TW201504378A - Polarizing film with adhesive layer, laminate, and image display device - Google Patents

Abstract

The present invention provides: a polarizing film with an adhesive layer, said film being characterized by having, on at least one surface of an iodine polarizing film having a transparent protective film on at least one side of an iodine polarizer that contains iodine and/or iodine ions, an adhesive layer formed from an acrylic adhesive composition containing a (meth)acrylic polymer and one or more phosphoric acid compounds selected from the group consisting of a compound represented by general formula (1) (in the formula, R1 and R2 each independently represent a C1-18 hydrocarbon residue which may include a hydrogen atom or an oxygen atom) and multimers of the compound represented by general formula (1); a laminate in which the polarizing film and a substrate having a transparent conductive layer are bonded; an image display device in which the polarizing film and a liquid crystal panel having a transparent conductive layer are bonded; and an image display device that uses the laminate as a touch panel.

Description

Polarizing film, laminated body and image display device with adhesive layer

The present invention relates to a polarizing film with an adhesive layer. Moreover, the present invention relates to a laminate in which the polarizing film of the adhesive layer is bonded to a substrate having a transparent conductive layer, and a polarizing film of the adhesive layer and a liquid crystal panel having a transparent conductive layer. The image display device and the image display device using the above laminated body as a touch panel.

In recent years, transparent conductive films such as indium tin oxide (ITO) films have been widely used in various applications in the industry. For example, it is known that the transparent conductive film is formed on the opposite side of the transparent substrate constituting the liquid crystal cell of the liquid crystal display device using the liquid crystal cell having a liquid crystal cell such as an IPS (In-Plane Switching) method and the side contacting the liquid crystal layer. As an antistatic layer. Further, the transparent conductive film in which the transparent conductive film is formed on the transparent resin film is used for an electrode substrate of a touch panel, and is used for, for example, a liquid crystal display device or an image display in a mobile phone or a portable music player or the like. Input devices used in combination with the touch panel are gradually becoming widespread.

As an input device used in combination with a touch panel and an image display device, a transparent conductive film in which a transparent conductive layer is formed on a transparent substrate including a glass plate or a transparent resin film is previously provided on a liquid crystal display device (liquid crystal) The Out-Cell type of the upper side of the viewing-side polarizing film of the display device is widely used. However, in recent years, it has been known to form an electrode including a transparent conductive film on the glass substrate above the liquid crystal cell (On -Cell type, in-cell type in which the electrode including the transparent conductive film is incorporated into the inside of the liquid crystal cell Various components. Further, 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 recent years, such a liquid crystal display device or an image display device using a transparent conductive film has been strongly demanded for weight reduction and thinning, and the polarizing film used in the liquid crystal display device or the like is also required to be thinner and lighter. . As a method of reducing the thickness and weight of the polarizing film, for example, a method of providing a transparent protective film on one surface of a polarizing element as a single-sided protective polarizing film or a thin polarizing film which thins the film thickness of the polarizing element itself is known. Manufacturing method, etc.

As a method for producing a thin polarizing film, a method for producing an optical film laminate comprising a thin polarizing film of a polyvinyl alcohol-based resin having iodine on a continuous network of an amorphous ester-based thermoplastic resin substrate is known. (For example, refer to Patent Documents 1 and 2).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 4751881

[Patent Document 2] 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 an antistatic layer containing a transparent conductive film is passed through the adhesive layer. The polarizing film is bonded. Further, when a transparent conductive film is used as the electrode of the touch panel, depending on the configuration of the touch panel, a polarizing film with an adhesive layer may be laminated on the transparent conductive film for the electrode, and the adhesive layer may be used. The antistatic layer containing the transparent conductive film is bonded to the polarizing film.

When the polarizing film is an iodine-based polarizing film, the transparent conductive layer is bonded to the iodine-based polarizing film as described above, and when the humidification endurance test (normal durability test) is performed, the resistance value of the transparent conductive layer may be obtained. Will rise. It is known that the above resistance value rises because the polarizer The iodine contained in the article oozes out to the adhesive layer, and the iodine reaches the transparent conductive layer to erode the transparent conductive layer.

For example, in the thin iodine-based polarizing element having a thickness of 10 μm or less as described in Patent Documents 1 and 2, it is known that the iodine concentration in the polarizing element must be increased in order to have the same polarizing characteristics as the conventional polarizing element. When the polarizing film of the higher polarizing element is bonded to the transparent conductive layer, iodine corrosion of the transparent conductive layer is liable to occur. Further, when a single-sided iodine-based polarizing film is used, it is known that the transparent conductive layer is directly bonded to the iodine-based polarizing element via the adhesive layer, and corrosion of the transparent conductive layer is also likely to occur.

Therefore, an object of the present invention is to provide a polarizing film with an adhesive layer which suppresses corrosion of the transparent conductive layer even when laminated on a transparent conductive layer, and can suppress surface resistance of the transparent conductive layer. rise. Moreover, an object of the present invention is to provide a laminate in which the polarizing film with the adhesive layer is bonded to a substrate having a transparent conductive layer, and a polarizing film of the adhesive layer and a transparent conductive layer. An image display device in which a liquid crystal panel is bonded, and an image display device using the laminated body as a touch panel.

The present inventors have made an effort to solve the above problems, and as a result, it has been found that the above-mentioned adhesive layer formed of an acrylic pressure-sensitive adhesive composition containing a phosphoric acid compound and a (meth)acrylic polymer can be used. The purpose is to complete the present invention.

In other words, the present invention relates to a polarizing film with an adhesive layer, characterized in that at least one surface of the iodine-based polarizing film having at least one surface of the iodine-based polarizing element containing iodine and/or iodide ions has a transparent protective film. An adhesive layer formed of an acrylic pressure-sensitive adhesive composition containing a phosphoric acid compound and a (meth)acrylic polymer, wherein the phosphate compound is selected from the following formula (1):

(wherein 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)

One or more of the group consisting of the compound represented by the compound represented by the above formula (1) and the polymer represented by the above formula (1). Here, the "iodine-based polarizing element containing iodine and/or iodide ion" means an iodine-based polarizing element containing iodine, an iodine-based polarizing element containing iodide ions, and an iodine-based polarizing element containing both iodine and iodine ions. In the present invention, either one may be suitably used.

The content of iodine and/or iodide ions in the iodine-based polarizing element may be 1 to 14% by weight or 3 to 12% by weight.

Preferably, the phosphoric acid-based compound contains phosphoric acid and contains a hydrocarbon selected from the group consisting of R ¹ and R ² of the formula (1) as a hydrogen atom and the other one having a carbon number of 1 to 18 which may contain an oxygen atom. The phosphate monoester of the residue and R ¹ and R ² of the formula (1) are at least ^one phosphate group of a group consisting of phosphodiesters having a hydrocarbon residue having 1 to 18 carbon atoms of an oxygen atom. mixture.

Preferably, the phosphoric acid compound contains a mixture of phosphoric acid and a phosphoric acid monoester. Further, the total amount of the phosphoric acid and the phosphoric acid monoester is preferably 80% by weight or more based on 100% by weight of the phosphoric acid compound.

Preferably, the hydrocarbon residue having 1 to 18 carbon atoms is a linear or branched alkyl group having 1 to 10 carbon atoms.

Preferably, the iodine-based polarizing film has a single-sided protective polarizing film having a transparent protective film on one side of the iodine-based polarizing element, and the adhesive layer is in surface contact with the one-side protective polarizing film without a transparent protective film. .

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

It is preferable that the total thickness of the iodine-based polarizing film is 80 μm or less.

Further, it is preferable to use the adhesive layer of the polarizing film with the adhesive layer in contact with the transparent conductive layer of the substrate having the transparent conductive layer.

The amount of the phosphoric acid compound added is preferably 0.001 to 4 parts by weight based on 100 parts by weight of the (meth)acrylic polymer.

It is preferred that the (meth)acrylic polymer contains a (meth)acrylic acid alkyl ester and a hydroxyl group-containing monomer as a monomer unit.

Preferably, the hydroxyl group-containing monomer is 4-hydroxybutyl acrylate.

Preferably, the (meth)acrylic polymer has a weight average molecular weight of from 1.2 million to 3,000,000.

It is preferable that the acrylic pressure-sensitive adhesive composition further contains a crosslinking agent, and more preferably the crosslinking agent is one or more types selected from the group consisting of a peroxide crosslinking agent and an isocyanate crosslinking agent. Agent.

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

Furthermore, the present invention relates to a laminate in which the polarizing film of the adhesive layer and the transparent conductive member having a transparent conductive layer are adhered to the polarizing film of the adhesive layer and the member. The transparent conductive layer is bonded in such a manner as to be in contact.

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

Further, the present invention relates to an image display device characterized in that an adhesive layer of a polarizing film of the adhesive layer and an adhesive layer of a polarizing film of the above-mentioned adhesive layer are provided on a liquid crystal panel having a transparent conductive layer. The bonding is performed in contact with the transparent conductive layer of the liquid crystal panel.

Further, the present invention relates to an image display device characterized by using the above laminated body as a touch panel.

In the polarizing film with an adhesive layer of the present invention, although an iodine-based polarizing element is used, even when a transparent conductive layer is laminated on the adhesive layer of the polarizing film of the adhesive layer, corrosion of the transparent conductive layer is suppressed. The surface resistance of the transparent conductive layer can be suppressed from rising. The reason for this is that the adhesive layer of the polarizing film with the adhesive layer of the present invention contains a phosphate compound. Specifically, it is considered that, for example, when the phosphoric acid compound contains phosphoric acid, a passive film is formed on the surface of the transparent conductive layer from metal ions in phosphoric acid and the transparent conductive layer, and as a result, iodine in the polarizing element is obtained. It does not transfer to the surface of the transparent conductive layer, but prevents corrosion of the transparent conductive layer. Further, it is considered that when the phosphoric acid compound is a phosphoric acid compound (for example, a phosphate ester or the like), the phosphoric acid compound is selectively adsorbed on the surface of the transparent conductive layer to form a film. As a result, in the polarizing element Iodine is not transferred to the surface of the transparent conductive layer, and corrosion of the transparent conductive layer is prevented.

1‧‧‧ polarizing film

2‧‧‧Adhesive layer

3‧‧‧Antistatic layer

4‧‧‧ glass substrate

5‧‧‧Liquid layer

6‧‧‧Drive electrode

7‧‧ ‧ double as the sensing layer of the antistatic layer

8‧‧‧Also as the sensing layer of the drive electrode

9‧‧‧Sensor layer

Fig. 1 is a cross-sectional view schematically showing an embodiment of an image display device of the present invention.

Fig. 2 is a cross-sectional view schematically showing an embodiment of an image display device of the present invention.

Fig. 3 is a cross-sectional view schematically showing an embodiment of an image display device of the present invention.

1. Polarized film with adhesive layer

The polarizing film with an adhesive layer of the present invention is characterized in that at least one surface of the iodine-based polarizing film having a transparent protective film on at least one side of the iodine-based polarizing element containing iodine and/or iodide ions has a phosphate-containing compound. And an adhesive layer formed of the acrylic pressure-sensitive adhesive composition of the (meth)acrylic polymer, wherein the phosphate compound is selected from the following formula (1):

(wherein 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)

One or more of the group consisting of the compound represented by the compound represented by the above formula (1) and the polymer represented by the above formula (1).

(1) iodine-based polarizing film

The iodine-based polarizing film used in the present invention is a one having a transparent protective film on at least one side of an iodine-based polarizing element containing iodine and/or iodide ions. In the present invention, the one-side protective polarizing film having a transparent protective film on one side of the iodine-based polarizing element may be a double-sided protective polarizing film having a transparent protective film on both sides of the iodine-based polarizing element, and is used. When the single side protects the polarized light, the effect of the present invention is remarkable. Further, even in the case where the thickness of the transparent protective film on the side in contact with the adhesive layer is thin (for example, 25 μm or less) in the double-sided protective polarizing film, the effect of the present invention is remarkable. Further, in the case where the polarizing film is a single-sided protective polarizing film, the adhesive layer may be directly provided on the surface of the polarizing element which does not have the side of the transparent protective film.

As the iodine-based polarizing element, any polarizing element containing iodine and/or iodide ions may be used. For example, iodine may be adsorbed on a polyvinyl alcohol (PVA, polyvinyl alcohol) film or a partially formalized PVA. A film or a hydrophilic polymer film such as an ethylene-vinyl acetate copolymer-based partially saponified film is uniaxially stretched. Among these, a polarizing element containing a PVA film and iodine is preferable. The thickness of the polarizing element is not particularly limited, but is usually about 5 to 80 μm.

A polarizing element obtained by dyeing a PVA film with iodine and uniaxially stretching, for example, It was produced by immersing PVA in an aqueous solution of iodine for dyeing, and extending it to 3 to 7 times the original length. If necessary, it may be immersed in an aqueous solution of potassium iodide or the like which may contain boric acid, zinc sulfate or zinc chloride. Further, if necessary, the PVA film may be immersed in water and washed with water before dyeing. By washing the PVA film with water, the dirt or the anti-blocking agent on the surface of the PVA film can be washed, and the PVA film can be swollen to prevent unevenness in dyeing unevenness. The extension may be carried out after dyeing with iodine, or may be extended while dyeing, or may be dyed with iodine after stretching. It can also be extended in an aqueous solution or a water bath such as boric acid or potassium iodide.

Further, in the present invention, a thin iodine-based polarizing element having a thickness of 10 μm or less can be suitably used. From the viewpoint of thinning, the thickness is preferably from 1 to 7 μm. Such a thin iodine-based polarizing element is excellent in visibility because of the small thickness unevenness, and is excellent in durability due to a small dimensional change, and further preferably has a thickness as a polarizing film in order to reduce the thickness.

Typical examples of the thin polarizing element include Japanese Patent Laid-Open No. 51-069644, Japanese Patent Laid-Open No. 2000-338329, International Publication No. 2010/100917, and International Publication No. 2010/100917. A thin polarizing film described in Japanese Patent No. 4751481 or Japanese Patent Laid-Open Publication No. 2012-073563. These thin polarizing films can be obtained by a production method including a step of stretching the PVA-based resin layer and the extending resin substrate in a state of being laminated, and a step of dyeing. According to this production method, even if the PVA-based resin layer is thin, it can be extended by a resin substrate for extension and without problems such as breakage due to elongation.

In the manufacturing method including the step of extending in the state of the laminated body and the step of dyeing, the thin polarizing film can be extended to a high magnification to improve the polarizing performance, and is preferably disclosed by, for example, international disclosure. Manual No. 2010/100917, International Publication No. 2010/100917, or Japanese Patent No. 4751481 or Japanese Patent Special The production method including the step of performing the step of stretching in an aqueous solution of boric acid described in Japanese Patent Publication No. 2012-073563 is preferably included in the specification of Japanese Patent No. 4751481 or Japanese Patent Laid-Open No. 2012-073563. A method of producing a step of assisting in the air extension step before stretching in an aqueous solution of boric acid.

Further, the content of iodine and/or iodide ion (hereinafter sometimes referred to as iodine content) of the iodine-based polarizing element used in the present invention may be 1 to 14% by weight or 3 to 12% by weight in the polarizing element. % can also be 4 to 7.5% by weight. In the polarizing film with an adhesive layer of the present invention, even if the iodine content in the iodine-based polarizing element is as large as the above range, the surface resistance of the transparent conductive layer laminated on the polarizing film of the adhesive layer can be suppressed from increasing. The reason for this is that a film is formed on the surface of the transparent conductive layer by the phosphoric acid compound contained in the adhesive layer. Therefore, iodine contained in the iodine-based polarizing film is not transferred to the surface of the transparent conductive layer. As a result, Prevent corrosion of the transparent conductive layer. Specifically, when the phosphoric acid compound contains phosphoric acid, the phosphoric acid forms a passive film on the surface of the transparent conductive layer and the metal ion in the transparent conductive layer, and the phosphate compound contains a phosphate compound (for example, a phosphate ester). In this case, the phosphoric acid compound is selectively adsorbed on the surface of the transparent conductive layer to form a film.

As a material for forming the transparent protective film provided on one surface or both surfaces of the iodine-based polarizing element, it is preferably excellent in transparency, mechanical strength, thermal stability, moisture barrier property, and isotropic property. For example, a polyester-based polymer such as polyethylene terephthalate or polyethylene naphthalate, a cellulose-based polymer such as diethyl phthalocyanine or triethylene fluorene cellulose, or polymethyl methacrylate may be mentioned. An acrylic polymer such as an ester, a styrene polymer such as polystyrene or an acrylonitrile-styrene copolymer (AS resin), or a polycarbonate polymer. Further, examples of the polymer forming the transparent protective film include polyethylene, polypropylene, and a ring system or a descending layer. a polyolefin polymer such as an olefin structure or a polyolefin polymer such as an ethylene-propylene copolymer; a vinyl chloride polymer; a guanamine polymer such as nylon or an aromatic polyamine; a ruthenium-based polymer; a polyether fluorene-based polymer, a polyetheretherketone polymer, a polyphenylene sulfide polymer, a vinyl alcohol polymer, a vinylidene chloride polymer, an ethylene butyral polymer, an aryl ester polymer, A polyoxymethylene polymer, an epoxy polymer or a blend of the above polymers. The transparent protective film may be formed as a hardened layer of a thermosetting type or an ultraviolet curable resin such as an acrylic type, an urethane type, an acrylamide type, an epoxy type or a polyoxymethylene type.

The thickness of the protective film can be appropriately determined, and is usually about 1 to 500 μm in terms of workability and film properties such as strength and workability.

The iodine-based polarizing element and the transparent protective film are usually adhered to 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, an ethylene-based latex, an aqueous polyurethane, and an aqueous polyester. In addition to the above, examples of the adhesive for the polarizing element and the transparent protective film include an ultraviolet curable adhesive, an electron beam curable adhesive, and the like. The adhesive for an electron beam curing type polarizing film exhibits an appropriate adhesion to the above various transparent protective films. Further, the binder used in the present invention may contain a metal compound filler.

The surface of the transparent protective film which is not followed by the iodine-based polarizing element may be subjected to a hard coat layer or an anti-reflection treatment, an anti-adhesive treatment, or a treatment for the purpose of diffusion or anti-glare.

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, still more preferably 60 μm or less, in order to meet the requirements for thinning of the polarizing film with an adhesive layer. The lower limit of the total thickness of the polarizing film is not particularly limited, and examples thereof include 10 μm.

(2) Adhesive layer

The adhesive layer used in the polarizing film of the adhesive layer of the present invention is formed of an acrylic adhesive composition. The acrylic adhesive composition contains a compound selected from the following formula (1): [Chemical 3]

(wherein 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)

A phosphate compound and a (meth)acrylic polymer in a group consisting of the compound represented by the compound represented by the above formula (1) and the polymer represented by the above formula (1).

Examples of the phosphoric acid-based compound include phosphoric acid, a phosphate ester, or a salt, a dimer or a trimer thereof. Hereinafter, the details will be described.

In the formula (1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon residue having 1 to 18 carbon atoms which may include an oxygen atom. Examples of the hydrocarbon residue having 1 to 18 carbon atoms which may include an oxygen atom include an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, and -(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 an integer of 0 to 15). Further, the alkyl group and the alkenyl group may be linear or branched. Among these, the hydrocarbon residue of 1 to 18 carbon atoms is preferably a linear or branched alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 18 carbon atoms, more preferably a carbon number. A linear or branched alkyl group of 2 to 6.

In the present invention, phosphoric acid (H ₃ PO ₄ ) in which both R ¹ and R ² of the formula (1) are hydrogen atoms can be suitably used. Further, a salt of the above phosphoric acid (a salt of a metal such as sodium, potassium or magnesium, or an ammonium salt) may be suitably used.

Further, in the present invention, the compound represented by the formula (1) is preferably an acid phosphate. Here, the acidic phosphate means that both R ¹ and R ² in the formula (1) are hydrocarbon residues having 1 to 18 carbon atoms which may contain an oxygen atom (diester), or R ¹ and R ^{2 .} When any of them is a hydrogen atom and the other is a hydrocarbon residue having a carbon number of 1 to 18 which may contain an oxygen atom (monoester), for example, the following formula (2): [Chemical 4]

(wherein R ¹ is the same as above, and 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 an integer of 0 to 15)

The phosphate compound represented.

R is the same general formula (2) R ¹ of the general formula (1) of ^1, a hydrogen atom or an oxygen atom may include the carbon number of the hydrocarbon residue of 1 to 18. The hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom may be the same as described above. R ^{1 of the} 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, more preferably a hydrogen atom or a carbon number of 1~ A linear or branched alkyl group of 10 is further preferably a hydrogen atom or a linear or branched alkyl group having 2 to 6 carbon atoms. Examples of R ³ include an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms, preferably an alkyl group having 1 to 18 carbon atoms and a carbon number of 6 to 18. The aryl group is more preferably an alkyl group having 1 to 10 carbon atoms, and further preferably an alkyl group having 2 to 6 carbon atoms. Further, n is an integer of 0 to 15, preferably an integer of 0 to 10. Further, in the present invention, from the viewpoint of resistance to deterioration, it is preferred that the polyethylene oxide structure (CH ₂ CH ₂ O) is not contained (that is, n = 0 in the formula (2)).

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

Further, in the present invention, two or more compounds represented by the formula (2) may be used in combination, and a mixture of the compound represented by the formula (2) and the above phosphoric acid may be used. Further, in general, the phosphate compound represented by the formula (2) is in many cases It is preferably obtained in the form of a mixture of a monoester and a diester, and is preferably added to the above mixture of the monoester and the diester.

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

As a commercial item of the phosphate ester compound represented by the above-mentioned general formula (2), "Phosphanol SM-172" manufactured by Toho Chemical Industry Co., Ltd. (R ¹ = R ³ = C of the general formula (2)) ₈ H ₁₇ , n=0, monoester-diester mixture, acid value: 219 mgKOH/g), "Phosphanol GF-185" (R ¹ = R ³ = C ₁₃ H _{27 of the} formula (2), n = 0 , monoester-diester mixture, acid value: 158 mgKOH/g), "Phosphanol BH-650" (R ¹ = R ³ = C ₄ H ₉ , n = 1, monoester-diester mixture of the formula (2) Acid value: 388 mgKOH/g), "Phosphanol RS-410" (R ¹ = R ³ = C ₁₃ H _{27 of the} formula (2), n = 4, a monoester-diester mixture, and an acid value: 105 mgKOH/g ), "Phosphanol RS-610" (R ¹ = C ₁₃ H _{27 of the} formula (2), R ³ = C ₁₃ H ₂₇ , n = 6, a monoester-diester mixture, an acid value: 82 mgKOH/g), "Phosphanol RS-710" (R ¹ = C ₁₃ H _{27 of the} formula (2), R ³ = C ₁₃ H ₂₇ , n = 10, a monoester-diester mixture, an acid value: 62 mgKOH/g), "Phosphanol"ML-220" (R ¹ = R ³ = C ₁₂ H _{25 of the} formula (2), n = 2, a monoester-diester mixture), "Phosphanol ML-200" (R ¹ = of the formula (2) _{^{R 3 = C 12 H 25,}} n = 0, mono - diester mixture), Phosphanol ED-200 "(the general formula (2) of _{^{R 1 = R 3 = C 8}} H 17, n = 1, monoesters - diester mixture)," Phosphanol RL-210 "(the general formula (2) of R ¹ =R ³ =C ₁₈ H ₃₇ , n=2, monoester-diester mixture), "Phosphanol GF-339 (mixture of R ¹ =R ³ =C ₆ H ₁₃ ~C ₁₀ H ₂₁ of formula (2) , n = 0, a monoester-diester mixture), "Phosphanol GF-199" (R ¹ = R ³ = C ₁₂ H ₂₅ , n = 0, a monoester-diester mixture of the formula (2)), Phosphanol RL-310" (R ¹ = R ³ = C ₁₈ H ₃₇ , n = 3, monoester-diester mixture of the formula (2)), "Phosphanol LP-700" (R ^{1 of the} formula (2) =R ³ =C ₆ H ₅ , n=6, monoester-diester mixture), "AP-1" manufactured by Daeba Chemical Industry Co., Ltd. (R ¹ = R ³ = CH _{3 of the} general formula (2) , n = 0, monoester-diester mixture, acid value: 650 mgKOH/g or more), "AP-4" (R ¹ = R ³ = C ₄ H ₉ , n = 0, monoester of the formula (2) - Diester mixture, acid value: 452 mgKOH/g), "DP-4" (R ¹ = R ³ = C ₄ H _{9 of the} formula (2), n = 0, a monoester-diester mixture, an acid value: 292 mgKOH/g), "MP-4" (R ¹ = H of the formula (2), R ³ = C ₄ H ₉ , n = 0, a monoester-diester mixture, an acid value: 670 mgKOH/g), AP-8 (R formula (2) of _{^{1 = R 3 = C 8 H}} 17, n = 0, mono - di-ester mixtures, acid value: 306mgKOH / g), "AP-10" R (formula (2) of ¹ = R ³ = C ₁₀ H ₂₁ , n = 0, monoester-diester mixture, acid value: 263 mg KOH/g), "MP-10" (R ¹ = H of the formula (2), R ³ = C ₁₀ H ₂₁ , n = 0, monoester-diester mixture, acid value: 400 mg KOH/g), "JP-508" manufactured by Seongbuk Chemical Co., Ltd. (R ¹ = R ³ = C _{8 of the} general formula (2) H ₁₇ , n = 0, monoester-diester mixture, acid value: 288 mg KOH / g), "JP-513" (R ¹ = R ³ = C ₁₃ H _{27 of the} formula (2), n = 0, single Ester-diester mixture), "JP-524R" (R ¹ = R ³ = C ₂₄ H _{49 of} formula (2), n = 0, monoester-diester mixture), "DBP" (formula (2) R ¹ = R ³ = C ₄ H ₉ , n = 0, monoester-diester mixture, acid value: 266 mg KOH/g), "LB-58" (R ¹ = R ³ = in the formula (2) C ₈ H ₁₇ , n = 0, diester, acid value: 173 mg KOH / g), "Nikkol DDP-2" manufactured by Nikko Chemical Co., Ltd. (R ¹ = R ³ = C ₁₂ H of the general formula (2) ₂₅ ~ C ₁₅ H ₃₁ mixture, n = 2), SIGMA-ALDRICH made of mono-n-butyl phosphate (O = P (OH) ₂ (OC ₄ H ₉ ), general formula (2) R ¹ = H, R ³ =C ₄ H ₉ , n=0, product No.: CDS001281, monoester), and the like. In addition, the above-mentioned "monoester-diester mixture" means a monoester (R ¹ = H of the formula (2)) and a diester (R ^{1 of the} formula (2) = a carbon number which may contain an oxygen atom 1 A mixture of hydrocarbon residues of ~18, for example, in the case of Phosphanol SM-172, means a monoester (R ¹ = H, R ³ = C ₈ H ₁₇ , n = 0 of the formula (2)) and A mixture of esters (R ¹ = R ³ = C ₈ H ₁₇ , n = 0) of the formula (2). The mixing ratio of the monoester to the diester of the above "monoester-diester mixture" can be calculated from the measurement result of ³¹ P-NMR. The measurement method is as described in the examples.

The phosphate-based compound used in the present invention is selected from the group consisting of a compound represented by the formula (1) (or a compound represented by the formula (2)) or a compound of the salt or polymer. One type may be used alone or two or more types may be used in combination, and it is considered from the viewpoint of the adsorption effect of the adherend (especially the adherend having a metal or a metal oxide or a layer containing a metal or a metal oxide). Preferably, it is a mixture of two or more selected from the group consisting of phosphoric acid, a phosphoric acid monoester, and a phosphoric acid diester, more preferably one containing phosphoric acid and one selected from the group consisting of a phosphoric acid monoester and a phosphoric acid diester. A mixture of the above phosphates is particularly preferably a mixture comprising a phosphoric acid monoester and phosphoric acid. In the present invention, one selected from the group consisting of phosphoric acid, a phosphoric acid monoester, and a phosphoric acid diester may be used alone. However, when phosphoric acid is used alone, the pot life of the adhesive composition may be insufficient. Further, since phosphoric acid is a compound having a very high polarity and the compatibility with the acrylic polymer is insufficient, phosphoric acid bleeds out to the surface of the pressure-sensitive adhesive layer, and as a result, there is a problem in terms of durability. Further, if only phosphoric acid ester (phosphoric acid monoester and/or phosphoric acid diester) is used without using phosphoric acid, there is a problem in durability (for example, a heat cycle test) under very severe conditions. In the present invention, it is preferable to use a phosphoric acid compound containing phosphoric acid and a phosphoric acid monoester from the viewpoint of the suppression of corrosion of the transparent conductive layer and the balance of durability under very severe conditions. Further, the total amount of the phosphoric acid and the phosphoric acid monoester is not particularly limited, but is preferably 80% by weight or more based on 100% by weight of the phosphoric acid compound. Here, the phosphoric acid monoester refers to a compound in which either one of R ¹ and R ² in the formula (1) is a hydrogen atom and the other is a hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom ( In the case of the formula (2), the compound wherein R ¹ is a hydrogen atom), the term "phosphoric acid diester" means that R ¹ and R ² of the formula (1) are hydrocarbons having 1 to 18 carbon atoms which may contain an oxygen atom. The compound of the residue (in the case of the formula (2), R ¹ is a compound which may contain a hydrocarbon residue having 1 to 18 carbon atoms of an oxygen atom).

Regarding the adsorption effect on the above-mentioned adherends (especially metals or metal oxides), it is considered that the adherend surface and the phosphate-based compound are defined by the HSAB rule (Hard and Soft Acids and bases, soft and hard acid-base rule), that is, In the "hard and soft acid-base rule", the adsorption effect is high by combining a hard base in a hard acid and combining a soft base in a soft acid, and as a result, it is considered that a high anti-deterioration effect is obtained. That is, for example, ITO In conforms to the HSAB rule The hard acid is defined, and the phosphate compound is a soft base from the hard base in the order of phosphoric acid, a phosphoric acid monoester, and a phosphodiester, so that it can be efficiently adsorbed on ITO in the above-described order, and as a result, it is considered that a higher resistance is obtained. Deterioration effect.

Further, in the case of using a mixture of a monoester body and a diester body, it is preferred to contain a mixture of a plurality of monoester bodies. The mixing ratio (weight ratio) of the mixture of the monoester body and the diester body is preferably a monoester body: a diester body = 6:4 to 9:1, more preferably 7:3 to 9:1. For the above reasons, it is preferred that the adsorption effect on the adherend is high by including a large amount of the monoester body.

Further, as described above, in the present invention, it is preferred to further add phosphoric acid to a phosphate ester compound (especially a phosphoric acid monoester), and in this case, the amount of phosphoric acid added is compared with 100 parts by weight of the phosphate ester compound. It is preferably 10 to 400 parts by weight, more preferably 10 to 100 parts by weight, and is preferably 10 to 50 parts by weight from the viewpoint of the adsorption effect on the adherend. Further, from the viewpoint of durability under very severe conditions, the amount of phosphoric acid added is preferably 10 to 100 parts by weight, more preferably 10 to 50 parts by weight, per 100 parts by weight of the phosphate ester compound.

Further, the acid value of the phosphoric acid compound used in the present invention is preferably 900 mgKOH/g or less, more preferably 50 to 800 mgKOH/g, and more preferably 10 to 700 mgKOH/g. Further, the acid value of the phosphoric acid compound is preferably 400 mgKOH/g or less, more preferably 50 to 400 mgKOH/g, still more preferably 50 to 350 mgKOH/g, and particularly preferably 100, from the viewpoint of operability in production. ~300mgKOH/g. The phosphoric acid compound may function as a reaction catalyst for the crosslinking reaction depending on the type of the crosslinking agent (for example, an isocyanate crosslinking agent), and in this case, the application period is short when it is used as an adhesive. . By setting the acid value of the phosphoric acid compound to the above range, the action as a reaction catalyst can be suppressed, and therefore, it is preferable from the viewpoint of the pot life of the adhesive. Further, from the viewpoint of efficiently exhibiting an effect, it is preferred to add a phosphoric acid compound having an acid value within the above range in the following addition amount.

In addition, examples of the polymer of the compound represented by the above formula (1) include a dimer and a trimer of the compound represented by the above formula (1).

The amount of the phosphoric acid compound added is preferably 0.001 to 4 parts by weight, more preferably 0.001 to 3 parts by weight, still more preferably 0.001 to 2 parts by weight, per 100 parts by weight of the following (meth)acrylic polymer. It is preferably 0.005 to 1 part by weight, more preferably 0.01 to 1 part by weight, still more preferably 0.02 to 0.2 part by weight. When the amount of the phosphoric acid-based compound added is in the above range, the increase in the surface resistance value of the transparent conductive layer can be suppressed, and the durability against heating and humidification can be improved, which is preferable. Further, in the present invention, a phosphoric acid compound such as phosphoric acid or a phosphate ester may be used in combination as described above, and in this case, it may be added in such a manner that the total amount is within the above range.

In the present invention, by forming a polarizing film having an adhesive layer of an adhesive layer formed of an acrylic adhesive composition containing the above-described phosphoric acid compound, even an adhesive layer layer of a polarizing film with an adhesive layer is formed. The transparent conductive layer can also suppress the surface resistance of the transparent conductive layer from rising. The reason is considered to be that when the phosphoric acid compound contains phosphoric acid, the phosphoric acid forms a passive film on the surface of the transparent conductive layer and the metal ions in the transparent conductive layer, and the iodine in the polarizing element is not transferred to the transparent conductive layer. As a result, the corrosion of the transparent conductive layer is prevented, and it is considered that the phosphoric acid compound selectively adsorbs to the transparent conductive layer when the phosphoric acid compound contains a phosphoric acid compound (for example, a phosphate ester or the like). The surface is formed into a film, so that iodine in the polarizing element is not transferred to the surface of the transparent conductive layer, and as a result, corrosion of the transparent conductive layer is prevented.

With regard to the corrosion mentioned herein, in the case of metal oxides, corrosion is caused by a mechanism different from the corrosion of commonly known metals. In the case of a metal oxide such as ITO, iodine from the polarizing element penetrates into the metal oxide layer to lower the carrier mobility of the metal oxide, so that an increase in the resistance value occurs.

The present invention can exhibit a corrosion-inhibiting effect excellent in corrosion of a metal oxide as described above, and in particular, can exert a better effect on a transparent conductive layer containing a metal oxide. By.

The (meth)acrylic polymer to be used in the present invention is not particularly limited. For example, it is preferred to obtain a monomer component containing an alkyl (meth)acrylate, and it is preferred to contain it. The monomer of the alkyl acrylate and the hydroxyl group-containing monomer is obtained by polymerization. Further, the alkyl (meth)acrylate means an alkyl acrylate and/or an alkyl methacrylate, and has the same meaning as the (meth) of the present invention.

As the alkyl group of the alkyl (meth)acrylate, various alkyl groups in a linear or branched form can be used. Specific examples of the alkyl (meth)acrylate include, for example, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, and (meth)acrylic acid. Dibutyl ester, tert-butyl (meth)acrylate, n-amyl (meth)acrylate, isopentyl (methaacrylate), isoamyl (meth)acrylate (isoamyl) Metha)acrylate), n-hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-decyl (meth)acrylate , isodecyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, isomyristyl (meth) acrylate, N-tridecyl (meth)acrylate, tetradecyl (meth)acrylate, stearyl (meth)acrylate, octadecyl (meth)acrylate, or (meth)acrylic acid Dialkyl esters and the like. These may be used singly or in combination. Among these, an alkyl (meth)acrylate having an alkyl group having 4 to 18 carbon atoms is preferred, and a (meth) acrylate having an alkyl group having 4 to 10 carbon atoms is more preferred, and further preferably. It is n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and particularly preferably n-butyl (meth)acrylate.

The alkyl (meth)acrylate is preferably 50 parts by weight or more, preferably 60 parts by weight or more, and more preferably 70 parts by weight, based on 100 parts by weight of the monomer component forming the (meth)acrylic polymer. The above is further preferably 80 parts by weight or more, and particularly preferably 90 parts by weight or more.

Further, as the hydroxyl group-containing monomer, (meth)acryl oxime may be used without particular limitation. A polymerizable functional group having an unsaturated double bond such as a vinyl group or a vinyl group and having a hydroxyl group. Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and (meth)acrylic acid 6-. Hydroxyhexyl ester, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, (meth)acrylic acid (4-hydroxymethylcyclohexyl) The methyl ester or the like may be used alone or in combination of two or more. Among these, 4-hydroxybutyl acrylate is preferred. Further, when an isocyanate crosslinking agent is used as the crosslinking agent described below, by using 4-hydroxybutyl acrylate as a hydroxyl group-containing monomer, the isocyanate group of the isocyanate crosslinking agent can be efficiently ensured. The cross-linking point is therefore preferred.

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

The monomer component of the (meth)acrylic polymer used in the formation of the present invention may contain the alkyl (meth)acrylate having an alkyl group having 4 to 18 carbon atoms, and any of the above-mentioned hydroxyl group-containing monomers. In addition to the monomers, a carboxyl group-containing monomer, an aryl group-containing monomer, and other copolymerized monomers may be used as the monomer component.

As the carboxyl group-containing monomer, a polymerizable functional group having an unsaturated double bond such as a (meth) acrylonitrile 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, and fumaric acid. Butenoic acid, etc., these may be used singly or in combination.

The monomer having a carboxyl group is preferably 10 parts by weight or less, more preferably 8 parts by weight or less, more preferably 8 parts by weight or less, based on 100 parts by weight of the monomer component of the (meth)acrylic polymer. The amount of the layer to be affected 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, a (meth) acrylonitrile group or a group may be used without particular limitation. A vinyl group or the like having a polymerizable functional group of an unsaturated double bond and having an aryl group. Examples of the aryl group-containing monomer include aryl (meth)acrylate such as phenyl (meth)acrylate or benzyl (meth)acrylate.

The ratio of the aryl group-containing monomer is preferably 30 parts by weight or less, more preferably 1 to 20 parts by weight, even more preferably 5 parts by weight based on 100 parts by weight of the monomer component forming the (meth)acrylic polymer. ~15 parts by weight.

The other copolymerizable monomer is not particularly limited as long as it is a polymerizable functional group having an unsaturated double bond such as a (meth) acrylonitrile group or a vinyl group, and examples thereof include cyclohexyl (meth)acrylate. ,(Methacrylate Ester, (meth)acrylic acid a (meth) acrylate cyclic hydrocarbon ester such as an ester; a vinyl ester such as vinyl acetate or vinyl propionate; a styrene monomer such as styrene; for example, glycidyl (meth)acrylate, (methyl) An epoxy group-containing monomer such as methyl glycidyl acrylate; an alkoxy group-containing monomer such as methoxyethyl (meth)acrylate or ethoxyethyl (meth)acrylate; for example, acrylonitrile a cyano group-containing monomer such as methacrylonitrile; a functional monomer such as 2-methylpropenyloxyethyl isocyanate; an olefin such as ethylene, propylene, isoprene, butadiene or isobutylene; A monomer; for example, a vinyl ether monomer such as vinyl ether; a halogen atom-containing monomer such as vinyl chloride or the like.

Further, examples of the copolymerizable monomer include N-cyclohexylmethyleneimine, N-isopropyl maleimide, N-lauryl maleimide, and N-lauryl maleimide. a maleimide-based monomer such as N-phenyl maleimide; for example, N-methyl Ikonide, N-ethyl Ikonide, N-butyl Itacon醯iamine, N-octyl ikyl imine, N-2-ethylhexyl ketimine, N-cyclohexyl ketimine, N-lauryl ketoimine, etc. Imine monomer; for example, N-(meth) propylene oxymethylene succinimide, N-(methyl) propylene fluorenyl-6-oxyhexamethylene succinimide, N- An amber quinone imine monomer such as (meth)acryloyl-8-oxy octamethylene succinimide; for example, styrenesulfonic acid, allylsulfonic acid, 2-(methyl) acrylamide- A sulfonic acid group-containing monomer such as 2-methylpropanesulfonic acid, (meth)acrylamide, propanesulfonic acid, sulfopropyl (meth)acrylate, or (meth)acryloxynaphthalenesulfonic acid.

Further, examples of the copolymerizable monomer include polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxy ethylene glycol (meth) acrylate, and methoxy polymerization. a diol-based acrylate monomer such as propylene glycol (meth) acrylate; and, for example, an acrylate-based monomer containing a heterocyclic ring or a halogen atom, such as tetrahydrofurfuryl (meth) acrylate or fluorine (meth) acrylate; .

Further, as the copolymerizable monomer, a polyfunctional monomer can be used. The polyfunctional monomer may, for example, be a compound having two or more unsaturated double bonds such as a (meth)acryl fluorenyl group or a vinyl group. For example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth)acrylic acid Ester, tetraethylene glycol di(meth)acrylate, etc. (mono or poly)ethylene glycol di(meth)acrylate; propylene glycol di(meth)acrylate or the like (mono or poly)propylene glycol di(methyl) Acrylate or the like (mono or poly) alkanediol di(meth)acrylate; in addition, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, pentaerythritol II Esters of (meth)acrylic acid and polyhydric alcohols such as (meth) acrylate, trimethylolpropane tri(meth) acrylate, pentaerythritol tri(meth) acrylate, dipentaerythritol hexa (meth) acrylate a polyfunctional vinyl compound such as divinylbenzene; a compound having a reactive unsaturated double bond such as allyl (meth) acrylate or vinyl (meth) acrylate. Further, as the polyfunctional monomer, (meth)acryl oxime which is added to two or more functional groups such as a polyester, an epoxy compound or a urethane, and which is the same as the monomer component, may be used. Polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, etc., which are unsaturated double bonds such as a vinyl group or a vinyl group.

The ratio of the other copolymerizable monomer is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, still more preferably 15 parts by weight, per 100 parts by weight of the monomer component forming the (meth)acrylic polymer. In the following, it is particularly preferably 10 parts by weight or less. When the ratio of the above-mentioned copolymerized monomer is too large, the adhesive layer formed of the above-mentioned acrylic pressure-sensitive adhesive composition has a low adhesive property such as a decrease in adhesion between various adherends such as glass, a film, and a transparent conductive layer. After that.

The weight average molecular weight of the (meth)acrylic polymer used in the present invention is preferably in the range of 1.2 million to 3,000,000, more preferably 1.2 million to 2.7 million, and still more preferably 1.2 million to 2.5 million. If the weight average molecular weight is less than 1.2 million, it may be inferior in terms of heat resistance. Further, when the weight average molecular weight is less than 1.2 million, the amount of the low molecular weight component increases in the adhesive composition, and the low molecular weight component may bleed out from the adhesive layer to impair the transparency. Further, the adhesive layer obtained by using a (meth)acrylic polymer having a weight average molecular weight of less than 1.2 million may have poor solvent resistance or mechanical properties. Further, when the weight average molecular weight is more than 3,000,000, it is necessary to dilute the solvent in a large amount in order to adjust the viscosity for coating, which is not preferable from the viewpoint of cost. Further, when the weight average molecular weight is within the above range, it is also preferable from the viewpoint of corrosion resistance and durability. The weight average molecular weight is a value measured by GPC (Gel Permeation Chromatography) and calculated based on polystyrene.

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

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

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

As a polymerization initiator, for example, 2,2'-azobisisobutyronitrile and 2,2'-azo double are mentioned. (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'-dimethylisobutylphosphonium), 2,2'-azobis[N-( Azo-based initiators such as 2-carboxyethyl)-2-methylpropionamidine hydrate (trade name: VA-057, manufactured by Wako Pure Chemical Industries, Ltd.); potassium persulfate, ammonium persulfate, etc. Sulfate; di(2-ethylhexyl) peroxydicarbonate, di(4-tert-butylcyclohexyl) peroxydicarbonate, dibutyl butyl dicarbonate, neodecanoic acid Tributyl ester, third hexyl peroxypivalate, tert-butyl peroxypivalate, dilaurin peroxide, di-n-octyl peroxide, peroxy-2-ethylhexanoic acid 1,1, 3,3-tetramethylbutyl ester, bis(4-methylbenzhydrazide) peroxide, benzamidine peroxide, tert-butyl peroxyisobutyrate, 1,1-di(third hexyl Oxidation) a peroxide-based initiator such as cyclohexane, dibutyl hydroperoxide or hydrogen peroxide; a combination of persulfate and sodium hydrogen sulfite; a combination of peroxide and sodium ascorbate; Oxidizing the reducing agent redox initiator and so forth; but are not limited to such.

The polymerization initiator may be used singly or in combination of two or more kinds thereof, and the total content is preferably 0.005 to 1 part by weight based on 100 parts by weight of the monomer component forming the (meth)acrylic polymer. about.

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 and the like. The chain transfer agent may be used singly or in combination of two or more kinds thereof, and the total content is about 0.1 part by weight or less based on 100 parts by weight of the total of the monomer components.

In the acrylic pressure-sensitive adhesive composition used in the present invention, various decane coupling agents may be added in order to improve the adhesion under high temperature and high humidity conditions. As the decane coupling agent, those having any appropriate functional groups can be used. Examples of the functional group include a vinyl group, an epoxy group, an amine group, a mercapto group, a (meth)acryloxy group, an ethyl oxime group, an isocyanate group, a styryl group, a polythio group, and the like. Specifically, for example, vinyl triethoxy fluorene is exemplified. a vinyl-containing decane coupling agent such as an alkane, a vinyl tripropoxy decane, a vinyl triisopropoxy decane or a vinyl tributoxy decane; γ-glycidoxypropyltrimethoxy decane, γ- Epoxy containing glycidoxypropyltriethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane Base decane coupling agent; γ-aminopropyltrimethoxydecane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxydecane, N-(2-amino B 3-aminopropylmethyldimethoxydecane, γ-triethoxydecyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-γ-aminopropyl An amine group-containing decane coupling agent such as a trimethoxy decane; a decyl group-containing decane coupling agent such as γ-mercaptopropylmethyldimethoxy decane; and a styrene-based decane coupling such as a styryltrimethoxydecane Mixture; γ-acryloxypropyltrimethoxydecane, γ-methylpropenyloxypropyltriethoxydecane, etc. (meth)acrylonitrile-containing decane coupling agent; 3-isocyanate propyl three Isocyanate group such as ethoxy decane Silane coupling agent; bis (triethoxysilylpropyl silicon alkyl) tetrasulfide Silane coupling agent-containing group of the plurality.

The decane coupling agent may be used singly or in combination of two or more kinds thereof, and the total content is preferably 1 part by weight or less based on 100 parts by weight of all the monomer components constituting the (meth)acrylic polymer. More preferably, it is 0.01 to 1 part by weight, further preferably 0.02 to 0.8 part by weight, particularly preferably 0.05 to 0.7 part by weight. When the compounding amount of the decane coupling agent exceeds 1 part by weight, an unreacted coupling agent component is produced, which is not preferable in terms of durability.

Further, when the above decane coupling agent can be copolymerized with the monomer component by radical polymerization, the decane coupling agent can be used as the monomer component. The ratio is preferably 0.005 to 0.7 parts by weight based on 100 parts by weight of all the monomer components constituting the (meth)acrylic polymer.

Further, since the crosslinking agent is added to the acrylic pressure-sensitive adhesive composition used in the present invention, the cohesive force with respect to the durability of the pressure-sensitive adhesive can be imparted, which is preferable.

As the crosslinking agent, a polyfunctional compound is used, and examples thereof include an organic crosslinking agent or a polyfunctional metal chelate compound. Examples of the organic crosslinking agent include an epoxy crosslinking agent, an isocyanate crosslinking agent, a carbodiimide crosslinking agent, and an imide crosslinking agent. An oxazoline crosslinking agent, an aziridine crosslinking agent, a peroxide crosslinking agent, and the like. Polyfunctional metal chelates are those in which a polyvalent metal atom is covalently bonded or coordinated to an organic compound. Examples of the polyvalent metal atom include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, Ti, and the like. . Examples of the atom in the organic compound which is a covalent bond or a coordinate bond include an oxygen atom and the like. Examples of the organic compound include an alkyl ester, an alcohol compound, a carboxylic acid compound, an ether compound, and a ketone compound. These crosslinking agents may be used alone or in combination of two or more. Among these, a peroxide-based crosslinking agent and an isocyanate-based crosslinking agent are preferable, and it is more preferable to use them in combination.

The isocyanate-based crosslinking agent is a compound having two or more isocyanate groups (including an isocyanate-regenerating functional group that temporarily protects an isocyanate group by a block agent or a quantitative amount) in one molecule.

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

More specifically, examples thereof include lower aliphatic polyisocyanates such as butyl diisocyanate and hexamethylene diisocyanate; and alicyclic groups such as cyclopentyl diisocyanate, cyclohexadiisocyanate and isophorone diisocyanate; Isocyanates; aromatic diisocyanates such as 2,4-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, benzodimethyl diisocyanate, polymethylene polyphenyl isocyanate; trimethylolpropane /Toluene diisocyanate trimer adduct (trade name: Coronate L, manufactured by Japan Polyurethane Industry Co., Ltd.), trimethylolpropane / hexamethylene diisocyanate trimer adduct ( Trade name: Coronate HL, manufactured by Japan Polyurethane Industry Co., Ltd., isocyanurate body of hexamethylene diisocyanate (trade name: Coronate HX, Japan Polyurethane Industry (shares) Manufactured) isocyanate adduct; trimethylolpropane adduct of benzyl diisocyanate (trade name: D110N, manufactured by Mitsui Chemicals Co., Ltd.), hexamethylene diisocyanate Ester trimethylolpropane adduct (trade name: D160N, manufactured by Mitsui Chemicals Co., Ltd.); polyether polyisocyanate, polyester polyisocyanate, and these adducts with various polyols, isocyanuric acid A polyfunctional polyisocyanate such as an ester bond, a biuret bond or an allophanate bond. Among these, in terms of a faster reaction rate, it is preferred to use an aliphatic isocyanate.

As the peroxide-based crosslinking agent, various peroxides are used. Examples of the peroxide include di(2-ethylhexyl) peroxydicarbonate, di(4-tert-butylcyclohexyl)peroxydicarbonate, and dibutyl butyl peroxydicarbonate. Oxidized neodecanoic acid tert-butyl ester, peroxidic pivalic acid trihexyl ester, peroxidic pivalic acid tert-butyl ester, dilaurin peroxide, di-n-octyl peroxide, isobutyric acid peroxide 1,1 ,3,3-tetramethylbutyl ester, 1,1,3,3-tetramethylbutyl peroxy 2-ethylhexanoate, bis(4-methylbenzhydryl) peroxide, diphenyl peroxide Formamidine, third butyl peroxybutyrate, and the like. Among these, in particular, di(4-tert-butylcyclohexyl)peroxydicarbonate, permanganese peroxide, and dibenzoyl peroxide can be preferably used, which are excellent in cross-linking reaction efficiency.

The blending ratio of the crosslinking agent in the acrylic pressure-sensitive adhesive composition is not particularly limited, and usually 10 parts by weight of the crosslinking agent (solid content) based on 100 parts by weight of the above (meth)acrylic polymer (solid content). The ratio is adjusted to the ratio below. The compounding ratio of the above crosslinking agent is preferably from 0.01 to 10 parts by weight, more preferably from about 0.01 to about 5 parts by weight. Further, in particular, when a peroxide-based crosslinking agent is used, it is preferably 0.05 to 1 part by weight, more preferably 0.06 to 100 parts by weight of the (meth)acrylic polymer (solid content). 0.5 parts by weight.

Further, by adding an ionic compound to the acrylic pressure-sensitive adhesive composition used in the present invention, it is preferable from the viewpoint of antistatic property of the film during the step 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 of an alkali metal and an inorganic salt can be used. In addition, the "organic cation-anion salt" as used in the present invention means an organic salt and a cationic portion thereof. In the case of an organic substance, the anion portion may be an organic substance or an inorganic substance. "Organic cation-anion salts" are also known as ionic liquids and ionic solids.

<alkali metal salt>

Examples of the alkali metal ion constituting the cation portion of the alkali metal salt include ions of lithium, sodium, and potassium. Among these alkali metal ions, lithium ions are preferred.

The anion portion of the alkali metal salt may be composed of an organic substance or an inorganic substance. As the anion portion constituting the organic salt, for example, CH ₃ COO ^- , CF ₃ COO ^- , CH ₃ SO ₃ ^- , CF ₃ SO ₃ ^- , (CF ₃ SO ₂ ) ₃ C ^- , 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 formula (4) )~(7), (4): (C _n F _2n+1 SO ₂ ) ₂ N ^- (where n is an integer from 1 to 10), and (5): CF ₂ (C _m F _2m SO ₂ ) ₂ N ^- (where m is an integer from 1 to 10), (6): ^- O ₃ S(CF ₂ ) _l SO ₃ ^- (where l is an integer from 1 to 10), (7): (C _p F _2p+1 SO ₂ )N ^- (C _q F _2q+1 SO ₂ ) (where p and q are integers from 1 to 10)

The person indicated, etc. In particular, in terms of obtaining an ionic compound having a preferred ion dissociation property, an anion portion containing a fluorine atom can be preferably used. As the anion portion constituting the inorganic salt, Cl ^- , Br ^- , I ^- , AlCl ₄ ^- , Al ₂ Cl ₇ ^- , BF ₄ ^- , PF ₆ ^- , ClO ₄ ^- , NO ₃ ^- , AsF ₆ ^- , SbF _{6 are used.} ^- , NbF ₆ ^- , TaF ₆ ^- , (CN) ₂ N ^-, etc. The anion moiety is preferably (CF ₃ SO ₂ ) ₂ N ^- , (C ₂ F ₅ SO ₂ ) ₂ N ^- or the like (perfluoroalkylsulfonyl) quinone imine represented by the above formula (4). Particularly preferred is (trifluoromethanesulfonyl) quinone imine represented by (CF ₃ SO ₂ ) ₂ N ^- .

Specific examples of the organic salt of an alkali metal include sodium acetate, sodium alginate, sodium lignosulfonate, sodium toluenesulfonate, lithium hexafluorophosphate (LiPF ₆ ), LiCF ₃ SO ₃ , and 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, etc., 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, etc., more preferably 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, etc., such as lithium hexafluorophosphate (LiPF ₆ ), bis(trifluoromethanesulfonyl) fluorene Lithium imide (LiTFSI, Li(CF ₃ SO ₂ ) ₂ N).

Further, examples of the inorganic salt of an alkali metal include lithium perchlorate and lithium iodide.

<Organic cation-anion salt>

The organic cation-anion salt used in the present invention is composed of a cationic component and an anionic component, and the cationic component is an organic substance. Specific examples of the cationic component include a pyridinium cation, a piperidinium cation, a pyrrolidinium cation, a cation having a pyrroline skeleton, a cation having a pyrrole skeleton, an imidazolium cation, a tetrahydropyrimidinium cation, and dihydrogen. Pyrimidine cation, pyrazolium cation, pyrazolinium cation, tetraalkylammonium cation, trialkyl phosphonium cation, tetraalkyl phosphonium cation, and the like.

As the anion component, for example, Cl ^- , Br ^- , I ^- , AlCl ₄ ^- , Al ₂ Cl ₇ ^- , BF ₄ ^- , PF ₆ ^- , ClO ₄ ^- , NO ₃ ^- , CH ₃ COO ^- , CF ₃ COO ^{- are used.} , 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 formula (4)~(7 ), (4): (C _n F _2n+1 SO ₂ ) ₂ N ^- (where n is an integer from 1 to 10), (5): CF ₂ (C _m F _2m SO ₂ ) ₂ N ^- (where , m is an integer from 1 to 10), (6): ^- O ₃ S(CF ₂ ) _l SO ₃ ^- (where l is an integer from 1 to 10), (7): (C _p F _2p+1 SO ₂ ) N ^- (C _q F _2q+1 SO ₂ ) (where p and q are integers from 1 to 10)

The person indicated, etc. Among these, an anion component containing a fluorine atom can be preferably used in terms of obtaining an ionic compound having a preferred ion dissociation property.

As a specific example of the organic cation-anion salt, a compound containing a combination of the above cationic component and anionic component can be appropriately selected and used. For example, 1-butylpyridinium tetrafluoroborate, 1-butylpyridinium hexafluorophosphate, 1-butyl-3-methylpyridinium tetrafluoroborate, 1-butyl-3-methyl Pyridinium trifluoromethanesulfonate, 1-butyl-3-methylpyridinium Bis(trifluoromethanesulfonyl) quinone imine, 1-butyl-3-methylpyridinium bis(pentafluoroethanesulfonyl) quinone imine, 1-hexylpyridinium tetrafluoroborate, 2-methyl Base-1-pyrroline tetrafluoroborate, 1-ethyl-2-phenylindole tetrafluoroborate, 1,2-dimethylindole tetrafluoroborate, 1-ethylcarbazole tetrafluoroboric acid Salt, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium trifluoroacetate, 1-ethyl-3-methylimidazolium heptafluorobutyrate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium perfluorobutane Acid salt, 1-ethyl-3-methylimidazolium dicyanamide, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-3-methyl Imidazolium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-3-methylimidazolium tris(trifluoromethanesulfonyl)methide, 1-butyl-3-methylimidazole Tetrafluoroborate, 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) quinone imine, 1-hexyl-3-methylimidazolium bromide, chlorine 1-hexyl-3-methylimidazolium, 1-hexyl-3-methylimidazolium tetrafluoroborate, 1-hexyl-3-methylimidazolium hexafluorophosphate, 1-hexyl-3-methyl Imidazolium trifluoromethanesulfonate, 1-octyl-3-methylimidazolium tetrafluoroborate, 1-octyl-3-methylimidazolium hexafluorophosphate, 1-hexyl-2,3-di Methylimidazolium tetrafluoroborate, 1,2-dimethyl-3-propylimidazolium bis(trifluoromethanesulfonyl) quinone imine, 1-methylpyrazolium tetrafluoroborate, 3- Methylpyrazolium tetrafluoroborate, tetrahexylammonium bis(trifluoromethanesulfonyl) quinone imine, diallyldimethylammonium tetrafluoroborate, diallyldimethylammonium trifluoride Sulfonate, diallyldimethylammonium bis(trifluoromethanesulfonyl) quinone imine, diallyldimethylammonium bis(pentafluoroethanesulfonyl) quinone imine, N,N- Diethyl-N-methyl-N-(2-methoxyethyl)ammonium tetrafluoroborate, N,N-diethyl-N-methyl-N-(2-methoxyethyl) Ammonium triflate, N,N-diethyl-N-methyl-N-(2-methoxy Ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(pentafluoroethanesulfonyl) Yttrium, glycidyl trimethylammonium triflate, glycidyl trimethylammonium bis(trifluoromethanesulfonyl)pyrene Amine, glycidyl trimethylammonium bis(pentafluoroethanesulfonyl) quinone imine, 1-butylpyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-butyl-3-methyl Pyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-ethyl-3-methylimidazolium (trifluoromethanesulfonyl) trifluoroacetamide, N,N-diethyl- N-methyl-N-(2-methoxyethyl)ammonium (trifluoromethanesulfonyl)trifluoroacetamide, diallyldimethylammonium (trifluoromethanesulfonyl)trifluoroethyl Indoleamine, glycidyl trimethylammonium (trifluoromethanesulfonyl) trifluoroacetamide, N,N-dimethyl-N-ethyl-N-propylammonium bis(trifluoromethanesulfonyl)醯imine, N,N-dimethyl-N-ethyl-N-butylammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-ethyl-N - amyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-ethyl-N-hexyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N, N - dimethyl-N-ethyl-N-heptyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-ethyl-N-decyl ammonium bis(trifluoro Methanesulfonyl) quinone imine, N,N-dimethyl-N,N-dipropylammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-propyl -N-butylammonium bis(trifluoromethanesulfonyl) Imine, N,N-dimethyl-N-propyl-N-pentyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-propyl-N-hexyl Ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-propyl-N-heptyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-di Methyl-N-butyl-N-hexyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-butyl-N-heptyl ammonium bis(trifluoromethanesulfonate)醯imino, N,N-dimethyl-N-pentyl-N-hexyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N,N-dihexyl Ammonium bis(trifluoromethanesulfonyl) quinone imine, trimethylheptyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-diethyl-N-methyl-N-propyl Ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-diethyl-N-methyl-N-pentyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-di Ethyl-N-methyl-N-heptyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-diethyl-N-propyl-N-amyl ammonium bis(trifluoromethanesulfonate Indenylamine, triethylpropylammonium bis(trifluoromethanesulfonyl) quinone imine, triethylammonium bis(trifluoromethanesulfonyl) quinone imine, triethylheptyl Ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dipropyl-N-methyl -N-ethylammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dipropyl-N-methyl-N-pentyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dipropyl-N-butyl-N-hexyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dipropyl-N,N-di Hexyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dibutyl-N-methyl-N-pentyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N- Dibutyl-N-methyl-N-hexyl ammonium bis(trifluoromethanesulfonyl) quinone imine, trioctylmethylammonium bis(trifluoromethanesulfonyl) quinone imine, N-methyl- N-ethyl-N-propyl-N-pentyl ammonium bis(trifluoromethanesulfonyl) quinone imine, 1-butyl-3-methylpyridine-1-fluorene trifluoromethanesulfonate, and the like. As such a commercial item, for example, "CIL-314" (manufactured by Japan Carlit Co., Ltd.), "ILA2-1" (manufactured by Kyoei Chemical Industry Co., Ltd.), or the like can be used.

Further, for example, tetramethylammonium bis(trifluoromethanesulfonyl) quinone imine, trimethylethylammonium bis(trifluoromethanesulfonyl) quinone imine, and trimethylbutylammonium bis ( Trifluoromethanesulfonyl) quinone imine, trimethylammonium bis(trifluoromethanesulfonyl) quinone imine, trimethylheptyl ammonium bis(trifluoromethanesulfonyl) quinone imine, three Methyl octyl ammonium bis(trifluoromethanesulfonyl) quinone imine, tetraethylammonium bis(trifluoromethanesulfonyl) quinone imine, triethyl butyl ammonium bis(trifluoromethanesulfonyl) Yttrium imine, tetrabutylammonium bis(trifluoromethanesulfonyl) ruthenium imine, tetrahexylammonium bis(trifluoromethanesulfonyl) ruthenium, and the like.

Further, for example, 1-dimethylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-ethylpyrrolidinium bis(trifluoromethanesulfonyl)pyrene Amine, 1-methyl-1-propylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-butylpyrrolidinium bis(trifluoromethanesulfonyl)pyrene Amine, 1-methyl-1-pentylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-hexylpyrrolidinium bis(trifluoromethanesulfonyl) quinone , 1-methyl-1-heptylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-propylpyrrolidinium bis(trifluoromethanesulfonyl) quinone , 1-ethyl-1-butylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-pentylpyrrolidinium bis(trifluoromethanesulfonyl) quinone , 1-ethyl-1-hexylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-heptylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1,1-dipropylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-propyl-1-butylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1, 1-dibutylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-propylpiperidinium bis (trifluoromethyl) Sulfhydryl) quinone imine, 1-pentylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1,1-dimethylpiperidinium bis(trifluoromethanesulfonyl)pyrene Amine, 1-methyl-1-ethylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-propylpiperidinium bis(trifluoromethanesulfonyl)pyrene Amine, 1-methyl-1-butylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-pentylpiperidinium bis(trifluoromethanesulfonyl)pyrene Amine, 1-methyl-1-hexylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-heptylpiperidinium bis(trifluoromethanesulfonyl) quinone , 1-ethyl-1-propylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-butylpiperidinium bis(trifluoromethanesulfonyl) quinone , 1-ethyl-1-pentylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-hexylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-heptylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1,1-dipropyl piperidinium bis(trifluoromethanesulfonyl) quinone imine, 1- Propyl-1-butylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1,1-dibutylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1,1- Dimethylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-ethylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1 -propylpyrrole Bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-butylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-pentylpyrrolidine Bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-hexylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-heptylpyrrolidinium Bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-propylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-butylpyrrolidinium Bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-pentylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-hexylpyrrolidinium double (pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-heptylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1,1-dipropylpyrrolidinium bis (five Fluoroethinyl) quinone imine, 1-propyl-1-butylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1,1-dibutylpyrrolidinium bis(pentafluoroethyl) Sulfhydryl) quinone imine, 1-propylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-pentylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1, 1-dimethylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-ethylpiperidinium bis(pentafluoroethyl) Sulfhydryl) quinone imine, 1-methyl-1-propylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-butylpiperidinium bis(pentafluoroethyl) Sulfhydryl) quinone imine, 1-methyl-1-pentylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-hexylpiperidinium bis(pentafluoroethanesulfonate醯基)醯亚 Amine, 1-methyl-1heptylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-propylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine , 1-ethyl-1-heptylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-pentylpiperidinium bis(pentafluoroethanesulfonyl) quinone , 1-ethyl-1-hexylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-heptylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-propyl-1-butylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1,1-dipropyl piperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1, 1-Dibutylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine and the like.

Further, a trimethyl phosphonium cation, a triethyl phosphonium cation, a tributyl phosphonium cation, a trihexyl phosphonium cation, a diethyl methyl phosphonium cation, a dibutyl ethyl hydrazine may be used instead of the cationic component of the above compound. a compound of a cation, a dimethylindenyl cation, a tetramethyl phosphonium cation, a tetraethyl phosphonium cation, a tetrabutyl phosphonium cation, a tetrahexyl phosphonium cation, or the like.

Further, in place of the above bis(trifluoromethanesulfonyl) quinone imine, bis(pentafluorosulfonyl) quinone imine, bis(heptafluoropropanesulfonyl) quinone imine, bis(nonafluorobutane) may be used. Sulfhydryl) imine, trifluoromethanesulfonyl nonafluorobutanesulfonyl imine, heptafluoropropanesulfonyltrifluoromethanesulfonylimine, pentafluoroethanesulfonylnonafluorobutane A compound such as an indole quinone imine, a cyclohexafluoropropane-1,3-bis(sulfonyl) quinone imine anion or the like.

Further, examples of the ionic compound include inorganic salts such as ammonium chloride, aluminum chloride, copper chloride, ferrous chloride, iron chloride, and ammonium sulfate, in addition to the above-mentioned alkali metal salt and organic cation-anion salt. . The plasma compound may be used singly or in combination of plural kinds.

The blending ratio of the ionic compound in the acrylic pressure-sensitive adhesive composition is not particularly limited, and is preferably about 10 parts by weight or less, more preferably about 10 parts by weight or less, based on 100 parts by weight of the (meth)acrylic polymer (solid content). It is 5 parts by weight or less, and more preferably 2 parts by weight or less. Further, the lower limit is not particularly limited, but is preferably 0.01 parts by weight or more.

Further, in the acrylic pressure-sensitive adhesive composition used in the present invention, a viscosity adjusting agent, a peeling adjuster, and a peeling adjuster may be appropriately used without departing from the object of the present invention. Adhesive imparting agent, plasticizer, softener, filler containing glass fiber, glass beads, metal powder, other inorganic powder, pigment, colorant (pigment, dye, etc.), pH adjuster (acid or alkali), Various additives such as antioxidants and ultraviolet absorbers. These additives can also be formulated in the form of a latex.

(3) Polarizing film with adhesive layer

The polarizing film of the pressure-sensitive adhesive layer of the present invention is obtained by forming an adhesive layer formed of the acrylic pressure-sensitive adhesive composition on at least one surface of the iodine-based polarizing film.

The method for forming the pressure-sensitive adhesive layer is not particularly limited, and the acrylic pressure-sensitive adhesive composition may be applied to various substrates, dried by a dryer such as a hot oven, and a solvent or the like may be volatilized to form an adhesive layer. The adhesive layer may be transferred onto the iodine-based polarizing film, or the acrylic pressure-sensitive adhesive composition may be directly applied onto the iodine-based polarizing film to form an adhesive layer.

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

As a method of applying the above substrate or a polarizing film, various methods can be used. Specific examples thereof include a spray coater, roll coating, contact roll coating, gravure coating, reverse coating, roll coating, spray coating, dip coating, and rod type. Coating, knife coating, air knife coating, curtain coating, lip coating, extrusion coating method using a die coater or the like.

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

The thickness of the adhesive layer (after drying) is, for example, preferably from 5 to 100 μm, more preferably from 10 to 60 μm, still more preferably from 12 to 40 μm. When the thickness of the adhesive layer is less than 10 μm, the adhesion to the adherend is deteriorated, and the durability at high temperature, high temperature and high humidity tends to be insufficient. On the other hand, when the thickness of the adhesive layer exceeds 100 μm, an adhesive layer is formed. In the case where the acrylic pressure-sensitive adhesive composition is applied and dried at the time of drying, bubbles are not sufficiently left, or thickness unevenness occurs on the surface of the pressure-sensitive adhesive layer, or the appearance problem tends to be conspicuous.

The constituent material of the release film may, for example, be a resin film such as polyethylene, polypropylene, polyethylene terephthalate or polyester film, or a porous material such as paper, cloth or nonwoven fabric, a mesh, or foaming. A resin film can be preferably used in terms of excellent surface smoothness, such as a sheet, a metal foil, and a suitable thin leaf body such as the laminate.

Examples of the resin film include a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, a vinyl chloride copolymer film, and a polyparaphenylene. A formic acid ethylene glycol film, a polybutylene terephthalate film, a polyurethane film, an ethylene-vinyl acetate copolymer film, or the like.

The thickness of the above release film is usually from 5 to 200 μm, preferably from 5 to 100 μm. The mold release film may be subjected to mold release and antifouling treatment or coating using a polyfluorene-based, fluorine-based, long-chain alkyl-based or fatty acid-amide-based release agent, cerium oxide powder or the like. Antistatic treatment of type, kneading type, vapor deposition type, etc. In particular, by appropriately performing a release treatment such as polyfluorination treatment, long-chain alkyl treatment, or fluorine treatment on the surface of the release film, the peeling property from the adhesive layer can be further improved.

The transparent resin film substrate is not particularly limited, and various resin films having transparency can be used. This resin film is formed by a single film. For example, examples thereof include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, acetate resins, polyether oxime resins, polycarbonate resins, and polyfluorenes. An amine resin, a polyimide resin, a polyolefin resin, a (meth)acrylic resin, a polyvinyl chloride resin, a polyvinylidene chloride resin, a polystyrene resin, a polyvinyl alcohol resin, A polyarylate resin, a polyphenylene sulfide resin, or the like. Among these, a polyester resin, a polyamidene resin, and a polyether oxime resin are particularly preferable.

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

Further, it may have an adhesion-promoting layer between the iodine-based polarizing film and the adhesive layer. The material for forming the adhesion-promoting layer is not particularly limited, and examples thereof include various polymers, sols of metal oxides, cerium sols, and the like. Among these, in particular, polymers can be preferably used. The use form of the above polymer may be any of a solvent-soluble type, a water-dispersible type, and a water-soluble type.

Examples of the polymer include a polyurethane resin, a polyester resin, an acrylic resin, a polyether resin, a cellulose resin, a polyvinyl alcohol resin, and a polyvinylpyrrolidone. Polystyrene resin or the like. Among these, a polyurethane resin, a polyester resin, and an acrylic resin are preferable. Among these resins, a crosslinking agent can be appropriately formulated. These other binder components can be used singly or in combination of two or more kinds depending on the use.

In the case where a water-dispersible material is used to form a tackifying layer, a water-dispersible polymer is used. Examples of the water-dispersible polymer include emulsifying various resins such as polyurethanes and polyesters with an emulsifier, or introducing water-dispersible anionic groups, cationic groups or nonionic groups into the above resins. Self-emulsifying and so on.

Further, the tackifier may contain an antistatic agent. The antistatic agent is not particularly limited as long as it is a material capable of imparting conductivity, and examples thereof include an ionic surfactant, a conductive polymer, a metal oxide, carbon black, and a carbon nanomaterial. It is preferably a conductive polymer, more preferably a water-dispersible conductive polymer.

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.), and examples of the water-dispersible conductive polymer include polythiophene-based conductive materials. Polymer (manufactured by Nagase Chemical Co., Ltd., Denatoron Series).

The amount of the antistatic agent to be added is, for example, 70 parts by weight or less, preferably 50 parts by weight or less, based on 100 parts by weight of the above-mentioned polymer used for the tackifier. In terms of the antistatic effect, it is preferably 10 parts by weight or more, and further preferably 20 parts by weight or more.

Further, in the above-mentioned tackifier, various additives may be blended in order to suppress deterioration of the adhesive layer or the polarizing element which are generated when the adhesive layer is brought into contact with the tackifying coating layer, and in order to impart a function to the tackifying coating layer, Various additives. For example, an antioxidant, an anti-deterioration agent, an ultraviolet absorber, a fluorescent whitening agent, or the like can be added.

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

The method for forming the tackifying layer is not particularly limited, and it can be carried out by a generally known method. Further, when the adhesion promoting layer is formed, the iodine-based polarizing film can be subjected to an activation treatment. The activation treatment can be carried out by various methods such as corona treatment, low pressure UV treatment, plasma treatment, and the like.

The method of forming the adhesive layer on the adhesion-promoting layer on the iodine-based polarizing film is as described above.

Further, in the case where the adhesive layer of the polarizing film with the adhesive layer of the present invention is exposed, the adhesive layer may be protected by a release film (separator) before being used for practical use. As a release film, the above is mentioned. When a release film is used as the substrate in the production of the above adhesive layer, the adhesive layer on the release film is bonded to the iodine-based polarizing film, whereby the release film can be used as a polarizing layer with an adhesive layer. The release film of the adhesive layer of the film can be simplified in steps.

2. Layered body

The laminate of the present invention is characterized in that the polarizing film with the adhesive layer and the transparent conductive layer of the member having the transparent conductive layer and the adhesive film of the polarizing film with the adhesive layer and the member having the transparent conductive layer Contact in a way that is in contact.

The polarizing film with the above adhesive layer can be used as described above.

The member having a transparent conductive layer is not particularly limited, and a known one may be used, and those having a transparent conductive layer on a transparent substrate such as a transparent film or a member having a transparent conductive layer and a liquid crystal cell may be used.

The transparent substrate may be any one having transparency, and examples thereof include a substrate such as a resin film or glass (for example, a sheet-like, film-shaped or plate-shaped substrate), and the like, and particularly preferably a tree. Lipid film. The thickness of the transparent substrate is not particularly limited, but is preferably about 10 to 200 μm, more preferably about 15 to 150 μm.

The material of the resin film is not particularly limited, and various plastic materials having transparency can be cited. For example, examples thereof include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, acetate resins, polyether oxime resins, polycarbonate resins, and polyfluorenes. An amine resin, a polyimide resin, a polyolefin resin, a (meth)acrylic resin, a polyvinyl chloride resin, a polyvinylidene chloride resin, a polystyrene resin, a polyvinyl alcohol resin, A polyarylate resin, a polyphenylene sulfide resin, or the like. Among these, a polyester resin, a polyamidene resin, and a polyether oxime resin are particularly preferable.

Further, the transparent substrate may be subjected to an etching treatment or a primer treatment such as sputtering, corona discharge, flame, ultraviolet ray irradiation, electron beam irradiation, chemical conversion, oxidation, or the like on the surface to enhance the transparent conductive layer provided thereon. Adhesion to the above transparent substrate. Further, before the transparent conductive layer is provided, it is also possible to perform dust removal and purification by solvent washing or ultrasonic cleaning.

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

Further, examples of the ITO include crystalline ITO and amorphous ITO. Crystalline ITO can be obtained by applying a high temperature during sputtering or heating amorphous ITO. The deterioration caused by iodine is remarkably generated on the amorphous ITO. Therefore, the polarizing film of the adhesive layer of the present invention is particularly effective for amorphous 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, still more preferably 12 to 60 nm, and further preferably set to 15 to 45 nm, more preferably 18 to 45 nm, and even more preferably 20 to 30 nm. When the thickness of the transparent conductive layer is less than 7 nm, deterioration of the transparent conductive layer caused by iodine is likely to occur, and the change in the resistance value of the transparent conductive layer tends to increase. On the other hand, in the case of more than 60 nm, the productivity of the transparent conductive layer is lowered, the cost is also increased, and the optical characteristics are also lowered.

The method for forming the transparent conductive layer is not particularly limited, and a conventionally known method can be employed. Specifically, for example, a vacuum deposition method, a sputtering method, or an ion plating method can be exemplified. Further, an appropriate method may be employed depending on the desired film thickness.

The thickness of the substrate having the above transparent conductive layer is, for example, 15 to 200 μm. Further, from the viewpoint of film formation, it is preferably 15 to 150 μm, more preferably 15 to 50 μm. When the substrate having the above transparent conductive layer is used as a resistive film, for example, a thickness of 100 to 200 μm can be mentioned. Further, in the case of being used in the form of a capacitance, for example, a thickness of preferably 15 to 100 μm is preferable, particularly in the case of further thin film formation in recent years, more preferably 15 to 50 μm, and still more preferably 20 to 20 50 μm thickness.

Further, an undercoat layer, an oligomer blocking layer, or the like may be provided between the transparent conductive layer and the transparent substrate as needed.

In addition, as a member having a transparent conductive layer and a liquid crystal cell, the substrate used in an image display device such as a liquid crystal display device, which is a liquid crystal cell including a substrate (for example, a glass substrate) or a liquid crystal layer/substrate, can be used. Those having no 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 of forming a transparent conductive layer on the substrate of the liquid crystal cell is the same as described above.

3. Image display device

The laminated body of the present invention can be preferably used for manufacturing an image display device (liquid crystal display device, organic EL (electroluminescence)) display device including an input device (touch panel or the like), A substrate (member) of a device such as a PDP (plasma display panel) or an electronic device, an input device (such as a touch panel), or a substrate (member) used in the devices, and particularly preferably used For the manufacture of optical substrates for touch panels. Further, it can be used in any manner such as a touch panel such as a resistive film method or a capacitive method.

The laminate of the present invention is subjected to treatment such as cutting, resist printing, etching, silver ink printing, etc., and the obtained transparent conductive film can be used as a substrate (optical member) for an optical element. The substrate for an optical element is not particularly limited as long as it is a substrate having optical characteristics, and examples thereof include an image display device (a liquid crystal display device, an organic EL (electroluminescence) display device, and a PDP (plasma display). A substrate (member) of a device such as a panel or an electronic paper, an input device (such as a touch panel), or a substrate (member) used in the devices.

Moreover, the polarizing film of the adhesive layer of the present invention suppresses the corrosion of the transparent conductive layer even when a transparent conductive layer is laminated on the adhesive layer of the polarizing film of the adhesive layer as described above. The surface resistance of the transparent conductive layer is suppressed from rising. Therefore, as long as the image display device having the adhesive layer having the polarizing film with the adhesive layer in contact with the transparent conductive layer is used, the polarizing film with the adhesive layer of the present invention can be preferably used. For example, the polarizing film with the adhesive layer of the present invention and the liquid crystal panel having the transparent conductive layer are bonded together with the adhesive layer of the polarizing film with the adhesive layer and the transparent conductive layer of the liquid crystal panel. Like a display device.

More specifically, an image display device using a transparent conductive layer as an antistatic layer or an image display device using a transparent conductive layer as an electrode for a touch panel can be cited. Specific examples of the image display device using the transparent conductive layer as the antistatic layer include a polarizing film 1 / an adhesive layer 2 / an antistatic layer 3 / a glass substrate 4 / a liquid crystal as shown in FIG. 1 . An image display device in which the layer 5/drive electrode 6/glass substrate 4/adhesive layer 2/polarizing film 1 is constituted and the antistatic layer 3 and the driving electrode 6 are formed of a transparent conductive layer. As the polarizing film (1, 2) with an adhesive layer on the upper side (viewing side) of the image display device, the polarizing film with the adhesive layer of the present invention can be used. Also, as a transparent conductive layer The image display device for the electrode use of the control panel may, for example, be a polarizing film 1 / an adhesive layer 2 / a sensing layer 7 serving as an antistatic layer / a glass substrate 4 / a liquid crystal layer 5 / a sensing layer serving as a driving electrode 8/glass substrate 4/adhesive layer 2/polarizing film 1 (In-Cell type touch panel, FIG. 2), or polarizing film 1/adhesive layer 2/sense layer 7 which is also used as an antistatic layer Detecting layer 9 / glass substrate 4 / liquid crystal layer 5 / driving electrode 6 / glass substrate 4 / adhesive layer 2 / polarizing film 1 (On-Cell type touch panel, Figure 3) and also as an antistatic layer sensing The layer 7, the sensing layer 9, and the driving electrode 6 are image display devices formed of a transparent conductive layer. As the polarizing film (1, 2) with an adhesive layer on the upper side (viewing side) of the image display device, the polarizing film with the adhesive layer of the present invention can be used.

[Examples]

Hereinafter, the present invention will be described in detail by way of examples, but the invention should not be construed as limited to Further, in each of the examples, the parts and % are based on the weight.

<Iodine content in polarizing element>

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

1) The intensity of the fluorescent X-rays is measured for a plurality of polarizing elements containing a specific amount of potassium iodide, and the relationship between the iodine content and the intensity of the fluorescent X-rays is derived.

2) The fluorescent X-ray of the iodine-based polarizing element having an unknown iodine content is measured, and the amount of iodine is calculated from the numerical value using the above relational expression.

Production Example 1 (Production of Polarizing Film (1))

The laminate was formed by laminating a laminate of a polyvinyl alcohol (PVA, polyvinyl alcohol) layer having a thickness of 9 μm formed on an amorphous PET substrate at an elongation temperature of 130 ° C to form an extended laminate. Next, the extended laminate was immersed in a dyeing liquid containing 0.1 part by weight of iodine and 0.7 part by weight of potassium iodide in 100 parts by weight of water to form a colored layered body. Further, using boric acid water at an extension temperature of 65 ° C, the total stretching ratio is 5.94 times. In this manner, the colored laminate was integrally molded with the amorphous PET substrate to form an optical film laminate including a PVA layer having a thickness of 4 μm. By the above two-stage extension, an optical film laminate comprising a PVA layer having a thickness of 4 μm constituting a highly functional polarizing layer which is a PVA layer of a PVA layer formed on an amorphous PET substrate can be produced. The high-order alignment of the molecules causes the iodine adsorbed by the dye to be aligned in a high direction as a polyiodide complex. Further, a PVA-based adhesive is applied to the surface of the polarizing layer of the optical film laminate, and a 40 μm-thick acrylic resin film (transparent protective film (1)) which is saponified is bonded thereto, and then amorphous PET is immediately applied. The substrate was peeled off to produce a polarizing film having a transparent protective film on one side of the thin iodine-based polarizing element. Hereinafter, this is called a polarizing film (1). The ionic content of the polarizing film (1) was 5.1% by weight.

Production Examples 2 and 3 (production of polarizing film (2), (3))

In the same manner as in Production Example 1, except that the thin iodine-based polarizing element was used, the one side was transparent, except that the dyeing time was changed from 60 seconds to 120 seconds (Production Example 2) and 180 seconds (Production Example 3). The polarizing film of the protective film. 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 dyed in a iodine solution having a speed ratio of different ratios at 30 ° C in a 0.3% concentration for 1 minute and extended to 3 times. Thereafter, it was immersed in an aqueous solution containing boric acid at a concentration of 4% and a 10% strength of potassium iodide at 60 ° C for 0.5 minutes, and was extended until the total stretching ratio was 6 times. Next, it was washed by immersing in an aqueous solution containing potassium iodide at a concentration of 1.5% and a concentration of 1.5% for 10 seconds, and then dried at 50 ° C for 4 minutes to obtain a polarizing element having a thickness of 25 μm and an iodine content of 2.3% by weight. An acrylic resin film (transparent protective film (1)) having a thickness of 40 μm was bonded to one surface of the polarizing element by a polyvinyl alcohol-based adhesive to prepare a polarizing film. Hereinafter, this is called a polarizing film (4). The ionic content of the polarizing film (4) was 2.3% by weight.

Production Example 5 (Production of Polarizing Film (5))

In Production Example 1, after the amorphous PET substrate was peeled off, the thickness of 25 μm was lowered by a polyvinyl alcohol-based adhesive. The olefinic film (transparent protective film (2)) was bonded to the other single side to prepare a polarizing film. Hereinafter, this is referred to as a thin polarizing film (5). The ionic content of the polarizing film (5) was 5.1% by weight.

Production Example 6 (Production of Polarizing Film (6))

An acrylic resin film (transparent protective film (1)) having a thickness of 40 μm and a thickness of 25 μm were lowered by a polyvinyl alcohol-based adhesive. The olefin film (transparent protective film (2)) was bonded to both surfaces of a polarizing element having an iodine content of 2.3% by weight obtained in Production Example 4 to prepare a polarizing film. Hereinafter, this is called a polarizing film (6). The ionic content of the polarizing film (6) was 2.3% by weight.

The polarizing elements (1) to (6) obtained in Production Examples 1 to 6 were collectively classified into a polarizing element, a thickness of a transparent protective film, a total thickness of a polarizing film, and an iodine content (contents of iodine and/or iodide ions in a polarizing element). In Table 1 below.

Production Example 7 (Production of Solution Containing Acrylic Polymer (A-1))

In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirring device, 99 parts of butyl acrylate, 1 part of 4-hydroxybutyl acrylate, and 100 parts of a monomer (solid content) were added together with ethyl acetate. 1 part of 2,2'-azobisisobutyronitrile (AIBN) as a starter was reacted at 60 ° C for 7 hours under a nitrogen stream. Thereafter, ethyl acetate was added to the reaction liquid to obtain an acrylic polymer (A-1) having a weight average molecular weight of 1.6 million. Solution (solids concentration 30% by weight).

Production Example 8 (Production of Solution Containing Acrylic Polymer (A-2))

In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirring device, 99 parts of butyl acrylate, 1 part of 2-hydroxyethyl acrylate, and 100 parts of a monomer (solid content) were added together with ethyl acetate. 1 part of AIBN as a starter was reacted under a nitrogen stream at 60 ° C for 7 hours. Then, ethyl acetate was added to the reaction liquid to obtain a solution (solid content concentration: 30% by weight) containing an acrylic polymer (A-2) having a weight average molecular weight of 1.6 million.

Production Example 9 (Production of Solution Containing Acrylic Polymer (A-3))

In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirring device, 100 parts of butyl acrylate and 100 parts of AIBN as a starter with respect to the monomer (solid content) were added together with ethyl acetate. The reaction was carried out under a nitrogen stream at 60 ° C for 7 hours. Thereafter, ethyl acetate was added to the reaction liquid to obtain a solution (solid content concentration: 30% by weight) containing an acrylic polymer (A-3) having a weight average molecular weight of 1.6 million.

Production Example 10 (Production of Solution Containing Acrylic Polymer (A-4))

In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirring device, 98.6 parts of butyl acrylate, 1 part of 4-hydroxybutyl acrylate, 0.4 parts of acrylic acid, and a monomer (solid form) were added together with ethyl acetate. 1 part of 100 parts of AIBN as a starter was reacted under a nitrogen stream at 60 ° C for 7 hours. Then, ethyl acetate was added to the reaction liquid to obtain a solution (solid content concentration: 30% by weight) containing an acrylic polymer (A-4) having a weight average molecular weight of 1.6 million.

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 a monomer (solid form) were added together with ethyl acetate. 1 part of 100 parts of AIBN as a starter was reacted under a nitrogen stream at 60 ° C for 7 hours. Thereafter, ethyl acetate was added to the reaction liquid. Further, a solution (solid content concentration: 30% by weight) containing an acrylic polymer (A-5) having a weight average molecular weight of 1.55 million was obtained.

Production Example 12 (Production of Solution Containing Acrylic Polymer (A-6))

In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirring device, 91 parts of butyl acrylate, 1 part of 2-hydroxyethyl acrylate, 8 parts of acrylic acid, and a monomer (solid form) were added together with ethyl acetate. 100 parts of 0.75 parts of AIBN as a starter was reacted under a nitrogen stream at 60 ° C for 9 hours. Then, ethyl acetate was added to the reaction liquid to obtain a solution (solid content concentration: 30% by weight) containing an acrylic polymer (A-6) having a weight average molecular weight of 1.9 million.

Production Example 13 (Production of Solution Containing Acrylic Polymer (A-7))

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

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 stirring device, 84.9 parts of butyl acrylate, 0.1 part of 4-hydroxybutyl acrylate, 5 parts of acrylic acid, 10 parts of benzyl acrylate, and the like were added together with ethyl acetate. One part of AIBN as a starter relative to 100 parts of the monomer (solid content) was reacted at 60 ° C for 7 hours under a nitrogen gas stream. Then, ethyl acetate was added to the reaction liquid to obtain a solution (solid content concentration: 30% by weight) containing an acrylic polymer (A-8) having a weight average molecular weight of 1.8 million.

Further, the weight average molecular weight of the acrylic polymer obtained in Production Examples 7 to 14 was measured by the following measurement method.

<Measurement of Weight Average Molecular Weight (Mw) of Acrylic Polymer>

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

Device: manufactured by Dongsuo Company, HLC-8220GPC

Column:

Sample column: manufactured by Dongsuo Co., Ltd., TSKguardcolumn Super HZ-H (1) + TSKgel Super HZM-H (2)

Reference column: manufactured by Dongsuo Co., Ltd., TSKgel Super H-RC (1 root)

Flow rate: 0.6mL/min

Injection volume: 10μL

Column temperature: 40 ° C

Dissolution: THF

Injection sample concentration: 0.2% by weight

Detector: differential refractometer

Further, the weight average molecular weight was calculated in terms of polystyrene.

Example 1

(Preparation of acrylic adhesive composition)

The solid content of the solution containing the acrylic polymer (A-1) (solid content concentration: 30% by weight) obtained in Production Example 7 was formulated as a crosslinking agent of trimethylolpropane phthalic acid per 100 parts. 0.1 parts of bis-isocyanate (trade name: Takenate D110N, manufactured by Mitsui Chemicals Co., Ltd.), 0.3 parts of diphenylguanidinium peroxide, and Phosphanol SM-172 (trade name, manufactured by Toho Chemical Industry Co., Ltd.) as a phosphoric acid compound 0.03 Γ-glycidoxypropyltrimethoxydecane (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) as a decane coupling agent, 0.075 parts, and pentaerythritol tetrakis as a phenolic antioxidant [3- (3,5-Di-t-butyl-4-hydroxyphenyl)propionic acid inner salt (IRGANAOX 1010, manufactured by BASF Japan Co., Ltd.) was 0.3 part, and an acrylic pressure-sensitive adhesive composition was obtained.

(Production of polarizing film with adhesive layer)

The acrylic adhesive composition was uniformly applied onto the surface of a poly(ethylene terephthalate)-treated polyethylene terephthalate film (substrate) by a spray coater, and air was used at 155 ° C. The pressure-sensitive oven was dried for 2 minutes to form an adhesive layer having a thickness of 20 μm on the surface of the substrate. Next, the separator in which the adhesive layer was formed was transferred to the surface of the polarizing film (1) which did not have the protective film, and the polarizing film with the adhesive layer was produced.

Example 2~5

A polarizing film with an adhesive layer was produced in the same manner as in Example 1 except that the amount of the phosphoric acid compound was changed from 0.03 parts to the parts described in Table 3.

Example 6

In the same manner as in Example 1, except that 0.03 parts of Phosphanol SM-172 (trade name, manufactured by Toho Chemical Co., Ltd.) was changed to 0.1 parts of Phosphanol RS-410 (manufactured by Toho Chemical Co., Ltd.). A polarizing film with an adhesive layer.

Example 7

In the same manner as in Example 1, except that 0.03 parts of Phosphanol SM-172 (trade name, manufactured by Toho Chemical Co., Ltd.) was changed to 0.1 parts of Phosphanol RS-710 (manufactured by Toho Chemical Co., Ltd.). A polarizing film with an adhesive layer.

Example 8

An adhesive layer was produced in the same manner as in Example 1 except that 0.03 parts of Phosphanol SM-172 (trade name, manufactured by Toho Chemical Co., Ltd.) was changed to 0.05 parts of DBP (manufactured by Seongbuk Chemical Co., Ltd.). Polarized film.

Example 9

In the same manner as in Example 1, except that 0.03 parts of Phosphanol SM-172 (trade name, manufactured by Toho Chemical Co., Ltd.) was changed to 0.03 parts of phosphoric acid (reagent grade) (manufactured by Wako Pure Chemical Industries, Ltd.). A polarizing film with an adhesive layer is produced in a manner.

Example 10~14

The solution containing the acrylic polymer (A-1) obtained in Production Example 7 was changed separately. A polarizing film with an adhesive layer was produced in the same manner as in Example 1 except that the solutions containing the acrylic polymers (A-2) to (A-6) obtained in Examples 8 to 12 were produced.

Examples 15~17

In the first embodiment (the production of the polarizing film with the adhesive layer), the polarizing film (1) was changed to the polarizing films (2), (3), and (4), and the same as in the first embodiment. In this way, a polarizing film with an adhesive layer is produced.

Example 18

(Preparation of acrylic adhesive composition)

The solid content of the solution containing the acrylic polymer (A-1) (solid content concentration: 30% by weight) obtained in Production Example 7 was formulated as a crosslinking agent of trimethylolpropane phthalic acid per 100 parts. 0.1 parts of bis-isocyanate (trade name: Takenate D110N, manufactured by Mitsui Chemicals Co., Ltd.), 0.3 parts of diphenylguanidinium peroxide, and Phosphanol SM-172 (trade name, manufactured by Toho Chemical Industry Co., Ltd.) as a phosphoric acid compound 0.03 Γ-glycidoxypropyltrimethoxydecane (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) as a decane coupling agent, 0.075 parts, as an ionic compound, bis(trifluoromethanesulfonate) Lithium sulfonate (manufactured by Morita Chemical Industry Co., Ltd.) 0.5 parts, and pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propanoic acid as a phenolic antioxidant Salt (IRGANAOX 1010, manufactured by BASF Japan Co., Ltd.) was 0.3 parts to obtain an acrylic pressure-sensitive adhesive composition.

(Production of polarizing film with adhesive layer)

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

Example 19

Conversion of 0.5 parts of lithium bis(trifluoromethanesulfonyl) phthalimide (manufactured by Morita Chemical Industry Co., Ltd.) to 1-methyl-1-ethylpyrrolidinium bis(trifluoromethanesulfonyl)pyrene A polarizing film with an adhesive layer was produced in the same manner as in Example 18 except that 0.5 part of an amine (manufactured by Kishida Chemical Co., Ltd.) was used.

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, Toho) was used. A polarizing film with an adhesive layer was produced in the same manner as in Example 1 except that 0.05 parts of the phosphoric acid (reagent grade) (manufactured by Wako Pure Chemical Industries, Ltd.) was changed to 0.03 parts.

Example 21

A polarizing film with an adhesive layer was produced in the same manner as in Example 20 except that the amount of phosphoric acid (reagent grade) (manufactured by Wako Pure Chemical Industries, Ltd.) was changed from 0.05 parts to 0.1 parts.

Example 22

0.03 parts of Phosphanol SM-172 (trade name, manufactured by Toho Chemical Industry Co., Ltd.) was changed to 0.01 parts of MP-4 (trade name, acid value: 670 mgKOH/g, manufactured by Daiba Chemical Industry Co., Ltd.), and A polarizing film with an adhesive layer was produced in the same manner as in Example 1.

Example 23

In the same manner as in Example 22, the adhesion was made in the same manner as in Example 22 except that the amount of the MP-4 (trade name, acid value: 670 mg KOH/g, manufactured by Daisaku Chemical Co., Ltd.) was changed from 0.01 part to 0.06 part. a polarizing film of the agent layer.

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-172 (trade name, Toho) was used. In the same manner as in the first embodiment, except that 0.03 parts of the chemical industry (manufactured by the company) was changed to 0.1 part of MP-4 (trade name, acid value: 670 mgKOH/g, manufactured by Daiba Chemical Industry Co., Ltd.). A polarizing film with an adhesive layer.

Examples 25, 26

In the same manner as in Example 24, except that the amount of addition of MP-4 (trade name, acid value: 670 mg KOH/g, manufactured by Daiba Chemical Industry Co., Ltd.) was changed from 0.1 part to 0.8 part and 3 parts. A polarizing film with an adhesive layer is prepared.

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, Toho) was used. 0.03 parts changed to MP-4 (trade name, acid value: 670 mgKOH/g, manufactured by Daiba Chemical Industry Co., Ltd.), 0.04 parts and phosphoric acid (reagent grade) (Wako Pure Chemical Industries Co., Ltd.) A polarizing film with an adhesive layer was produced in the same manner as in Example 1 except that 0.01 part of the mixture was produced.

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, Toho) was used. 0.03 parts of a mixture of 0.04 parts of Phosphanol SM-172 (trade name, manufactured by Toho Chemical Industry Co., Ltd.) and 0.01 parts of phosphoric acid (reagent grade) (manufactured by Wako Pure Chemical Industries, Ltd.) A polarizing film with an adhesive layer was produced in the same manner as in Example 1 except the above.

Examples 29~34

The adhesive was prepared in the same manner as in Example 1 except that the type of the solution containing the acrylic polymer and the type and amount of the phosphoric acid compound were changed to the types and parts described in Table 3. Layer of polarizing film.

Comparative example 1

The solution containing the acrylic polymer (A-1) was changed to the solution containing the acrylic polymer (A-2) obtained in Production Example 8, and the phosphate ester was not used. A polarizing film with an adhesive layer was produced in the same manner.

Comparative example 2

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. A polarizing film with an adhesive layer was produced in the same manner.

Comparative example 3

The solution containing the acrylic polymer (A-1) was changed to the solution containing the acrylic polymer (A-5) obtained in Production Example 11, and the phosphate ester was not used. A polarizing film with an adhesive layer was produced in the same manner.

Comparative example 4

The solution containing the acrylic polymer (A-1) was changed to the solution containing the acrylic polymer (A-7) obtained in Production Example 13, and the phosphate ester was not used, and Example 1 was used. A polarizing film with an adhesive layer was produced in the same manner.

Example 35, 36

In the same manner as in the first embodiment, the polarizing film (1) was changed to the polarizing films (5) and (6) in the first embodiment (the production of the polarizing film with the adhesive layer). A polarizing film of the adhesive layer. Further, an adhesive layer is laminated on the side of the protective film (2).

Example 37

In the same manner as in Example 24, an adhesive layer was produced in the same manner as in Example 24 except that the polarizing film (1) was changed to the polarizing film (5) in Example 24 (manufacture of a polarizing film with an adhesive layer). Polarized film. Further, an adhesive layer is laminated on the side of the protective film (2).

Comparative Example 5

In the first embodiment (preparation of the acrylic pressure-sensitive adhesive composition), the phosphoric acid ester was not used, and the polarizing film (1) was changed to the polarizing film (5) in the production of the polarizing film with the adhesive layer. A polarizing film with an adhesive layer was produced in the same manner as in Example 1 except for the same manner as in Example 1. Further, an adhesive layer is laminated on the side of the protective film (2).

Comparative Example 6

In Example 1 (preparation of acrylic adhesive composition), acrylic acid will be contained. The solution of the 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, and (in the production of the polarizing film with the adhesive layer) A polarizing film with an adhesive layer was produced in the same manner as in Example 1 except that the polarizing film (1) was changed to the polarizing film (6). Further, an adhesive layer is laminated on the side of the protective film (2).

The phosphoric acid compounds used in the examples and the comparative examples were analyzed as follows. The results are shown in Table 2.

(Analytical method)

The composition of the phosphoric acid compound used in the examples and the comparative examples was calculated based on the measurement results of ³¹ P-NMR (Acetone-d6, room temperature). After measuring mol% based on the integrated value of the obtained peak, the content ratio (% by weight) of the alkyl chain of the alcohol component of the ester was calculated.

( ³¹ P-NMR measurement conditions)

Measuring device: Bruker Biospin, AVANCE III-400

Observation frequency: 160MHz ( ³¹ P)

Flip angle: 30°

Determination of solvent: Acetone-d6 (dihydroacetone)

Measuring 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 means that any of R ¹ and R ² in the formula (1) is a hydrogen atom and the other is a hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom. a compound (in the case of the formula (2), a compound in which R ¹ is a hydrogen atom), and a phosphodiester means that R ¹ and R ^{2 in the} formula (1) are carbon atoms 1 to 18 which may contain an oxygen atom. The compound of the hydrocarbon residue (in the case of the formula (2), R ¹ is a compound which may contain a hydrocarbon residue having 1 to 18 carbon atoms of an oxygen atom). For example, in the case of Phosphanol SM-172, "monoester" means a compound of the formula (2) wherein R ¹ = H, R ³ = C ₈ H ₁₇ , n = 0, and "diester" means a formula (2) a compound of R ¹ = R ³ = C ₈ H ₁₇ , n=0.

<Corrosion resistance test>

A conductive film (trade name: Elecrysta (P400L), manufactured by Nitto Denko (share)) having an ITO layer formed on the surface thereof was cut into 15 mm × 15 mm, and the samples obtained in the examples and the comparative examples were cut into 8 mm × 8 mm. After bonding to the center portion of the conductive film, the autoclave was applied at 50 ° C and 5 atm for 15 minutes, and the obtained one was used as a corrosion resistance measurement sample. The resistance value of the obtained sample for measurement was measured using the following measuring apparatus, and this was made into the " initial resistance value."

Thereafter, the sample for measurement was placed in an environment of a temperature of 60 ° C and a humidity of 90% for 500 hours, and then the resistance value was measured, and the obtained one was referred to as "resistance value after moist heat". Further, the above resistance value was measured using HL5500PC manufactured by Accent Optical Technologies. The "initial resistance value" and the "resistance value after wet heat" measured in the above manner were used to calculate the resistance value change rate (%) according to the following formula, and were evaluated according to the following evaluation criteria.

(evaluation benchmark)

◎: The change rate of resistance value is less than 150% (the increase in resistance value caused by damp heat is small (corrosion resistance is good))

○: The resistance value change rate is 150% or more and less than 300%

△: The resistance value change rate is 300% or more and less than 400%

×: The change rate of the resistance value is 400% or more (the increase in the resistance value caused by the damp heat is large (corrosion resistance is poor))

<Adhesion test of adhesive (peeling and foaming)>

The separator of the polarizing film sample with the adhesive layer obtained in the examples and the comparative examples was peeled off, and bonded to the ITO surface of the alkali-free glass and the glass in which the amorphous ITO was formed, and the temperature was 50 ° C and 5 atm. After 15 minutes of autoclave treatment, the mixture was placed in a heating oven at 80 ° C and 100 ° C and a constant temperature and humidity machine 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 it evaluated based on the following evaluation criteria. Further, the peeling and foaming of the polarizing film after 300 cycles per cycle (heat shock test (HS test)) were performed by visual observation at 85 ° C and -40 ° C for one hour. The evaluation was carried out in accordance with the following evaluation criteria.

◎: No peeling or foaming was found at all.

○: Peeling or foaming was found to the extent that it could not be visually confirmed.

△: Small peeling or foaming which was visually confirmed was found.

×: Obvious peeling or blistering was found

(Manufacturing method of glass in which amorphous ITO is formed)

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

The abbreviations in the table are as follows.

(phosphoric acid compound)

B-1: Phosphanol SM-172, acid value: 219 mg KOH/g, monoester-diester mixture, manufactured by Toho Chemical Industry Co., Ltd.

B-2: Phosphanol RS-410, acid value: 105 mg KOH/g, monoester-diester mixture, manufactured by Toho Chemical Industry Co., Ltd.

B-3: Phosphanol RS-710, acid value: 62 mg KOH/g, monoester-diester mixture, manufactured by Toho Chemical Industry Co., Ltd.

B-4: DBP, acid value: 266 mgKOH/g, monoester-diester mixture, manufactured by Chengbei Chemical Co., Ltd.

B-5: Phosphoric acid (reagent grade), Wako Pure Chemical Industries (stock) manufacturing

B-6: MP-4, acid value: 670 mgKOH/g, monoester-diester mixture, Da Ba Chemical Industry Co., Ltd.

B-7: mono-n-butyl phosphate (O=P(OH) ₂ (OC ₄ H ₉ ), product number: CDS001281), manufactured by SIGMA-ALDRICH

(crosslinking agent)

Peroxide: benzoic acid peroxide

Isocyanate type: trimethylolpropane phthalyl diisocyanate (trade name: Takenate D110N) (manufactured by Mitsui Chemicals Co., Ltd.)

(ionic compound)

E-1: lithium bis(trifluoromethanesulfonyl) phthalimide (manufactured by Morita Chemical Industry Co., Ltd.)

E-2: 1-methyl-1-ethylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine (manufactured by Kishida Chemical Co., Ltd.)

Further, the iodine content in Tables 3 and 5 is the content (% by weight) of iodine and/or iodide ions in the polarizing element.

Claims (22)

A polarizing film with an adhesive layer, characterized in that at least one surface of the iodine-based polarizing film having a transparent protective film on at least one side of an iodine-based polarizing element containing iodine and/or iodide ions contains a phosphate compound and An adhesive layer formed of an acrylic pressure-sensitive adhesive composition of a (meth)acrylic polymer selected from the following general formula (1): (wherein R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon residue having a carbon number of 1 to 18 which may include an oxygen atom) and a polymer represented by the compound represented by the above formula (1) One or more of the group consisting of. The polarizing film of the adhesive layer of claim 1, wherein the iodine-based polarizing element has a iodine and/or iodide ion content of 1 to 14% by weight. The polarizing film of the adhesive layer of claim 2, wherein the content of iodine and/or iodide ions in the iodine-based polarizing element is from 3 to 12% by weight. The polarizing film with an adhesive layer according to any one of claims 1 to 3, wherein the phosphate compound is a hydrogen atom and comprises a hydrogen atom selected from the group consisting of R ¹ and R ² of the formula (1). The other one is a phosphoric acid monoester which may contain a hydrocarbon residue having 1 to 18 carbon atoms of an oxygen atom, and R ¹ and R ² of the formula (1) are hydrocarbon residues having 1 to 18 carbon atoms which may contain an oxygen atom. A mixture of one or more phosphates in the group consisting of phosphodiesters. The polarizing film of the adhesive layer of claim 4, wherein the phosphate compound is a mixture comprising phosphoric acid and a phosphoric acid monoester. The polarizing film with an 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 polarizing film with an adhesive layer according to any one of claims 1 to 6, wherein the iodine-based polarizing film is a single-sided protective polarizing film having a transparent protective film on only one side of the iodine-based polarizing element, and the adhesion is the same The agent layer is in contact with the surface of the single-sided protective polarizing film which does not have a transparent protective film. The polarizing film with an adhesive layer according to any one of claims 1 to 7, wherein the iodine-based polarizing element has a thickness of 10 μm or less. The polarizing film with an adhesive layer according to any one of claims 1 to 8, wherein the total thickness of the iodine-based polarizing film is 80 μm or less. The polarizing film with an adhesive layer according to any one of claims 1 to 9, which is an adhesive layer of a polarizing film with an adhesive layer according to any one of claims 1 to 9 and a transparent conductive layer. The transparent conductive layer of the member is used in such a manner as to be bonded. The polarizing film with an adhesive layer according to any one of claims 1 to 10, wherein the amount of the phosphate compound added is 0.001 to 4 parts by weight based on 100 parts by weight of the (meth)acrylic polymer. 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 a monomer unit. The polarizing film of the adhesive layer of claim 12, wherein the hydroxyl group-containing monomer is 4-hydroxybutyl acrylate. The polarizing film with an adhesive layer according to any one of claims 1 to 13, wherein the (meth)acrylic polymer has a weight average molecular weight of from 1.2 million to 3,000,000. The polarizing film with an adhesive layer according to any one of claims 1 to 14, wherein the propylene is The acid-based adhesive composition further contains a crosslinking agent. The polarizing film of the adhesive layer of claim 15, wherein the crosslinking agent is one or more selected from the group consisting of a peroxide crosslinking agent and an isocyanate crosslinking agent. The polarizing film with an adhesive layer according to any one of claims 1 to 16, wherein the acrylic pressure-sensitive adhesive composition further contains an ionic compound. A laminated body characterized in that the polarizing film of the adhesive layer of any one of claims 1 to 17 and the transparent conductive member having a transparent conductive layer are adhered to the polarizing film of the adhesive layer Bonding is performed in contact with the transparent conductive layer of the above substrate. The laminate of claim 18, wherein the transparent conductive layer is formed of indium tin oxide. The laminate according to claim 19, wherein the indium tin oxide is amorphous indium tin oxide. An image display device characterized in that the adhesive layer of the polarizing film with the adhesive layer of any one of claims 1 to 17 and the liquid crystal panel having the transparent conductive layer are polarized with the above adhesive layer The adhesive layer is bonded to the transparent conductive layer of the liquid crystal panel. An image display device using the laminate according to any one of claims 18 to 20 as a touch panel.