tetrahex Le ammonium bis (trifluoromethanesulfonyl) imide, and the like.

  Further, for example, 1-dimethylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-ethylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpyrrolidinium bis (trifluoromethane) Sulfonyl) imide, 1-methyl-1-butylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-pentylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-hexylpyrrolidinium Bis (trifluoromethanesulfonyl) imide, 1-methyl-1-heptylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-propylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl- -Butyl pyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-pentylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-hexylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-heptylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1,1-dipropylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-propyl-1-butylpyrrolidinium bis (trifluoromethane) Sulfonyl) imide, 1,1-dibutylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-propylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-pentylpiperidinium bis (trifluoromethane) Sulfonyl) imide, 1,1-dimethylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-ethylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpiperidinium bis ( Trifluoromethanesulfonyl) imide, 1-methyl-1-butylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-pentylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-hexylpi Peridinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-heptylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-propylpiperidinium bis (trifluoromethanesulfonyl) imide, 1- Ethyl-1-butylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-pentylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-hexylpiperidinium bis (trifluoromethanesulfonyl) Imido, 1-ethyl-1-heptylpiperidinium bis (trifluoromethanesulfonyl) imide, 1,1-dipropylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-propyl-1-butylpiperidinium bis (trifluoro) Lomethanesulfonyl) imide, 1,1-dibutylpiperidinium bis (trifluoromethanesulfonyl) imide, 1,1-dimethylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-ethylpyrrolidinium (Pentafluoroethanesulfonyl) imide, 1-methyl-1-propylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-butylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl -1-pentylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-hexylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-heptylpyrrolidinium bis (pentafluoro) Ethanesulfonyl) imide, 1-ethyl-1-propylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-butylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-pentyl Pyrrolidine Bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-hexylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-heptylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1, 1-dipropylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-propyl-1-butylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1,1-dibutylpyrrolidinium bis (pentafluoroethanesulfonyl) Imido, 1-propylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-pentylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1,1-dimethylpiperidinium bis (pentafluoroethanesulfonyl) i 1-methyl-1-ethylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-propylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-butylpiperidinium Bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-pentylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-hexylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl -1 heptylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-propylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-heptylpiperidinium bis (pentafluoroethane) Sulfonyl) imi , 1-ethyl-1-pentylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-hexylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-heptylpi Peridinium bis (pentafluoroethanesulfonyl) imide, 1-propyl-1-butylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1,1-dipropylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1, Examples include 1-dibutylpiperidinium bis (pentafluoroethanesulfonyl) imide.

  Also, instead of the cation component of the above compound, trimethylsulfonium cation, triethylsulfonium cation, tributylsulfonium cation, trihexylsulfonium cation, diethylmethylsulfonium cation, dibutylethylsulfonium cation, dimethyldecylsulfonium cation, tetramethylphosphonium cation, tetraethylphosphonium Examples thereof include compounds using a cation, a tetrabutylphosphonium cation, and a tetrahexylphosphonium cation.

Further, instead of the above bis (trifluoromethanesulfonyl) imide, bis (pentafluorosulfonyl) imide, bis (heptafluoropropanesulfonyl) imide, bis (nonafluorobutanesulfonyl) imide, trifluoromethanesulfonylnonafluorobutanesulfonylimide, And compounds using heptafluoropropanesulfonyl trifluoromethanesulfonylimide, pentafluoroethanesulfonylnonafluorobutanesulfonylimide, cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide anion, and the like.

  Examples of the ionic compound include inorganic salts such as ammonium chloride, aluminum chloride, copper chloride, ferrous chloride, ferric chloride, and ammonium sulfate in addition to the alkali metal salts and organic cation-anion salts. . These ionic compounds can be used alone or in combination.

  The mixing ratio of the ionic compound in the acrylic pressure-sensitive adhesive composition is not particularly limited, but is preferably about 10 parts by weight or less with respect to 100 parts by weight of the (meth) acrylic polymer (solid content). More preferably, it is more preferably 2 parts by weight or less. Moreover, although a lower limit is not specifically limited, 0.01 weight part or more is preferable.

  Furthermore, the acrylic pressure-sensitive adhesive composition used in the present invention includes, as necessary, a viscosity modifier, a release modifier, a tackifier, a plasticizer, a softener, glass fiber, glass beads, metal powder, and others. Various kinds of fillers, pigments, colorants (pigments, dyes, etc.), pH adjusters (acids or bases), antioxidants, ultraviolet absorbers, etc., which do not depart from the object of the present invention. These additives can also be used as appropriate. These additives can also be blended as an emulsion.

(3) Polarizing film with pressure-sensitive adhesive layer The polarizing film with a pressure-sensitive adhesive layer of the present invention forms a pressure-sensitive adhesive layer formed from the acrylic pressure-sensitive adhesive composition on at least one surface of the iodine-based polarizing film. It is obtained by.

  The method for forming the pressure-sensitive adhesive layer is not particularly limited, but the pressure-sensitive adhesive layer is formed by applying the acrylic pressure-sensitive adhesive composition on various substrates, drying it with a dryer such as a heat oven, and evaporating the solvent. And forming the pressure-sensitive adhesive layer by directly applying the acrylic pressure-sensitive adhesive composition onto the iodine-based polarizing film. May be.

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

  Various methods are used as a coating method on the substrate or polarizing film. Specifically, for example, fountain coater, roll coat, kiss roll coat, gravure coat, reverse coat, roll brush, spray coat, dip roll coat, bar coat, knife coat, air knife coat, curtain coat, lip coat, Daiko Examples of the method include an extrusion coating method using a catalyst.

  The drying conditions (temperature, time) are not particularly limited, and can be appropriately set depending on the composition, concentration, etc. of the acrylic pressure-sensitive adhesive composition. For example, about 80 to 170 ° C., preferably 90 to 200. C. for 1 to 60 minutes, preferably 2 to 30 minutes.

  The thickness (after drying) of the pressure-sensitive adhesive layer is, for example, preferably 5 to 100 μm, more preferably 10 to 60 μm, and further preferably 12 to 40 μm. When the thickness of the pressure-sensitive adhesive layer is less than 10 μm, the adhesion to the adherend becomes poor, and the durability under high temperature and high temperature and humidity tends to be insufficient. On the other hand, when the thickness of the pressure-sensitive adhesive layer exceeds 100 μm, the acrylic pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer cannot be fully dried at the time of drying and air bubbles remain, or the pressure-sensitive adhesive layer There is a tendency that unevenness in thickness occurs on the surface of the surface, and problems in appearance tend to become obvious.

  Examples of the constituent material of the release film include resin films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films, porous materials such as paper, cloth, and nonwoven fabric, nets, foam sheets, metal foils, and laminates thereof. An appropriate thin leaf body can be used, but a resin film is preferably used from the viewpoint of excellent surface smoothness.

  Examples of the resin film include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, and ethylene. -A vinyl acetate copolymer film etc. are mentioned.

  The thickness of the release film is usually 5 to 200 μm, preferably about 5 to 100 μm. For the release film, if necessary, release agent and antifouling treatment with a silicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based release agent, silica powder, etc., coating type, kneading type, An antistatic treatment such as a vapor deposition type can also be performed. In particular, the release property from the pressure-sensitive adhesive layer can be further improved by appropriately performing a release treatment such as silicone treatment, long-chain alkyl treatment, or fluorine treatment on the surface of the release film.

  The transparent resin film substrate is not particularly limited, and various resin films having transparency are used. The resin film is formed of a single layer film. For example, the materials include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, acetate resins, polyethersulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth) acrylic resins. , Polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl alcohol resin, polyarylate resin, polyphenylene sulfide resin, and the like. Of these, polyester resins, polyimide resins and polyethersulfone resins are particularly preferable.

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

  Moreover, you may have an anchor layer between an iodine type polarizing film and an adhesive layer. The material for forming the anchor layer is not particularly limited, and examples thereof include various polymers, metal oxide sols, and silica sols. Among these, polymers are particularly preferably used. The polymer may be used in any of a solvent-soluble type, a water-dispersed type, and a water-soluble type.

  Examples of the polymers include polyurethane resins, polyester resins, acrylic resins, polyether resins, cellulose resins, polyvinyl alcohol resins, polyvinyl pyrrolidone, polystyrene resins, and the like. Among these, polyurethane resins, polyester resins, and acrylic resins are particularly preferable. These resins can be appropriately mixed with a crosslinking agent. These other binder components can be used singly or in combination of two or more as appropriate.

  When the anchor layer is formed of a water dispersion type material, a water dispersion type polymer is used. Examples of the water-dispersible polymer include those obtained by emulsifying various resins such as polyurethane and polyester using an emulsifier, and introducing a water-dispersible anionic group, cationic group, or nonionic group into the resin. Examples include self-emulsified ones.

  The anchor agent can contain an antistatic agent. The antistatic agent is not particularly limited as long as it is a material that can impart conductivity, and examples thereof include ionic surfactants, conductive polymers, metal oxides, carbon black, and carbon nanomaterials. 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 of 150,000 in terms of polystyrene, manufactured by Mitsubishi Rayon Co., Ltd.). TRON series).

  The blending amount of the antistatic agent is, for example, 70 parts by weight or less, preferably 50 parts by weight or less with respect to 100 parts by weight of the polymers used for the anchor agent. From the viewpoint of the antistatic effect, it is preferably 10 parts by weight or more, and more preferably 20 parts by weight or more.

  In addition, the anchor agent can be blended with various additives for the purpose of suppressing deterioration of the pressure-sensitive adhesive layer and the polarizer generated when contacting the anchor coat layer, and imparts a function to the anchor coat layer. Various additives can be blended for the purpose. For example, antioxidants, deterioration inhibitors, ultraviolet absorbers, fluorescent brighteners, and the like can be added.

  The thickness of the anchor layer is not particularly limited, but is preferably 5 to 300 nm.

  The method for forming the anchor layer is not particularly limited and can be performed by a generally known method. In forming the anchor layer, the iodine polarizing film can be activated. Various methods can be employed for the activation treatment, such as corona treatment, low-pressure UV treatment, plasma treatment, and the like.

  The method for forming the pressure-sensitive adhesive layer on the anchor layer on the iodine-based polarizing film is as described above.

  Moreover, when the adhesive layer of the polarizing film with an adhesive layer of this invention is exposed, you may protect an adhesive layer with a release film (separator) until it uses for practical use. The above-mentioned thing can be mentioned as a release film. When a release film is used as a base material in the production of the above-mentioned pressure-sensitive adhesive layer, the release film is bonded to the iodine-type polarizing film by bonding the pressure-sensitive adhesive layer on the release film to the pressure-sensitive adhesive layer. It can be used as a release film for the pressure-sensitive adhesive layer of the attached polarizing film, and the process can be simplified.

2. Laminated body The laminated body of this invention is the transparent conductive layer of the member which has the adhesive layer of the said polarizing film with an adhesive layer, and the member which has the said transparent conductive layer. It is characterized by being bonded so as to be in contact with each other.

  The said polarizing film with an adhesive layer can use the above-mentioned thing.

  The member having a transparent conductive layer is not particularly limited, and a known member can be used. However, a member having a transparent conductive layer on a transparent substrate such as a transparent film, a transparent conductive layer and a liquid crystal can be used. The member which has a cell can be mentioned.

  The transparent substrate may be any material as long as it has transparency, and examples thereof include a resin film and a substrate made of glass (for example, a sheet-like, film-like, or plate-like substrate). A film is particularly preferred. Although the thickness of a transparent base material is not specifically limited, About 10-200 micrometers is preferable and about 15-150 micrometers is more preferable.

  Although it does not restrict | limit especially as a material of the said resin film, Various plastic materials which have transparency are mentioned. For example, the materials include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, acetate resins, polyethersulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth) acrylic resins. , Polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl alcohol resin, polyarylate resin, polyphenylene sulfide resin, and the like. Of these, polyester resins, polyimide resins and polyethersulfone resins are particularly preferable.

  In addition, the transparent base material is subjected to an etching process such as sputtering, corona discharge, flame, ultraviolet irradiation, electron beam irradiation, chemical conversion, oxidation, or undercoating treatment on the surface in advance, and the transparent conductive layer provided thereon You may make it improve the adhesiveness with respect to a transparent base material. Moreover, before providing a transparent conductive layer, you may remove and clean by solvent washing | cleaning, ultrasonic washing | cleaning, etc. as needed.

  The constituent material of the transparent conductive layer is not particularly limited and is selected from the group consisting of indium, tin, zinc, gallium, antimony, titanium, silicon, zirconium, magnesium, aluminum, gold, silver, copper, palladium, and tungsten. A metal oxide of at least one metal is used. The metal oxide may further contain a metal atom shown in the above group, if necessary. For example, indium oxide (ITO) containing tin oxide and tin oxide containing antimony are preferably used, and ITO is particularly preferably used. As ITO, it is preferable to contain 80 to 99 weight% of indium oxide and 1 to 20 weight% of tin oxide.

  Examples of the ITO include crystalline ITO and non-crystalline (amorphous) ITO. Crystalline ITO can be obtained by applying a high temperature during sputtering or by further heating amorphous ITO. Since the deterioration due to iodine occurs remarkably in non-crystalline ITO, the polarizing film with the pressure-sensitive adhesive layer of the present invention is particularly effective in non-crystalline ITO.

  The thickness of the transparent conductive layer is not particularly limited, but is preferably 7 nm or more, more preferably 10 nm or more, further preferably 12 to 60 nm, further preferably 15 to 45 nm, 18 It is more preferable to set it to -45 nm, and it is especially preferable to set it to 20-30 nm. If the thickness of the transparent conductive layer is less than 7 nm, the transparent conductive layer is likely to be deteriorated by iodine, and the change in the electric resistance value of the transparent conductive layer tends to increase. On the other hand, when it exceeds 60 nm, the productivity of the transparent conductive layer decreases, the cost also increases, and the optical characteristics tend to decrease.

  It does not specifically limit as a formation method of the said transparent conductive layer, A conventionally well-known method is employable. Specifically, for example, a vacuum deposition method, a sputtering method, and an ion plating method can be exemplified. In addition, an appropriate method can be adopted depending on the required film thickness.

  As thickness of the base material which has the said transparent conductive layer, 15-200 micrometers can be mentioned. Furthermore, it is preferable that it is 15-150 micrometers from a viewpoint of thin film formation, and it is more preferable that it is 15-50 micrometers. When the base material having the transparent conductive layer is used in a resistive film system, for example, a thickness of 100 to 200 μm can be mentioned. In addition, when used in the electrostatic capacity method, for example, a thickness of 15 to 100 μm is suitable, in particular, a thickness of 15 to 50 μm is more preferable, and a thickness of 20 to 50 μm is more preferable in accordance with the recent demand for further thinning. .

  Moreover, an undercoat layer, an oligomer prevention layer, etc. can be provided between a transparent conductive layer and a transparent base material as needed.

  In addition, as a member having a transparent conductive layer and a liquid crystal cell, the substrate of the liquid crystal cell including the configuration of a substrate (for example, a glass substrate) / liquid crystal layer / substrate used in an image display device such as various liquid crystal display devices. There may be mentioned those having a transparent conductive layer on the side not in contact with the liquid crystal layer. Further, 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 for forming the transparent conductive layer on the substrate of the liquid crystal cell is the same as described above.

3. Image display device The laminate of the present invention includes an image display device (liquid crystal display device, organic EL (electroluminescence) display device, PDP (plasma display panel), electronic paper, etc.) provided with an input device (touch panel, etc.), input device Although it can be used suitably in manufacture of the base material (member) which comprises apparatuses, such as (a touch panel etc.), or the base material (member) used for these apparatuses, it is especially suitable in manufacture of the optical base material for touch panels. Can be used. Moreover, it can be used irrespective of systems, such as a touch panel, such as a resistive film system and a capacitive system.

  The laminated body of the present invention is subjected to treatments such as cutting, resist printing, etching, and silver ink printing, and the resulting transparent conductive film can be used as a substrate for optical devices (optical member). The substrate for an optical device is not particularly limited as long as it is a substrate having optical characteristics. For example, an image display device (liquid crystal display device, organic EL (electroluminescence) display device, PDP (plasma display panel), Examples include base materials (members) constituting devices such as electronic paper) and input devices (touch panels, etc.) or base materials (members) used in these devices.

  In addition, as described above, the polarizing film with the pressure-sensitive adhesive layer of the present invention can suppress corrosion of the transparent conductive layer even when the transparent conductive layer is laminated on the pressure-sensitive adhesive layer of the polarizing film with the pressure-sensitive adhesive layer. The increase in surface resistance of the transparent conductive layer can be suppressed. Therefore, if it is an image display apparatus which has the structure which the adhesive layer of the polarizing film with an adhesive layer touches a transparent conductive layer, the polarizing film with an adhesive layer of this invention can be used conveniently. For example, the liquid crystal panel having the polarizing film with the pressure-sensitive adhesive layer and the transparent conductive layer of the present invention is bonded so that the pressure-sensitive adhesive layer of the polarizing film with the pressure-sensitive adhesive layer and the transparent conductive layer of the liquid crystal panel are in contact with each other, An image display device can be obtained.

  More specifically, an image display device using the transparent conductive layer as an antistatic layer application or an image display device using the transparent conductive layer as an electrode for a touch panel can be used. Specifically, as an image display device using the transparent conductive layer as an antistatic layer, for example, as shown in FIG. 1, a polarizing film 1 / adhesive layer 2 / antistatic layer 3 / glass substrate 4 / liquid crystal Examples thereof include an image display device comprising a layer 5 / driving electrode 6 / glass substrate 4 / adhesive layer 2 / polarizing film 1 wherein the antistatic layer 3 and the driving electrode 6 are formed of a transparent conductive layer. The polarizing film with an adhesive layer of the present invention can be used as the polarizing film with an adhesive layer (1, 2) on the upper side (viewing side) of the image display device. Further, as an image display device using the transparent conductive layer as an electrode for a touch panel, for example, polarizing film 1 / adhesive layer 2 / antistatic layer / sensor layer 7 / glass substrate 4 / liquid crystal layer 5 / driving electrode / sensor Layer 8 / glass substrate 4 / adhesive layer 2 / polarizing film 1 configuration (in-cell type touch panel, FIG. 2), polarizing film 1 / adhesive layer 2 / antistatic layer / sensor layer 7 / sensor layer 9 / glass substrate 4 / liquid crystal layer 5 / drive electrode 6 / glass substrate 4 / adhesive layer 2 / polarizing film 1 (on-cell type touch panel, FIG. 3), antistatic layer / sensor layer 7, sensor layer 9, drive electrode An image display device 6 is formed of a transparent conductive layer. The polarizing film with an adhesive layer of the present invention can be used as the polarizing film with an adhesive layer (1, 2) on the upper side (viewing side) of the image display device.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, this invention is not limited to a following example, unless the summary is exceeded. In each example, both parts and% are based on weight.

<Iodine content in polarizer>
The iodine content (iodine and / or iodine ion content) in the polarizer was measured by the following procedure.
1) X-ray fluorescence intensity was measured for a plurality of polarizers containing a predetermined amount of potassium iodide, and a relational expression between iodine content and fluorescence X-ray intensity was derived.
2) Fluorescent X-rays of an iodine polarizer with unknown iodine content were measured, and the iodine amount was calculated from the numerical values using the relational expression.

Production Example 1 (Production of Polarizing Film (1))
A stretched laminate was produced from the laminate in which a 9 μm-thick polyvinyl alcohol (PVA) layer was formed on an amorphous PET substrate by air-assisted stretching at a stretching temperature of 130 ° C. Next, 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 to produce a colored laminate. Further, an optical film laminate including a 4 μm-thick PVA layer in which the colored laminate is stretched integrally with an amorphous PET substrate so that the total draw ratio is 5.94 times by stretching in boric acid water at a stretching temperature of 65 ° C. Generated body. The PVA molecules in the PVA layer formed on the amorphous PET substrate by such two-stage stretching are oriented in the higher order, and the iodine adsorbed by the dyeing is oriented in the one direction as the polyiodine ion complex. It was possible to produce an optical film laminate including a PVA layer having a thickness of 4 μm, which constitutes a highly functional polarizing layer. Further, after applying a saponified 40 μm thick acrylic resin film (transparent protective film (1)) while applying a PVA adhesive to the surface of the polarizing layer of the optical film laminate, an amorphous PET group The material was peeled off to produce a polarizing film having a transparent protective film only on one side using a thin iodine-based polarizer. Hereinafter, this is referred to as a polarizing film (1). The iodine content of the polarizing film (1) was 5.1% by weight.

Production Examples 2 and 3 (Production of polarizing films (2) and (3))
Transparent protection only on one side using a thin iodine-based polarizer, as in Production Example 1, except that the dyeing time was changed from 60 seconds to 120 seconds (Production Example 2) and 180 seconds (Production Example 3). A polarizing film having a film was prepared. Hereinafter, these are referred to as polarizing films (2) and (3). The iodine contents of the polarizing films (2) and (3) were 7.2% by weight and 11.1% by weight, respectively.

Production Example 4 (Production of Polarizing Film (4))
A polyvinyl alcohol film having a thickness of 80 μm was stretched up to 3 times while being dyed for 1 minute in an iodine solution of 0.3% concentration at 30 ° C. between rolls having different speed ratios. Then, the total draw ratio was drawn up to 6 times while being immersed in an aqueous solution containing 60%, 4% concentration boric acid and 10% concentration potassium iodide for 0.5 minutes. Next, after washing by immersing in an aqueous solution containing potassium iodide at 30 ° C. and 1.5% concentration for 10 seconds, it was dried at 50 ° C. for 4 minutes, having a thickness of 25 μm and an iodine content of 2.3% by weight. A polarizer was obtained. An acrylic resin film (transparent protective film (1)) having a thickness of 40 μm was bonded to one surface of the polarizer with a polyvinyl alcohol-based adhesive to produce a polarizing film. Hereinafter, this is referred to as a polarizing film (4). The iodine content of the polarizing film (4) was 2.3% by weight.

Production Example 5 (Production of Polarizing Film (5))
After peeling off the amorphous PET substrate in Production Example 1, a norbornene-based film (transparent protective film (2)) having a thickness of 25 μm was bonded to the other surface with a polyvinyl alcohol-based adhesive to obtain a polarizing film. Produced. Hereinafter, this is referred to as a thin polarizing film (5). The iodine content of the polarizing film (5) was 5.1% by weight.

Production Example 6 (Production of Polarizing Film (6))
A 40 μm thick acrylic resin film (transparent protective film (1)) and a 25 μm thick norbornene film (transparent protective film (transparent protective film (1)) are formed on both sides of a polarizer having an iodine content of 2.3% by weight obtained in Production Example 4. 2)) was bonded with a polyvinyl alcohol adhesive to produce a polarizing film. Hereinafter, this is referred to as a polarizing film (6). The iodine content of the polarizing film (6) was 2.3% by weight.

Polarizers of the polarizing films (1) to (6) obtained in Production Examples 1 to 6, transparent protective film thickness, total polarizing film thickness, and iodine content (content of iodine and / or iodine ions in the polarizer) Are summarized in Table 1 below.

Production Example 7 (Preparation of a solution containing an acrylic polymer (A-1))
In a reaction vessel equipped with a cooling pipe, a nitrogen introduction pipe, a thermometer and a stirrer, 99 parts of butyl acrylate, 1 part of 4-hydroxybutyl acrylate, and 2,2′-azobisisobutyronitrile (initiator) 1 part of AIBN) was added to 100 parts of monomer (solid content) together with ethyl acetate and reacted at 60 ° C. for 7 hours under a nitrogen gas stream. Thereafter, ethyl acetate was added to the reaction solution to obtain a solution containing an acrylic polymer (A-1) having a weight average molecular weight of 1,600,000 (solid content concentration 30% by weight).

Production Example 8 (Production of solution containing acrylic polymer (A-2))
In a reaction vessel equipped with a cooling pipe, a nitrogen introduction pipe, a thermometer and a stirrer, 99 parts of butyl acrylate, 1 part of 2-hydroxyethyl acrylate, and AIBN as an initiator for 100 parts of monomer (solid content) 1 part was added with ethyl acetate, and it was made to react at 60 degreeC under nitrogen gas stream for 7 hours. Thereafter, ethyl acetate was added to the reaction solution to obtain a solution containing an acrylic polymer (A-2) having a weight average molecular weight of 1,600,000 (solid content concentration 30% by weight).

Production Example 9 (Production of solution containing acrylic polymer (A-3))
To a reaction vessel equipped with a cooling tube, a nitrogen introducing tube, a thermometer and a stirrer, 100 parts of butyl acrylate and, as an initiator, 1 part of AIBN with 100 parts of monomer (solid content) are added together with ethyl acetate. The reaction was carried out at 60 ° C. for 7 hours under a nitrogen gas stream. Thereafter, ethyl acetate was added to the reaction solution to obtain a solution containing an acrylic polymer (A-3) having a weight average molecular weight of 1,600,000 (solid content concentration: 30% by weight).

Production Example 10 (Preparation of solution containing acrylic polymer (A-4))
In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirrer, 98.6 parts of butyl acrylate, 1 part of 4-hydroxybutyl acrylate, 0.4 part of acrylic acid, and AIBN as a monomer (Solid content) 1 part with 100 parts of ethyl acetate was added and reacted at 60 ° C. for 7 hours under a nitrogen gas stream. Thereafter, ethyl acetate was added to the reaction solution to obtain a solution containing an acrylic polymer (A-4) having a weight average molecular weight of 1,600,000 (solid content concentration 30% by weight).

Production Example 11 (Production of Solution Containing Acrylic Polymer (A-5))
In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirring device, 95 parts of butyl acrylate, 1 part of 4-hydroxybutyl acrylate, 4 parts of acrylic acid, and AIBN as a monomer (solid content) One part was added with ethyl acetate to 100 parts, and reacted at 60 ° C. for 7 hours under a nitrogen gas stream. Thereafter, ethyl acetate was added to the reaction solution to obtain a solution containing an acrylic polymer (A-5) having a weight average molecular weight of 150,000 (solid content concentration: 30% by weight).

Production Example 12 (Production of Solution Containing Acrylic Polymer (A-6))
In a reaction vessel equipped with a cooling pipe, a nitrogen introduction pipe, a thermometer and a stirring device, 91 parts of butyl acrylate, 1 part of 2-hydroxyethyl acrylate, 8 parts of acrylic acid, and AIBN as a monomer (solid content) To 100 parts, 0.75 part was added together with ethyl acetate and reacted at 60 ° C. for 9 hours under a nitrogen gas stream. Thereafter, ethyl acetate was added to the reaction solution to obtain a solution containing an acrylic polymer (A-6) having a weight average molecular weight of 1,900,000 (solid content concentration 30% by weight).

Production Example 13 (Production of Solution Containing Acrylic Polymer (A-7))
In a reaction vessel equipped with a cooling pipe, a nitrogen introduction pipe, a thermometer, and a stirring device, 99 parts of butyl acrylate, 1 part of 4-hydroxybutyl acrylate, and AIBN as an initiator for 100 parts of monomer (solid content) 1.5 parts was added with ethyl acetate and reacted at 60 ° C. for 7 hours under a nitrogen gas stream. Thereafter, ethyl acetate was added to the reaction solution to obtain a solution containing an acrylic polymer (A-7) having a weight average molecular weight of 900,000 (solid content concentration: 30% by weight).

Production Example 14 (Production of Solution Containing Acrylic Polymer (A-8))
In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirrer, 84.9 parts of butyl acrylate, 0.1 part of 4-hydroxybutyl acrylate, 5 parts of acrylic acid, 10 parts of benzyl acrylate, and an initiator Then, 1 part of AIBN was added to 100 parts of monomer (solid content) together with ethyl acetate and reacted at 60 ° C. for 7 hours under a nitrogen gas stream. Thereafter, ethyl acetate was added to the reaction solution to obtain a solution containing an acrylic polymer (A-8) having a weight average molecular weight of 1,800,000 (solid content concentration 30% by weight).

Moreover, the weight average molecular weight of the acrylic polymer obtained in Production Examples 7 to 14 was measured by the following measuring method.
<Measurement of weight average molecular weight (Mw) of acrylic polymer>
The weight average molecular weight of the prepared acrylic polymer was measured by GPC (gel permeation chromatography).
Device: HLC-8220GPC, manufactured by Tosoh Corporation
column:
Sample column: TSK guard column Super HZ-H manufactured by Tosoh Corporation
(1) + TSKgel Super HZM-H (2)
Reference column: TSKgel Super H-RC (1) manufactured by Tosoh Corporation
Flow rate: 0.6mL / min
Injection volume: 10 μL
Column temperature: 40 ° C
Eluent: THF
Injection sample concentration: 0.2% by weight
Detector: differential refractometer The weight average molecular weight was calculated in terms of polystyrene.

Example 1
(Adjustment of acrylic adhesive composition)
Trimethylolpropan xylylene diisocyanate (trade name: Takenate D110N) as a cross-linking agent per 100 parts of the solid content of the solution (solid concentration 30% by weight) containing the acrylic polymer (A-1) obtained in Production Example 7 0.1 part of Mitsui Chemicals Co., Ltd.), 0.3 part of dibenzoyl peroxide and 0.3 parts of phosphanol SM-172 (trade name, manufactured by Toho Chemical Industry Co., Ltd.) as a phosphoric acid compound. 0.03 part of γ-glycidoxypropyltrimethoxysilane (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent and 0.075 part of a phenolic antioxidant as a silane coupling agent Erythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (IRGANAOX 1010, ASF manufactured by Japan KK) were blended 0.3 part, to obtain an acrylic pressure-sensitive adhesive composition.

(Preparation of polarizing film with adhesive layer)
The acrylic pressure-sensitive adhesive composition is uniformly applied to the surface of a polyethylene terephthalate film (base material) treated with a silicone-based release agent with a fountain coater, and dried in an air circulation type thermostatic oven at 155 ° C. for 2 minutes. A pressure-sensitive adhesive layer having a thickness of 20 μm was formed on the surface of the substrate. Subsequently, the separator which formed the adhesive layer was transferred to the surface which does not have a protective film of a polarizing film (1), and the polarizing film with an adhesive layer was produced.

Examples 2-5
A polarizing film with a pressure-sensitive adhesive layer was produced in the same manner as in Example 1 except that the addition amount of the phosphoric acid compound was changed from 0.03 part to the number of parts shown in Table 3.

Example 6
Except for changing 0.03 part of Phosphanol SM-172 (trade name, manufactured by Toho Chemical Industry Co., Ltd.) to 0.1 part of Phosphanol RS-410 (manufactured by Toho Chemical Industry Co., Ltd.) In the same manner as in Example 1, a polarizing film with a pressure-sensitive adhesive layer was produced.

Example 7
Except that 0.03 part of Phosphanol SM-172 (trade name, manufactured by Toho Chemical Industry Co., Ltd.) was changed to 0.1 part of Phosphanol RS-710 (manufactured by Toho Chemical Industry Co., Ltd.) In the same manner as in Example 1, a polarizing film with a pressure-sensitive adhesive layer was produced.

Example 8
Except for changing 0.03 part of Phosphanol SM-172 (trade name, manufactured by Toho Chemical Co., Ltd.) to 0.05 part of DBP (manufactured by Johoku Chemical Co., Ltd.), the same as in Example 1. A polarizing film with an adhesive layer was prepared.

Example 9
Except for changing 0.03 part of Phosphanol SM-172 (trade name, manufactured by Toho Chemical Industry Co., Ltd.) to 0.03 part of phosphoric acid (reagent special grade) (manufactured by Wako Pure Chemical Industries, Ltd.), In the same manner as in Example 1, a polarizing film with a pressure-sensitive adhesive layer was produced.

Examples 10-14
Solutions containing the acrylic polymers (A-1) obtained in Production Example 7 and the solutions containing acrylic polymers (A-2) to (A-6) obtained in Production Examples 8 to 12, respectively. A polarizing film with a pressure-sensitive adhesive layer was produced in the same manner as in Example 1, except that the change was made.

Examples 15-17
In the same manner as in Example 1 except that the polarizing film (1) is changed to the polarizing films (2), (3), and (4) in (Preparation of polarizing film with pressure-sensitive adhesive layer) in Example 1, A polarizing film with an agent layer was produced.

Example 18
(Adjustment of acrylic adhesive composition)
Trimethylolpropan xylylene diisocyanate (trade name: Takenate D110N) as a cross-linking agent per 100 parts of the solid content of the solution (solid concentration 30% by weight) containing the acrylic polymer (A-1) obtained in Production Example 7 0.1 part of Mitsui Chemicals Co., Ltd.), 0.3 part of dibenzoyl peroxide and 0.3 parts of phosphanol SM-172 (trade name, manufactured by Toho Chemical Industry Co., Ltd.) as a phosphoric acid compound. 0.03 part of γ-glycidoxypropyltrimethoxysilane (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent, and lithium bistrifluoromethane as an ionic compound Methanesulfonylimide (Morita Chemical Industry Co., Ltd.) 0.5 part, as a phenolic antioxidant, pentaerythritol tetrakis [ - (3,5-di -tert- butyl-4-hydroxyphenyl) propionate (IRGANAOX 1010, manufactured by BASF Japan Ltd.) were blended 0.3 part, to obtain an acrylic pressure-sensitive adhesive composition.

(Preparation of polarizing film with adhesive layer)
A polarizing film with a pressure-sensitive adhesive layer was produced in the same manner as in Example 1 except that the acrylic pressure-sensitive adhesive composition was used.

Example 19
0.5 parts of lithium bistrifluoromethanesulfonylimide (Morita Chemical Co., Ltd.) 0.5 parts of 1-methyl-1-ethylpyrrolidinium bis (trifluoromethanesulfonyl) imide (Kishida Chemical Co., Ltd.) A polarizing film with a pressure-sensitive adhesive layer was produced in the same manner as in Example 18 except for changing to.

Example 20
The solution containing the acrylic polymer (A-1) obtained in Production Example 7 was changed to the acrylate copolymer (A-8) obtained in Production Example 14, and Phosphanol SM- 172 (trade name, manufactured by Toho Chemical Industry Co., Ltd.) 0.03 parts was changed to 0.05 parts of phosphoric acid (special reagent grade) (manufactured by Wako Pure Chemical Industries, Ltd.), as in Example 1. Thus, a polarizing film with an adhesive layer was produced.

Example 21
A polarizing film with a pressure-sensitive adhesive layer was prepared in the same manner as in Example 20, except that the addition amount of phosphoric acid (special grade reagent) (manufactured by Wako Pure Chemical Industries, Ltd.) was changed from 0.05 part to 0.1 part. Produced.

Example 22
Phosphanol SM-172 (trade name, manufactured by Toho Chemical Industry Co., Ltd.) 0.03 part, MP-4 (trade name, acid value: 670 mg KOH / g, manufactured by Daihachi Chemical Industry Co., Ltd.) 0.01 Except having changed into the part, it carried out similarly to Example 1, and produced the polarizing film with an adhesive layer.

Example 23
Except for changing the addition amount of MP-4 (trade name, acid value: 670 mg KOH / g, manufactured by Daihachi Chemical Industry Co., Ltd.) from 0.01 part to 0.06 part, the same as in Example 22, A polarizing film with an adhesive layer was prepared.

Example 24
The solution containing the acrylic polymer (A-1) obtained in Production Example 7 was changed to the acrylate copolymer (A-8) obtained in Production Example 14, and Phosphanol SM- Except for changing 0.03 part of 172 (trade name, manufactured by Toho Chemical Co., Ltd.) to 0.1 part of MP-4 (trade name, acid value: 670 mg KOH / g, manufactured by Daihachi Chemical Industry Co., Ltd.) Produced a polarizing film with an adhesive layer in the same manner as in Example 1.

Examples 25 and 26
Example 24, except that the amount of MP-4 (trade name, acid value: 670 mg KOH / g, manufactured by Daihachi Chemical Industry Co., Ltd.) was changed from 0.1 part to 0.8 part and 3 parts. In the same manner, a polarizing film with a pressure-sensitive adhesive layer was produced.

Example 27
The solution containing the acrylic polymer (A-1) obtained in Production Example 7 was changed to the acrylate copolymer (A-8) obtained in Production Example 14, and Phosphanol SM- 172 (trade name, manufactured by Toho Chemical Industry Co., Ltd.) 0.03 parts, MP-4 (trade name, acid value: 670 mg KOH / g, manufactured by Daihachi Chemical Industry Co., Ltd.) 0.04 parts and phosphoric acid ( A polarizing film with a pressure-sensitive adhesive layer was produced in the same manner as in Example 1, except that the mixture was changed to 0.01 parts of a reagent special grade (Wako Pure Chemical Industries, Ltd.).

Example 28
The solution containing the acrylic polymer (A-1) obtained in Production Example 7 was changed to the acrylate copolymer (A-8) obtained in Production Example 14, and Phosphanol SM- 172 (trade name, manufactured by Toho Chemical Co., Ltd.) 0.03 parts, Phosphanol SM-172
Except for changing to a mixture of 0.04 parts (trade name, manufactured by Toho Chemical Industry Co., Ltd.) and 0.01 parts phosphoric acid (special grade reagent) (manufactured by Wako Pure Chemical Industries, Ltd.), the same as in Example 1 Thus, a polarizing film with an adhesive layer was produced.

Examples 29-34
Polarized light with pressure-sensitive adhesive layer in the same manner as in Example 1 except that the type of solution containing the acrylic polymer and the type and amount added of the phosphoric acid compound were changed to the types and parts shown in Table 3. A film was prepared.

Comparative Example 1
Implementation was performed except that the solution containing the acrylic polymer (A-1) was changed to a solution containing the acrylic polymer (A-2) obtained in Production Example 8, and the phosphate ester was not used. In the same manner as in Example 1, a polarizing film with a pressure-sensitive adhesive layer was produced.

Comparative Example 2
Implementation was performed except that the solution containing the acrylic polymer (A-1) was changed to the solution containing the acrylic polymer (A-3) obtained in Production Example 9 and the phosphate ester was not used. In the same manner as in Example 1, a polarizing film with a pressure-sensitive adhesive layer was produced.

Comparative Example 3
Implementation was performed except that the solution containing the acrylic polymer (A-1) was changed to a solution containing the acrylic polymer (A-5) obtained in Production Example 11 and the phosphate ester was not used. In the same manner as in Example 1, a polarizing film with a pressure-sensitive adhesive layer was produced.

Comparative Example 4
Implementation was performed except that the solution containing the acrylic polymer (A-1) was changed to a solution containing the acrylic polymer (A-7) obtained in Production Example 13 and the phosphate ester was not used. In the same manner as in Example 1, a polarizing film with a pressure-sensitive adhesive layer was produced.

Examples 35 and 36
In the same manner as in Example 1 except that the polarizing film (1) was changed to the polarizing films (5) and (6) in (Preparation of polarizing film with pressure-sensitive adhesive layer) in Example 1, polarized light with pressure-sensitive adhesive layer. A film was prepared. The pressure-sensitive adhesive layer was laminated on the protective film (2) side.

Example 37
A polarizing film with an adhesive layer was prepared in the same manner as in Example 24 except that the polarizing film (1) was changed to the polarizing film (5) in (Preparation of polarizing film with an adhesive layer) in Example 24. . The pressure-sensitive adhesive layer was laminated on the protective film (2) side.

Comparative Example 5
In Example 1 (Adjustment of acrylic pressure-sensitive adhesive composition), a phosphoric acid ester was not used, and in (Preparation of polarizing film with pressure-sensitive adhesive layer), the polarizing film (1) was changed to a polarizing film (5). In the same manner as in Example 1, a polarizing film with a pressure-sensitive adhesive layer was produced. The pressure-sensitive adhesive layer was laminated on the protective film (2) side.

Comparative Example 6
In Example 1 (adjustment of acrylic pressure-sensitive adhesive composition), the solution containing the acrylic polymer (A-1) was changed to a solution containing the acrylic polymer (A-3) obtained in Production Example 9. In the same manner as in Example 1, except that the polarizing film (1) was changed to the polarizing film (6) in (Preparation of polarizing film with pressure-sensitive adhesive layer) without using a phosphate ester. A polarizing film with a layer was produced. The pressure-sensitive adhesive layer was laminated on the protective film (2) side.

The phosphoric acid compounds used in Examples and Comparative Examples were analyzed as follows. The results are shown in Table 2.
(Analysis method)
The composition of the phosphoric acid compound used in Examples and Comparative Examples was calculated based on the measurement results of ³¹ P-NMR (Acetone-d6, room temperature). After calculating mol% from the integrated value of the peak obtained by measurement, the content ratio (% by weight) was calculated from the alkyl chain of the alcohol component of the ester.
⁽³¹ P-NMR measurement conditions)
Measuring apparatus: Bruker Biospin, AVANCE III-400
Observation frequency: 160 MHz ( ³¹ P)
Flip angle: 30 °
Measurement solvent: Acetone-d6 (heavy acetone)
Measurement temperature: room temperature chemical shift standard: P = (OCH ₃ ) ₃ in Acetone-d6 ( ³¹ P; 140 ppm external standard)

In Table 2, the phosphoric acid monoester has 1 to 18 carbon atoms in which ^one of R ¹ and R ^{2 in} the general formula (1) is a hydrogen atom and the other may contain an oxygen atom. It is a compound that is a hydrocarbon residue (in the case of general formula (2), a compound in which R ¹ is a hydrogen atom), and a phosphoric acid diester is a compound in which R ¹ and R ^{2 in} general formula (1) are oxygen atoms A compound having a carbon residue of 1 to 18 carbon atoms (in the case of general formula (2), R ¹ may contain an oxygen atom and a hydrocarbon group having 1 to 18 carbon atoms) Compound that is a residue). For example, in the case of phosphanol SM-172, “monoester” is a compound in which R ¹ = H, R ³ = C ₈ H ₁₇ , and n = 0 in the general formula (2), and “diester” The compound in which R ¹ = R ³ = C ₈ H ₁₇ and n = 0 in (2) is shown.

（評価基準）
◎：抵抗値変化率が、１５０％未満（湿熱による抵抗値の上昇幅小さい（耐腐食性良好））
○：抵抗値変化率が、１５０％以上３００％未満
△：抵抗値変化率が、３００％以上４００％未満
×：抵抗値変化率が、４００％以上（湿熱による抵抗値の上昇幅大きい（耐腐食性不良）） <Corrosion resistance test>
A conductive film (trade name: Electrysta (P400L), manufactured by Nitto Denko Co., Ltd.) with an ITO layer formed on the surface is cut into 15 mm × 15 mm. The sample obtained in the example was cut to 8 mm × 8 mm and bonded together, and then subjected to autoclaving at 50 ° C. and 5 atm for 15 minutes was used as a corrosion resistance measurement sample. The resistance value of the obtained measurement sample was measured using a measuring device described later, and this was set as “initial resistance value”.
Thereafter, the resistance value measured after putting the measurement sample in an environment of temperature 60 ° C. and humidity 90% for 500 hours was defined as “resistance value after wet heat”. In addition, said resistance value was measured using HL5500PC by Accent Optical Technologies. From the “initial resistance value” and “resistance value after wet heat” measured as described above, the resistance value change rate (%) was calculated by the following equation, and evaluated according to the following evaluation criteria.

(Evaluation criteria)
A: Resistance value change rate is less than 150% (small increase in resistance value due to wet heat (corrosion resistance is good))
○: Resistance value change rate is 150% or more and less than 300% Δ: Resistance value change rate is 300% or more and less than 400% ×: Resistance value change rate is 400% or more Corrosive failure))

<Durability test of adhesive (peeling and foaming)>
The separator film of the polarizing film sample with the pressure-sensitive adhesive layer obtained in Examples and Comparative Examples was peeled off and bonded to the ITO surface of the glass on which the alkali-free glass and the following amorphous ITO were formed, 50 ° C., After autoclaving at 5 atm for 15 minutes, it was put into a heating oven at 80 ° C. and 100 ° C. and a constant temperature and humidity chamber at 60 ° C./90% RH and 85 ° C./85% RH. The peeling and foaming of the polarizing film after 500 hours were visually observed and evaluated according to the following evaluation criteria. In addition, the peeling and foaming of the polarizing film after visually applying the environment at 85 ° C. and −40 ° C. for 300 cycles per cycle for 1 hour (heat shock test (HS test)) were visually observed and evaluated according to the following evaluation criteria. .
A: No peeling or foaming was observed.
○: Exfoliation or foaming to the extent that it cannot be visually confirmed was observed.
(Triangle | delta): The small peeling or foaming which can be confirmed visually was recognized.
X: Clear peeling or foaming was observed

(Production method of glass on which amorphous ITO is formed)
An ITO film was formed on one surface of the alkali-free glass by a sputtering method to produce an adherend having an amorphous ITO thin film. The Sn ratio of the crystalline ITO thin film was 3% by weight. The Sn ratio of the ITO thin film was calculated from the weight of Sn atoms / (weight of Sn atoms + weight of In atoms).

Abbreviations in the table are as follows.
(Phosphate compound)
B-1: Phosphanol SM-172, acid value: 219 mg KOH / g, mono-di mixture, manufactured by Toho Chemical Industry Co., Ltd. B-2: phosphanol RS-410, acid value: 105 mg KOH / g, mono- Di-mixture, Toho Chemical Industries B-3: Phosphanol RS-710, acid value: 62 mgKOH / g, Mono-di mixture, Toho Chemical Industries B-4: DBP, acid value: 266 mgKOH / G, mono-di mixture, Johoku Chemical Co., Ltd. B-5: phosphoric acid (special grade reagent), Wako Pure Chemical Industries, Ltd. B-6: MP-4, acid value: 670 mg KOH / g, mono- Dimix, B-8 manufactured by Daihachi Chemical Industry Co., Ltd .: Mono-N-butyl phosphate (O = P (OH) ₂ (OC ₄ H ₉ ), Product Number: CDS001281), manufactured by SIGMA-ALDRICH

(Crosslinking agent)
Peroxide type: dibenzoyl peroxide isocyanate type: trimethylolpropane xylylene diisocyanate (trade name: Takenate D110N) (manufactured by Mitsui Chemicals, Inc.)

(Ionic compound)
E-1: Lithium bistrifluoromethanesulfonylimide (Morita Chemical Co., Ltd.)
E-2: 1-methyl-1-ethylpyrrolidinium bis (trifluoromethanesulfonyl) imide (manufactured by Kishida Chemical Co., Ltd.)

  Moreover, the iodine content in Tables 3 and 5 is the content (% by weight) of iodine and / or iodine ions in the polarizer.

DESCRIPTION OF SYMBOLS 1 Polarizing film 2 Adhesive layer 3 Antistatic layer 4 Glass substrate 5 Liquid crystal layer 6 Drive electrode 7 Antistatic layer and sensor layer 8 Drive electrode and sensor layer 9 Sensor layer

Claims (22)

On at least one surface of an iodine-based polarizing film having a transparent protective film on at least one surface of an iodine-based polarizer containing iodine and / or iodine ions, the following general formula (1):

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom.)
And an acrylic pressure-sensitive adhesive containing one or more phosphoric acid compounds selected from the group consisting of a compound represented by formula (1) and a multimer of compounds represented by the general formula (1), and a (meth) acrylic polymer A polarizing film with a pressure-sensitive adhesive layer, comprising a pressure-sensitive adhesive layer formed from the composition. The content of iodine and / or iodine ion in the iodine-based polarizer is 1 to 14% by weight, The polarizing film with a pressure-sensitive adhesive layer according to claim 1. The content of iodine and / or iodine ions in the iodine-based polarizer is 3 to 12% by weight, The polarizing film with a pressure-sensitive adhesive layer according to claim 2. The phosphoric acid compound contains phosphoric acid, and one of R ¹ and R ^{2 in} the general formula (1) is a hydrogen atom, and the other may contain an oxygen atom. Phosphoric acid monoester which is a hydrocarbon residue of ˜18, and R ¹ and R ² of the general formula (1) are hydrocarbon residues having 1 to 18 carbon atoms which may contain an oxygen atom The polarizing film with a pressure-sensitive adhesive layer according to claim 1, which is a mixture containing one or more phosphates selected from the group consisting of phosphoric acid diesters. The polarizing film with an adhesive layer according to claim 4, wherein the phosphoric acid compound is a mixture containing phosphoric acid and phosphoric acid monoester. The polarized light with pressure-sensitive adhesive layer according to any one of claims 1 to 5, wherein the hydrocarbon residue having 1 to 18 carbon atoms is a linear or branched alkyl group having 1 to 10 carbon atoms. the film. The iodine-based polarizing film is a single-sided protective polarizing film having a transparent protective film only on one side of the iodine-based polarizer, and the surface of the single-sided protective polarizing film that does not have a transparent protective film, and the adhesive The layer is contacting, The polarizing film with an adhesive layer in any one of Claims 1-6 characterized by the above-mentioned. The thickness of the said iodine type polarizer is 10 micrometers or less, The polarizing film with an adhesive layer in any one of Claims 1-7 characterized by the above-mentioned. The total thickness of the said iodine type polarizing film is 80 micrometers or less, The polarizing film with an adhesive layer in any one of Claims 1-8 characterized by the above-mentioned. The pressure-sensitive adhesive layer of the polarizing film with a pressure-sensitive adhesive layer according to any one of claims 1 to 9 and the transparent conductive layer of a member having a transparent conductive layer are bonded together and used. Item 10. The polarizing film with a pressure-sensitive adhesive layer according to any one of Items 1 to 9. The pressure-sensitive adhesive according to any one of claims 1 to 10, wherein the addition amount of the phosphoric acid compound is 0.001 to 4 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer. Layered polarizing film. The polarizing film with an adhesive layer according to any one of claims 1 to 11, wherein the (meth) acrylic polymer contains an alkyl (meth) acrylate and a hydroxyl group-containing monomer as monomer units. The polarizing film with an adhesive layer according to claim 12, wherein the hydroxyl group-containing monomer is 4-hydroxybutyl acrylate. The polarizing film with a pressure-sensitive adhesive layer according to any one of claims 1 to 13, wherein the (meth) acrylic polymer has a weight average molecular weight of 1,200,000 to 3,000,000. The said acrylic adhesive composition contains a crosslinking agent further, The polarizing film with an adhesive layer in any one of Claims 1-14 characterized by the above-mentioned. The polarizing film with a pressure-sensitive adhesive layer according to claim 15, wherein the crosslinking agent is at least one crosslinking agent selected from the group consisting of a peroxide crosslinking agent and an isocyanate crosslinking agent. The polarizing film with a pressure-sensitive adhesive layer according to claim 1, wherein the acrylic pressure-sensitive adhesive composition further contains an ionic compound. The polarizing film with an adhesive layer in any one of Claims 1-17, and the transparent conductive member which has a transparent conductive layer, the adhesive layer of the polarizing film with an adhesive layer, and the transparent conductive layer of the said base material A laminated body characterized by being bonded so as to be in contact with each other. The laminate according to claim 18, wherein the transparent conductive layer is made of indium tin oxide. The laminate according to claim 19, wherein the indium tin oxide is amorphous indium tin oxide. The pressure-sensitive adhesive layer of the polarizing film with a pressure-sensitive adhesive layer according to any one of claims 1 to 17 and the liquid crystal panel having a transparent conductive layer, the pressure-sensitive adhesive layer of the polarizing film with a pressure-sensitive adhesive layer, and the transparency of the liquid crystal panel. An image display device which is bonded so as to be in contact with a conductive layer. An image display device using the laminate according to any one of claims 18 to 20 as a touch panel.

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