KR20160027012A - Polarizing film with adhesive layer, laminate, and image display device - Google Patents

Abstract

(식 중, R¹ 및 R² 는, 각각 독립적으로, 수소 원자, 또는 산소 원자를 포함하고 있어도 되는, 탄소수 1 ∼ 18 의 탄화수소 잔기를 나타낸다.) 로 나타내는 화합물, 및 상기 일반식 (1) 로 나타내는 화합물의 다량체로 이루어지는 군에서 선택되는 1 종 이상의 인산계 화합물, 및 (메트)아크릴계 폴리머를 함유하는 아크릴계 점착제 조성물로 형성되는 점착제층을 갖는 것을 특징으로 하는 점착제층이 형성된 편광 필름, 상기 편광 필름과 투명 도전층을 갖는 기재를 첩합한 적층체, 상기 편광 필름과 투명 도전층을 갖는 액정 패널을 첩합한 화상 표시 장치, 상기 적층체를 터치 패널로서 사용하는 화상 표시 장치이다.The present invention relates to an iodine-based polarizing film having iodine and / or iodine ion-containing iodine polarizer and at least one side of the iodine-based polarizer having a transparent protective film on at least one side thereof,

(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), and a compound represented by the general formula (1) And a pressure-sensitive adhesive layer formed of an acrylic pressure-sensitive adhesive composition containing a (meth) acryl-based polymer, at least one phosphoric acid compound selected from the group consisting of a polarizer And a transparent conductive layer, a liquid crystal panel having the polarizing film and the transparent conductive layer, and an image display apparatus using the laminate as a touch panel.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a polarizing film, a laminate, and an image display device having a pressure-

The present invention relates to a polarizing film on which a pressure-sensitive adhesive layer is formed. The present invention also relates to a laminated body obtained by bonding a polarizing film on which a pressure-sensitive adhesive layer is formed and a substrate having a transparent conductive layer to each other, a liquid crystal panel having a polarizing film on which the pressure- And an image display apparatus using the stacked body as a touch panel.

Recently, transparent conductive films such as indium tin oxide (ITO) thin films have been widely used in various applications. For example, the transparent conductive film is formed on the side opposite to the side of the transparent substrate constituting the liquid crystal cell which is in contact with the liquid crystal layer of the liquid crystal display device using a liquid crystal cell such as an in-plane switching (IPS) . The transparent conductive film having the transparent conductive film formed on the transparent resin film is used for an electrode substrate of a touch panel. For example, a liquid crystal display device or an image display device used for a cellular phone, a portable music player, And an input device for use is widely spread.

As an input device using a combination of a touch panel and an image display device, a transparent conductive film having a transparent conductive layer formed on a transparent substrate made of a glass plate or a transparent resin film is laminated on a liquid crystal display device Cell type in which an electrode made of a transparent conductive film is formed on an upper glass substrate of a liquid crystal cell or an electrode made of a transparent conductive film is placed in the liquid crystal cell And the like are known. It is also known that the touch panel function is realized by patterning the ITO layer serving as the antistatic layer of the image display device as a touch sensor.

In liquid crystal display devices and image display devices using these transparent conductive films, there is a strong demand for weight reduction and thinness in recent years, and it is desired to reduce the thickness and weight of polarizing films used in the liquid crystal display devices and the like. As a method of making the polarizing film thinner and lighter, for example, there is known a method of forming a single-side protective polarizing film in which a transparent protective film is provided on only one side of a polarizer, and a method of manufacturing a thin polarizing film in which the thickness of the polarizing element itself is reduced.

As a process for producing a thin polarizing film, there is known a process for producing an optical film laminate in which a thin polarizing film composed of a polyvinyl alcohol-based resin in which iodine is oriented is formed on an amorphous ester-based thermoplastic resin base material of a continuous web , Patent Documents 1 and 2).

Japanese Patent No. 4751481 Japanese Patent No. 4691205 Specification

For example, when a transparent conductive film is used as an antistatic layer application, a polarizing film on which a pressure-sensitive adhesive layer is formed is laminated on a liquid crystal cell having the antistatic layer, and an antistatic layer made of a transparent conductive film and a polarizing film are laminated on the pressure- Respectively. When a transparent conductive film is used for an electrode of a touch panel, a polarizing film having a pressure-sensitive adhesive layer formed thereon is laminated on the transparent conductive film for the electrode, depending on the configuration of the touch panel, There is a case where the film is bonded via the pressure-sensitive adhesive layer.

In the case where the polarizing film is an iodine polarizing film, as described above, when the moisture-proof durability test (ordinary endurance test) is performed by bonding the transparent conductive layer and the iodine polarizing film to each other and the resistance value of the transparent conductive layer rises There was a case. It has been found that the increase in the resistance value is due to the fact that the iodine contained in the polarizer exudes to the pressure-sensitive adhesive layer, and the iodine reaches the transparent conductive layer, thereby corroding the transparent conductive layer.

For example, in a thin iodine polarizer having a thickness of 10 m or less as described in Patent Documents 1 and 2, it is necessary to increase the iodine concentration in the polarizer in order to have the same polarization characteristic as that of the conventional polarizer. It has been found that when a polarizing film including a high polarizer is attached to a transparent conductive layer, corrosion by iodine of the transparent conductive layer tends to occur. It has also been found that even when an iodine polarizing film having a one-side protection is used, corrosion of the transparent conductive layer tends to occur because the transparent conductive layer is directly bonded to the iodine polarizer via the pressure-sensitive adhesive layer.

Accordingly, the present invention provides a polarizing film provided with a pressure-sensitive adhesive layer capable of suppressing corrosion of the transparent conductive layer and suppressing an increase in the surface resistance value of the transparent conductive layer even when the transparent conductive layer is laminated on the transparent conductive layer . The present invention also provides an image display device comprising a laminate in which a polarizing film on which the pressure-sensitive adhesive layer is formed and a substrate having a transparent conductive layer are laminated, a liquid crystal panel having a polarizing film on which the pressure- And an object of the present invention is to provide an image display apparatus using the laminate as a touch panel.

Means for Solving the Problems The present inventors have intensively studied in order to solve the above problems and found that by using a pressure-sensitive adhesive layer formed of an acrylic pressure sensitive adhesive composition containing a phosphate compound and a (meth) acrylic polymer, , Thereby completing the present invention.

That is, the present invention relates to an iodine-based polarizing film comprising iodine-based polarizing film having iodine and / or iodine ion-containing iodine-based polarizer having a transparent protective film on at least one side thereof,

(1): < EMI ID =

[Chemical 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.)

, And a pressure sensitive adhesive layer formed of an acrylic pressure sensitive adhesive composition containing at least one phosphoric acid compound selected from the group consisting of a compound represented by the general formula (1) and a (meth) acrylic polymer, Sensitive adhesive layer is formed. Here, the "iodine-based polarizer containing iodine and / or iodine ions" is an iodine-based polarizer containing iodine, an iodine-based polarizer containing iodine ions, an iodine-based polarizer containing both iodine and iodine ions, Any of them can be preferably used in the invention.

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

Wherein the phosphoric acid compound comprises phosphoric acid and the phosphoric acid residue of a hydrocarbon residue having 1 to 18 carbon atoms, wherein either one of R ¹ and R ² in the general formula (1) is a hydrogen atom and the other may contain an oxygen atom, And monoester and at least one phosphoric acid ester selected from the group consisting of phosphoric acid diesters in which R ¹ and R ² in the general formula (1) may contain an oxygen atom and hydrocarbon residues of 1 to 18 carbon atoms Mixture.

It is preferable that the phosphate compound is a mixture containing phosphoric acid and phosphoric acid monoester. The total amount of phosphoric acid and phosphoric acid monoesters is preferably 80% by weight or more based on 100% by weight of the phosphoric acid compound.

It is preferable that the hydrocarbon residue having 1 to 18 carbon atoms is a linear or branched alkyl group having 1 to 10 carbon atoms.

Wherein the iodine-based polarizing film is a one-side protective polarizing film having a transparent protective film on only one side of the iodine-based polarizer, and a surface of the one-side protective polarizing film having no transparent protective film and the pressure- desirable.

The thickness of the iodine-based polarizer is preferably 10 m or less.

The total thickness of the iodine-based polarizing film is preferably 80 m or less.

It is also preferable that the adhesive layer of the polarizing film on which the pressure-sensitive adhesive layer is formed and the transparent conductive layer of the substrate having the transparent conductive layer are in contact with each other.

The amount of the phosphate compound added is preferably 0.001 to 4 parts by weight based on 100 parts by weight of the (meth) acryl-based polymer.

It is preferable that the (meth) acryl-based polymer contains, as a monomer unit, an alkyl (meth) acrylate and a monomer containing a hydroxyl group.

It is preferable that the hydroxyl group-containing monomer is 4-hydroxybutyl acrylate.

The weight average molecular weight of the (meth) acryl-based polymer is preferably 1.2 to 3 million.

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

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

The present invention is also characterized in that a polarizing film on which the pressure-sensitive adhesive layer is formed and a transparent conductive member having a transparent conductive layer are laminated so that the pressure-sensitive adhesive layer of the polarizing film on which the pressure-sensitive adhesive layer is formed is in contact with the transparent conductive layer of the member And the like.

It is preferable that the transparent conductive layer is formed of indium tin oxide, and it is more preferable that the indium tin oxide is amorphous indium tin oxide.

The present invention also provides a liquid crystal display device comprising a liquid crystal panel having a pressure sensitive adhesive layer of a polarizing film on which the pressure sensitive adhesive layer is formed and a transparent conductive layer so that the pressure sensitive adhesive layer of the polarizing film on which the pressure sensitive adhesive layer is formed is brought into contact with the transparent conductive layer of the liquid crystal panel The present invention relates to an image display apparatus.

Further, the present invention relates to an image display device characterized in that the above-mentioned laminate is used as a touch panel.

Although the polarizing film in which the pressure-sensitive adhesive layer of the present invention is formed uses an iodine-based polarizer, even when a transparent conductive layer is laminated on the pressure-sensitive adhesive layer of the polarizing film on which the pressure-sensitive adhesive layer is formed, corrosion of the transparent conductive layer can be suppressed, The increase in the surface resistance of the conductive layer can be suppressed. This is because the pressure-sensitive adhesive layer of the polarizing film on which the pressure-sensitive adhesive layer of the present invention is formed contains a phosphoric acid-based compound. Specifically, for example, when the phosphoric acid-based compound contains phosphoric acid, a passive film is formed of a metal ion in the phosphoric acid and the transparent conductive layer on the surface of the transparent conductive layer, and as a result, the iodine in the polarizer And the corrosion of the transparent conductive layer is inhibited. When the phosphoric acid compound contains a phosphoric acid compound (for example, phosphoric acid ester), the phosphoric acid compound is selectively adsorbed on the surface of the transparent conductive layer to form a film. As a result, The surface is not transferred to the surface and the corrosion of the transparent conductive layer is inhibited.

1 is a cross-sectional view schematically showing an embodiment of an image display apparatus according to the present invention.
2 is a cross-sectional view schematically showing an embodiment of an image display apparatus of the present invention.
3 is a cross-sectional view schematically showing an embodiment of the image display apparatus of the present invention.

1. A polarizing film on which a pressure-sensitive adhesive layer is formed

The polarizing film on which the pressure-sensitive adhesive layer of the present invention is formed is formed on at least one surface of an iodine-based polarizing film having a transparent protective film on at least one side of an iodine-based polarizer containing iodine and /

(1): < EMI ID =

(2)

(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.)

, And a pressure sensitive adhesive layer formed of an acrylic pressure sensitive adhesive composition containing at least one phosphoric acid compound selected from the group consisting of a compound represented by the general formula (1) and a (meth) acrylic polymer, do.

(1) iodine polarizing film

The iodine-based polarizing film used in the present invention has a transparent protective film on at least one side of an iodine-based polarizer containing iodine and / or iodine ions. In the present invention, a single-side protective polarizing film having a transparent protective film on one side of the iodine polarizer and a double-side protective polarizing film having a transparent protective film on both sides of the iodine polarizer may be used. However, The effect of the present invention is remarkable. Even when the double-sided protective polarizing film is used, the effect of the present invention is remarkable even when the thickness of the transparent protective film on the side in contact with the pressure-sensitive adhesive layer is thin (for example, 25 m or less). When the polarizing film is a one-side protective polarizing film, the pressure-sensitive adhesive layer can be formed directly on the polarizer surface on the side not having the transparent protective film.

As the iodine polarizer, any polarizer containing iodine and / or iodine ions can be used, and examples thereof include a polyvinyl alcohol (PVA) film, a partially polarized PVA film, an ethylene / vinyl acetate copolymerization system And a partially saponified film or the like, which is uniaxially stretched by adsorbing iodine to a hydrophilic polymer film. Among them, a polarizer comprising a PVA-based film and iodine is preferable. The thickness of these polarizers is not particularly limited, but is generally about 5 to 80 占 퐉.

The monoaxially polarized polarizer obtained by dying a PVA film with iodine can be produced by, for example, dying PVA in an aqueous solution of iodine and stretching 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, zinc chloride or the like. If necessary, the PVA film may be dipped in water and washed with water before dyeing. The PVA film is washed with water to clean the surface of the PVA film and the anti-blocking agent. In addition, the PVA film is swollen to prevent unevenness such as uneven dyeing. The stretching may be carried out after dyeing with iodine, followed by stretching while dyeing, or after stretching, followed by dyeing with iodine. It can be stretched in an aqueous solution such as boric acid or potassium iodide or in a water bath.

In the present invention, a thin iodine-based polarizer having a thickness of 10 mu m or less can also be preferably used. From the viewpoint of thinning, the thickness is preferably 1 to 7 mu m. It is preferable that such a thin iodine polarizer is excellent in durability because the thickness irregularity is small, the visibility is excellent, the dimensional change is small, and further, the thickness and thickness of the polarizing film can be reduced.

Typical examples of the thin polarizer include those described in Japanese Laid-Open Patent Publication Nos. 51-069644 and 2000-338329, International Publication No. 2010/100917, International Publication No. 2010/100917, and Japanese Patent No. 4751481 And a thin polarizing film described in JP-A-2012-073563. These thin polarizing films can be obtained by a manufacturing method including a step of stretching a PVA resin layer and a lead resin base material in a laminate state and a step of dyeing. With this method, even if the PVA resin layer is thin, it can be stretched without problems such as breakage due to stretching because it is supported on the resin base material for drawing.

As the thin polarizing film, from the viewpoint of being capable of stretching at a high magnification and improving the polarization performance even in a process including a step of stretching in the form of a laminate and a step of dyeing, the pamphlet of International Publication No. 2010/100917, It is preferably obtained by a production method comprising a step of stretching in an aqueous solution of boric acid as disclosed in the specification of Japanese Patent No. 4751481 or the specification of Japanese Patent Publication No. 2012-073563, In a boric acid aqueous solution described in Japanese Laid-Open Patent Publication No. 2012-073563, a method of auxiliary drawing publicly before stretching.

The content of iodine and / or iodide ion (hereinafter also referred to as iodine content) of the iodine-based polarizer used in the present invention may be 1 to 14% by weight of the polarizer, 3 to 12% by weight And may be 4 to 7.5% by weight. The polarizing film in which the pressure-sensitive adhesive layer of the present invention is formed can suppress an increase in the surface resistance of the transparent conductive layer laminated on the polarizing film on which the pressure-sensitive adhesive layer is formed, even if the iodine content in the iodine polarizer is as large as the above range. This is because iodine contained in the iodine-based polarizing film does not migrate to the surface of the transparent conductive layer because the phosphoric acid compound contained in the pressure-sensitive adhesive layer forms a film on the surface of the transparent conductive layer. As a result, I think it is because it is inhibited. Specifically, when the phosphoric acid-based compound contains phosphoric acid, the phosphoric acid forms a passive film with the metal ion in the transparent conductive layer on the surface of the transparent conductive layer, and the phosphoric acid compound is a phosphoric acid compound (for example, phosphoric acid Ester, etc.), the phosphoric acid compound is selectively adsorbed on the surface of the transparent conductive layer to form a film.

As a material for forming the transparent protective film formed on one side or both sides of the iodine polarizer, it is preferable that the material is excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy and the like. For example, a polyester polymer such as polyethylene terephthalate or polyethylene naphthalate, a cellulose polymer such as diacetylcellulose or triacetylcellulose, an acrylic polymer such as polymethyl methacrylate, a polystyrene or an acrylonitrile styrene copolymer (AS resin), and polycarbonate-based polymers. In addition, a polyolefin-based polymer such as polyethylene, polypropylene, a cycloolefin-based or norbornene-based structure, a polyolefin-based polymer such as an ethylene-propylene copolymer, an amide-based polymer such as nylon or aromatic polyamide, Based polymers, polyether sulfone-based polymers, polyetheretherketone-based polymers, polyphenylene sulfide-based polymers, vinyl alcohol-based polymers, vinylidene chloride-based polymers, vinyl butyral-based polymers, arylate- An epoxy-based polymer, or a blend of the above polymer may be mentioned as an example of the polymer forming the transparent protective film. The transparent protective film may be formed as a cured layer of a thermosetting or ultraviolet curing resin such as acrylic, urethane, acrylic urethane, epoxy or silicone.

The thickness of the protective film can be suitably determined, but generally it is about 1 to 500 占 퐉 in view of workability such as strength and handling properties and thin film properties.

The iodine polarizer and the transparent protective film are usually in close contact with each other through an aqueous adhesive or the like. Examples of the water-based adhesive include an isocyanate-based adhesive, a polyvinyl alcohol-based adhesive, a gelatin-based adhesive, a vinyl-based latex-based, a water-based polyurethane, and a water-based polyester. Examples of the adhesive for the polarizer 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 preferable adhesiveness to the above various transparent protective films. The adhesive used in the present invention may contain a metal compound filler.

The surface of the transparent protective film on which the iodine polarizer is not adhered may be subjected to treatment for the purpose of hard coat layer, antireflection treatment, anti-sticking, diffusion or anti-glare treatment.

The total thickness of the iodine polarizing film used in the present invention is preferably not more than 80 탆, more preferably not more than 70 탆, and even more preferably not more than 60 탆 in order to meet the demand for thinning of the polarizing film on which the pressure-sensitive adhesive layer is formed . The lower limit of the total thickness of the polarizing film is not particularly limited, but may be 10 탆, for example.

(2) Pressure-sensitive adhesive layer

The pressure-sensitive adhesive layer used in the polarizing film in which the pressure-sensitive adhesive layer of the present invention is formed is formed of an acrylic pressure-sensitive adhesive composition. The acrylic pressure-

(1): < EMI ID =

(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.)

(Meth) acryl-based polymer selected from the group consisting of a compound represented by the general formula (1) and a compound represented by the general formula (1).

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

In the general formula (1), R ¹ and R ² are each independently a hydrogen atom or a hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom. Examples of the hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom include an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, - (CH ₂ CH ₂ O) _n R ³ (R ³ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms, and n is an integer of 0 to 15). The alkyl group and the alkenyl group may be linear or branched. Among them, the hydrocarbon residue having 1 to 18 carbon atoms is preferably a linear or branched alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 18 carbon atoms, and a linear or branched alkyl group having 2 to 6 carbon atoms is preferable. desirable.

In the present invention, phosphoric acid (H ₃ PO ₄ ) in which all of R ¹ and R ^{2 in the} general formula (1) are hydrogen atoms is also preferably used. Salts of the above phosphoric acids (metal salts such as sodium, potassium, and magnesium, ammonium salts, etc.) may also be preferably used.

In the present invention, it is preferable that the compound represented by the general formula (1) is an acidic phosphate ester. Here, the acidic phosphate is a residue of a hydrocarbon residue having 1 to 18 carbon atoms (diester body) in which all of R ¹ and R ^{2 in the} general formula (1) may contain an oxygen atom, and R ¹ and R ² is a hydrocarbon residue of 1 to 18 carbon atoms (a monoester form) in which one of R 1 and R ² is a hydrogen atom and the other may contain an oxygen atom. For example, the following general formula (2):

[Chemical Formula 4]

(Wherein R ¹ is as defined above, R ³ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms, and n is an integer of 0 to 15 .)

And phosphoric acid ester compounds represented by the following general formula (1).

R ¹ of formula (2) is a hydrocarbon residue having 1 to 18 carbon atoms that is the same as R ¹ of formula (1), and may contain a hydrogen atom, or an oxygen atom. Examples of the hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom include the same ones as described above. R ^{1 in the} general formula (2) is preferably a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms, and is preferably a hydrogen atom or a linear or branched More preferably a hydrogen atom or a linear or branched alkyl group having 2 to 6 carbon atoms. As R ³ , 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 can be mentioned, and it is preferably an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms, More preferably an alkyl group having 1 to 10 carbon atoms, and still more preferably an alkyl group having 2 to 6 carbon atoms. Also, n is an integer of 0 to 15, preferably an integer of 0 to 10. In the present invention, it is preferable from the viewpoint of prevention of deterioration that it does not include the polyethylene oxide structure (CH ₂ CH ₂ O) (that is, n = 0 in the formula (2)).

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

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

In the present invention, salts of compounds represented by the general formula (2) (metal salts such as sodium, potassium and magnesium, ammonium salts and the like) can also be preferably used.

As a commercially available product of the phosphate ester compound represented by the general formula (2), "Phosphanol SM-172" (R ¹ = R ³ = C ₈ H _{17 in the} general formula (2) n = 0, mono-di mixture, acid value: 219 mgKOH / g), "Phosphanol GF-185" (R ¹ = R ³ = C ₁₃ H ₂₇ , (Phosphophenol BH-650) (R ¹ = R ³ = C ₄ H ₉ , n = 1 in the formula (2), mono-di mixture, acid value: 388 mgKOH / g), "Phosphanol RS-410" (R ¹ = R ³ = C ₁₃ H ₂₇ , n = 4, mono-di mixture in the general formula (2), acid value: 105 mgKOH / g) RS-610 "(R ¹ = C ₁₃ H ₂₇ , R ³ = C ₁₃ H ₂₇ , n = 6, mono-di mixture, acid value: 82 mg KOH / g in the general formula (2))," Phosphanol RS- 710 "(R ¹ = C ₁₃ H ₂₇ , R ³ = C ₁₃ H ₂₇ , n = 10, mono-di mixture, acid value: 62 mgKOH / g in the general formula (2))," Phosphanol ML- (R ¹ = R ³ = C ₁₂ H ₂₅ , n = 2, mono-di mixture in the general formula (2)), "Phosphanol ML- 200 "(R ¹ in the formula ^{(2) = R 3 = C} 12 H 25, n = 0, mono-, di-mixture)," Force propanol ED-200 "(R ¹ in the formula (2) = R ³ = C ₈ H ₁₇ , n = 1, mono-di mixture), "Phosphanol RL-210" (R ¹ = R ³ = C ₁₈ H ₃₇ , n = 2, mono-di mixture of general formula "Phosphanol GF-339 (mixture of R ¹ = R ³ = C ₆ H ₁₃ to C ₁₀ H ₂₁ in general formula (2), n = 0, mono-di mixture) formula (2) _{^{R 1 = R 3 = C 12}} H 25, n = 0, mono-, ^{di-mixture), R 1 = R 3 =} C 18 H 37 of "Force propanol RL-310" (the general formula (2) , n = 3, mono-di mixture), "Phosphanol LP-700" (R ¹ = R ³ = C ₆ H ₅ , n = 6, mono-di mixture in the general formula (2) AP-1 "(R ¹ = R ³ = CH ₃ , n = 0, mono-di mixture, acid value: 650 mg KOH / g or more in the general formula (2) DP-4 (represented by R ^{1 in the} general formula (2) (R ¹ = R ³ = C ₄ H ₉ , n = 0, mono-di mixture, acid value: 452 mgKOH / g) _{^{= R 3 = C 4 H 9}} , (R ¹ = H, R ³ = C ₄ H ₉ , n = 0, mono-di (n = 0), mono-di mixture, acid value: 292 mgKOH / g) AP-8 (R ¹ = R ³ = C ₈ H ₁₇ , n = 0, mono-di mixture, acid value: 306 mg KOH / g in the formula (2) ), "AP-10" (R ¹ = R ³ = C ₁₀ H ₂₁ , n = 0 in the general formula (2), mono-di mixture, acid value: 263 mgKOH / g) JP-508 "(trade name, manufactured by Joho Chemical Co., Ltd.) (R ¹ = H, R ³ = C ₁₀ H ₂₁ , n = 0, mono-di mixture and acid value: 400 mgKOH / R ¹ of formula (2) = R ³ = C ₈ H _17, n = 0, mono, di mixture, acid value: 288 ㎎KOH / g), R 1 of "JP-513" (formula (2) = R ³ = C ₁₃ H ₂₇ , n = 0, mono-di mixture), JP-524R (R ¹ = R ³ = C ₂₄ H ₄₉ , , "DBP" (R ¹ = R ³ = C ₄ H ₉ , n = 0, mono-di mixture, acid value: 266 mgKOH / g in the general formula (2)), "LB- ) of _{^{R 1 = R 3 = C 8}} H 17, n = 0, diester body, acid value: 173 KOH / g), Nikko Chemicals's R (Note) "nitkol DDP-2" (Formula (2, Ltd.) ¹ = a mixture of _{^{R 3 = C 12 H 25 ~}} C 15 H 31, n = 2), SIGMA (O = P (OH) ₂ (OC ₄ H ₉ ), R ¹ = H, R ³ = C ₄ H ₉ , n = 0, Product Nomber : CDS001281, monoester), and salts thereof. The term "mono-di mixture" as used herein refers to a mixture of a monoester (R ¹ = H in the formula (2)) and a diester (R ^{1 in the} formula (2) For example, a monoester (R ¹ = H, R ³ = C ₈ H ₁₇ , n = 0 in the general formula (2)) in the case of phosphanol SM-172, Diester (R ¹ = R ³ = C ₈ H ₁₇ , n = 0 in the general formula (2)). The mixing ratio of the monoester and diester of the "mono-di mixture" can be calculated from the measurement results of ³¹ P-NMR. The measurement method is as described in the examples.

The phosphoric acid compound used in the present invention may be a compound selected from the group consisting of a compound represented by the general formula (1) (or a compound represented by the general formula (2)), (In particular, an adherend having a metal or a metal oxide or a layer composed of a metal or a metal oxide) from the viewpoint of the effect of adsorption on the adherend (particularly, a metal or a metal oxide or a layer comprising a metal or a metal oxide) And a phosphoric acid diester, and it is preferably a mixture containing phosphoric acid and at least one phosphoric acid ester selected from the group consisting of phosphoric acid monoester and phosphoric acid diester Particular preference is given to mixtures comprising phosphoric acid monoester and phosphoric acid. In the present invention, one kind selected from the group consisting of phosphoric acid, phosphoric acid monoester and phosphoric acid diester may be used alone, but if phosphoric acid is used alone, the pot life of the pressure-sensitive adhesive composition may be insufficient. Further, since phosphoric acid is a compound having a very high polarity and compatibility with the acrylic polymer is not sufficient, phosphoric acid may bleed out to the surface of the pressure-sensitive adhesive layer, resulting in a problem in terms of durability. In addition, if phosphoric acid is not used and only phosphoric acid ester (phosphoric acid monoester and / or phosphoric acid diester) is used, there may be a problem in durability under very severe conditions (for example, heat cycle test). In the present invention, it is most preferable to use a phosphoric acid-based compound containing phosphoric acid and phosphoric acid monoester from the viewpoint of balance between corrosion inhibition of the transparent conductive layer and durability under extremely severe conditions. 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 is a compound which is a hydrocarbon residue having 1 to 18 carbon atoms, in which one of R ¹ and R ² in the general formula (1) is a hydrogen atom and the other may contain an oxygen atom (general formula (2) ) is, R ¹ is a hydrogen atom) in the case of a phosphoric acid diester is, is represented by the general formula ⁽¹⁾ R 1 and R ^2, may contain an oxygen atom, a hydrocarbon residue having 1 to 18 carbon atoms is a compound (In the case of the general formula (2), a compound wherein R ¹ is a hydrocarbon residue having 1 to 18 carbon atoms, which may contain an oxygen atom).

The adsorption effect on the adherend (in particular, metal or metal oxide) is considered to be related to the adhered surface and the phosphate-based compound defined by the HSAB rule, that is, the " rule of hard and soft acid bases " It is considered that the combination of a base and a weak base with an acid in the base and the mullulan has a high adsorption effect, and as a result, a high deterioration preventing effect is obtained. That is, for example, In of ITO corresponds to a hard acid defined by the HSAB rule, and since the phosphoric acid-based compound becomes a soft base from a solidified base in the order of phosphoric acid, phosphoric acid monoester and phosphoric acid diester, It can be effectively adsorbed to ITO, and as a result, a high deterioration preventing effect is obtained.

 When a mixture of a monoester and a diester is used, the mixture is preferably a mixture containing a large amount of monoester. The mixing ratio (weight ratio) of the mixture of monoester and diester is preferably from 6: 4 to 9: 1, more preferably from 7: 3 to 9: 1 . For these reasons, it is preferable to include a large amount of the monoester compound because the adsorption effect on the adherend is high.

As described above, in the present invention, it is preferable to add phosphoric acid in addition to the phosphoric acid ester compound (particularly phosphoric acid monoester). In this case, the amount of phosphoric acid to be added is preferably in the range of , Preferably 10 to 400 parts by weight, more preferably 10 to 100 parts by weight, and more preferably 10 to 50 parts by weight in view of the adsorption effect on an adherend. From the viewpoint of durability under extremely severe conditions, the addition amount of phosphoric acid 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.

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 preferably 10 to 700 mgKOH / g. From the viewpoint of production handling, the acid value of the phosphate 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 from 100 to 300 mgKOH / g. The phosphoric acid compound sometimes acts as a reaction catalyst for the crosslinking reaction depending on the kind of the crosslinking agent (for example, an isocyanate crosslinking agent) to be described later. In that case, the pot life as the pressure-sensitive adhesive may be shortened. By setting the acid value of the phosphoric acid compound within the above range, it is possible to suppress the action as a reaction catalyst, which is preferable in view of the pot life of the pressure-sensitive adhesive. It is preferable to add the phosphoric acid compound having an acid value in the above range in an amount to be described later from the viewpoint of being able to exert an effective effect.

Examples of the oligomer of the compound represented by the general formula (1) include dimers and trimer of the compound represented by the general formula (1).

The amount of the phosphoric acid compound to be added is preferably 0.001 to 4 parts by weight, more preferably 0.001 to 3 parts by weight, further preferably 0.001 to 2 parts by weight, relative to 100 parts by weight of the (meth) acryl- Particularly preferably 0.005 to 1 part by weight, more preferably 0.01 to 1 part by weight, particularly preferably 0.02 to 0.2 part by weight. The addition amount of the phosphoric acid compound within the above range is preferable because 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. In the present invention, as described above, a phosphoric acid or phosphate compound such as phosphoric acid ester can be used in combination. In that case, the total amount can be added in the above range.

In the present invention, by forming the polarizing film having the pressure-sensitive adhesive layer having the pressure-sensitive adhesive layer formed of the acrylic pressure-sensitive adhesive composition containing the phosphate compound, even if the transparent conductive layer is laminated on the pressure-sensitive adhesive layer surface of the polarizing film on which the pressure- The increase in the surface resistance of the conductive layer can be suppressed. When phosphoric acid is contained in the phosphoric acid compound, the phosphoric acid forms a passive film with the metal ion in the transparent conductive layer on the surface of the transparent conductive layer so that the iodine in the polarizer does not migrate to the surface of the transparent conductive layer, And corrosion of the conductive layer is inhibited. When the phosphate compound contains a phosphoric acid compound (for example, phosphoric acid ester or the like), the phosphoric acid compound is selectively adsorbed on the surface of the transparent conductive layer to form a film The iodine in the polarizer does not migrate to the surface of the transparent conductive layer, and as a result, corrosion of the transparent conductive layer is inhibited.

With respect to the corrosion referred to herein, metal oxides are corroded by a mechanism that is different from commonly known metal corrosion. In the case of a metal oxide such as ITO, iodine originating from the polarizer penetrates into the metal oxide layer and lowers the carrier mobility of the metal oxide, so that the resistance value increases.

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

The (meth) acryl-based polymer used in the present invention is not particularly limited, but for example, it is preferably obtained by polymerizing a monomer component containing an alkyl (meth) acrylate, and the alkyl (meth) acrylate and the hydroxyl Containing monomer is preferably obtained by polymerizing a monomer component containing a practical group-containing monomer. The alkyl (meth) acrylate refers to alkyl acrylate and / or alkyl methacrylate and has the same meaning as (meth) of the present invention.

As the alkyl group related to the alkyl (meth) acrylate, various types of linear or branched alkyl groups can be used. Specific examples of the alkyl (meth) acrylate include propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec- (Meth) acrylate, isobutyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, (Meth) acrylate, n-decyl (meth) acrylate, isooctyl (meth) acrylate, isooctyl (meth) acrylate, stearyl (meth) acrylate, octadecyl (meth) acrylate, n-dodecyl ) Acrylate, and dodecyl (meth) acrylate. . These can be used alone or in combination. Among these, alkyl (meth) acrylates having an alkyl group having 4 to 18 carbon atoms are preferable, and (meth) acrylates having an alkyl group having 4 to 10 carbon atoms are more preferable, and n-butyl (meth) acrylate, 2- Ethylhexyl (meth) acrylate is more preferable, and n-butyl (meth) acrylate is particularly preferable.

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

As the hydroxyl group-containing monomer, those having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and having a hydroxyl group can be used without particular limitation. Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (Meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, (Meth) acrylate, etc. These may be used singly or in combination of two or more kinds. Of these, 4-hydroxybutyl acrylate is preferred. When an isocyanate-based crosslinking agent is used as a crosslinking agent to be described later, it is preferable to use 4-hydroxybutyl acrylate as the hydroxyl group-containing monomer since a crosslinking point of the isocyanate-based crosslinking agent with the isocyanate group can be efficiently ensured .

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

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

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

The carboxyl group-containing monomer is preferably 10 parts by weight or less, more preferably 8 parts by weight or less, particularly preferably 100 parts by weight or less, based on 100 parts by weight of the monomer component forming the (meth) acryl- More preferably 6 parts by weight or less, further preferably 2 parts by weight or less, and particularly preferably 0.5 part by weight or less.

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

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

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

Examples of the copolymerizable monomer include maleimide-based monomers such as N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide and N-phenylmaleimide; For example, there may be mentioned N-methyl itaconimide, N-ethyl itaconimide, N-butyl itaconimide, N-octyl itaconimide, N-2-ethylhexyl itaconimide, Itaconimide monomers such as hexyl itaconimide and N-lauryl itaconimide; (Meth) acryloyloxymethylenesuccinimide, N- (meth) acryloyl-6-oxyhexamethylenesuccinimide, N- (meth) acryloyloxymethylenesuccinimide, N- Succinimide monomers such as succinimide; (Meth) acrylamide-2-methylpropanesulfonic acid, (meth) acrylamidopropanesulfonic acid, sulfopropyl (meth) acrylate, (meth) acryloyloxynaphthalenesulfonic acid and the like Of sulfonic acid group-containing monomers.

Examples of the copolymerizable monomers include glycol type acrylic esters such as (meth) acrylic acid polyethylene glycol, (meth) acrylic acid polypropylene glycol, (meth) acrylic acid methoxyethylene glycol and (meth) acrylic acid methoxypolypropylene glycol Monomers; In addition, examples thereof include heterocycles such as (meth) acrylate tetrahydrofurfuryl and fluorine (meth) acrylate, and acrylic ester monomers containing a halogen atom.

Further, as the copolymerizable monomer, a polyfunctional monomer can be used. Examples of the polyfunctional monomer include compounds having two or more unsaturated double bonds such as a (meth) acryloyl group and a vinyl group. (Meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetraethylene glycol di (Mono or poly) ethylene glycol di (meth) acrylate such as (meth) acrylate and (mono or poly) propylene glycol di (meth) acrylate such as propylene glycol di (Meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri Esters of (meth) acrylic acid and polyhydric alcohols such as acrylate, pentaerythritol tri (meth) acrylate and dipentaerythritol hexa (meth) acrylate; Polyfunctional vinyl compounds such as divinylbenzene; (Meth) acrylate, vinyl (meth) acrylate, and other reactive unsaturated double bonds. Examples of the polyfunctional monomer include polyester (meth) acrylate having two or more unsaturated double bonds such as (meth) acryloyl groups and vinyl groups as the same functional group as the monomer component in the backbone of polyester, epoxy, Epoxy (meth) acrylate, urethane (meth) acrylate, and the like.

The proportion of other copolymerizable monomer is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, further preferably 15 parts by weight or less, based on 100 parts by weight of the monomer component forming the (meth) acrylic polymer , And particularly preferably 10 parts by weight or less. If the proportion of the copolymerizable monomer is excessively large, there is a possibility that the adhesive property such as deterioration of adhesiveness to various adherends such as glass, film, and transparent conductive layer of the pressure-sensitive adhesive layer formed of the acrylic pressure-sensitive adhesive composition may decrease.

The weight average molecular weight of the (meth) acryl-based polymer used in the present invention is preferably in a range of from 1.2 million to 3 million, more preferably from 1.2 million to 2.7 million, and even more preferably from 1.2 million to 2.5 million. If the weight-average molecular weight is less than 1,200,000, the heat-resistant property may not be preferable. On the other hand, if the weight average molecular weight is less than 1,200,000, the low molecular weight component increases in the pressure-sensitive adhesive composition, and the low molecular weight component bleeds out from the pressure-sensitive adhesive layer, which may hinder transparency. In addition, the pressure-sensitive adhesive layer obtained using a (meth) acryl-based polymer having a weight average molecular weight of less than 1,200,000 has poor solvent resistance and mechanical properties. On the other hand, if the weight average molecular weight is larger than 3,000,000, a large amount of a diluting solvent is required to adjust the viscosity for coating, which is not preferable from the viewpoint of cost. Also, since the weight average molecular weight is within the above range, it is preferable from the viewpoint of corrosion resistance and durability. The weight average molecular weight refers to a value measured by GPC (Gel Permeation Chromatography) and calculated by polystyrene conversion.

The production of such (meth) acrylic polymers can be suitably selected from known production methods such as solution polymerization, bulk polymerization, emulsion polymerization, various kinds of radical polymerization, and the like, and is not particularly limited. The (meth) acryl-based polymer to be obtained may be a random copolymer, a block copolymer, or a graft copolymer.

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

The polymerization initiator, chain transfer agent and emulsifier used in the radical polymerization are not particularly limited and can be appropriately selected and used. The weight average molecular weight of the (meth) acryl-based polymer can be controlled depending on the amount of the polymerization initiator, the amount of the chain transfer agent used, and the reaction conditions.

Examples of the polymerization initiator include azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis [2- Azobis (2-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'- Azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate (trade name: VA-057, manufactured by Wako Pure Chemical Industries, Ltd.) (2-ethylhexyl) peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate, di-sec-butylperoxydicarbonate t-butyl peroxyneodecanoate, t-hexyl peroxy pivalate, t-butyl peroxy pivalate, dilauryl peroxide, di-n-octanoyl peroxide, 1,1,3,3- Tetramethylbutylperoxy-2-ethylhexanoate Di (t-hexylperoxy) cyclohexane, t-butyl hydroperoxide, hydrogen peroxide and the like, such as di (4-methylbenzoyl) peroxide, dibenzoyl peroxide, t-butyl peroxyisobutyrate, But are not limited to, a peroxide initiator, a combination of persulfate and sodium hydrogen sulfite, a redox initiator in combination with a peroxide such as a combination of peroxide and sodium ascorbate, and a reducing agent.

The polymerization initiator may be used singly or in admixture of two or more. The content of the polymerization initiator is preferably 0.005 to 1 part by weight per 100 parts by weight of the monomer component forming the (meth) acrylic polymer .

Examples of the chain transfer agent include lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolate, 2,3-dimercapto- -Propanol and the like. The chain transfer agent may be used singly or in admixture of two or more, but the total content is about 0.1 part by weight or less based on 100 parts by weight of the total amount of the monomer components.

To the acrylic pressure sensitive adhesive composition used in the present invention, various silane coupling agents may be added in order to improve the adhesion under high temperature and high humidity conditions. As the silane coupling agent, those having any appropriate functional group can be used. Examples of the functional group include a vinyl group, an epoxy group, an amino group, a mercapto group, a (meth) acryloyl group, an acetoacetyl group, an isocyanate group, a styryl group and a polysulfide group. Specific examples thereof include vinyl group-containing silane coupling agents such as vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane and vinyltributoxysilane; ? -glycidoxypropyltrimethoxysilane,? -glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. An epoxy group-containing silane coupling agent; (aminoethyl) -? - aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane,? -triethoxysilyl Amino group-containing silane coupling agents such as -N- (1,3-dimethylbutylidene) propylamine and N-phenyl- gamma -aminopropyltrimethoxysilane; a mercapto group-containing silane coupling agent such as? -mercaptopropylmethyl dimethoxysilane; styryl group-containing silane coupling agents such as p-styryltrimethoxysilane; (meth) acryl group-containing silane coupling agents such as? -acryloxypropyltrimethoxysilane and? -methacryloxypropyltriethoxysilane; Isocyanate group-containing silane coupling agents such as 3-isocyanatepropyltriethoxysilane; And polysulfide group-containing silane coupling agents such as bis (triethoxysilylpropyl) tetrasulfide.

The silane coupling agent may be used alone or in admixture of two or more, but the total content is preferably 1 part by weight or less based on 100 parts by weight of the total monomer component constituting the (meth) acrylic polymer More preferably 0.01 to 1 part by weight, still more preferably 0.02 to 0.8 part by weight, particularly preferably 0.05 to 0.7 part by weight. If the blending amount of the silane coupling agent exceeds 1 part by weight, an unreacted coupling agent component is generated, which is not preferable from the standpoint of durability.

When the silane coupling agent can be copolymerized with the monomer component by radical polymerization, the silane coupling agent can be used as the monomer component. The ratio is preferably 0.005 to 0.7 part by weight based on 100 parts by weight of the total monomer component constituting the (meth) acrylic polymer.

Furthermore, the acrylic pressure-sensitive adhesive composition used in the present invention is preferably added with a crosslinking agent because cohesive force relating to the durability of the pressure-sensitive adhesive can be imparted.

As the crosslinking agent, a polyfunctional compound is used, and examples thereof include an organic crosslinking agent and a polyfunctional metal chelate. Examples of the organic crosslinking agent include an epoxy crosslinking agent, an isocyanate crosslinking agent, a carbodiimide crosslinking agent, an imine crosslinking agent, an oxazoline crosslinking agent, an aziridine crosslinking agent and a peroxide crosslinking agent. The polyfunctional metal chelate is a covalent bond or a coordination bond of a polyvalent metal atom with an organic compound. Examples of the multivalent metal atom include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, have. Examples of the reactive group in the covalent bond or the coordination 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 them, a peroxide-based cross-linking agent and an isocyanate-based cross-linking agent are preferable, and it is more preferable to use them in combination.

The isocyanate-based crosslinking agent refers to a compound having two or more isocyanate groups (including an isocyanate regenerated functional group temporarily protected by an isocyanate group as a blocking agent or a quantification agent) in one molecule.

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

More specifically, examples thereof include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate, alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate, alicyclic isocyanates such as 2,4- Aromatic diisocyanates such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate and polymethylene polyphenyl isocyanate, trimethylolpropane / tolylene diisocyanate trimer addition product (trade name: Coronate L, Nippon Polyurethane Industry Co., Ltd.), trimethylolpropane / hexamethylene diisocyanate trimer addition product (trade name: Coronate HL, manufactured by Nippon Polyurethane Industry Co., Ltd.), hexamethylene diisocyanate isocyanurate ( Product name: Coronate HX, Nippon Polyurethane (Trade name: D110N, manufactured by Mitsui Chemicals, Inc.), trimethylol propane adduct of hexamethylene diisocyanate (trade name: D160N, manufactured by Mitsui Chemicals, Inc.), trimethylol propane adduct of xylylene diisocyanate Manufactured by Mitsui Chemicals, Inc.); Polyether polyisocyanates, polyester polyisocyanates, polyisocyanates that are multifunctionalized by adducts of these with various polyols, isocyanurate bonds, biuret bonds, allophanate bonds, and the like. Of these, it is preferable to use an aliphatic isocyanate because the reaction rate is fast.

As the peroxide-based crosslinking agent, various peroxides are used. Examples of the peroxide include di (2-ethylhexyl) peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate, di-sec-butylperoxydicarbonate, t- 1,1,3,3-tetramethylbutylperoxyisobutyrate, 1,1,3,3-tetramethylbutylperoxyisobutyrate, 1,1,3,3-tetramethylbutylperoxyisobutyrate, 1,1,3,3-tetramethylbutylperoxyisobutyrate, 1,1,3,3- 3,3-tetramethylbutylperoxy 2-ethylhexanoate, di (4-methylbenzoyl) peroxide, dibenzoyl peroxide, t-butylperoxyisobutyrate and the like. Of these, di (4-t-butylcyclohexyl) peroxydicarbonate, dilauryl peroxide, and dibenzoyl peroxide, which are particularly excellent in the efficiency of the crosslinking reaction, are preferably used.

The blending ratio of the crosslinking agent in the acrylic pressure-sensitive adhesive composition is not particularly limited, but is usually blended at a ratio of about 10 parts by weight or less of the crosslinking agent (solid content) to 100 parts by weight of the (meth) acrylic polymer (solid content). The blending ratio of the crosslinking agent is preferably 0.01 to 10 parts by weight, more preferably 0.01 to 5 parts by weight. Particularly, when a peroxide-based crosslinking agent is used, the amount is preferably 0.05 to 1 part by weight, more preferably 0.06 to 0.5 part by weight per 100 parts by weight of the (meth) acrylic polymer (solid content).

The addition of an ionic compound to the acrylic pressure-sensitive adhesive composition used in the present invention is preferable from the viewpoint of preventing electrification of the film during processing.

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. The term "organic cation-anion salt" in the present invention means an organic salt, and the cation portion thereof is composed of an organic substance, and the anion portion may be an organic substance or an inorganic substance. The term "organic cation-anion salt" is also referred to as an ionic liquid or an ionic solid.

<Alkali metal salt>

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

The anion portion of the alkali metal salt may be composed of an organic material or may be composed of an inorganic material. Anion portion constituting the organic salt is, 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 to general formula ( 4) to (7),

(4): _???????? (C _n F _{2n + 1} SO ₂ ) ₂ N ^- wherein n is an integer of 1 to 10,

(5): CF ₂ (C _m F _{2 m} SO ₂ ) ₂ N ^- (wherein m is an integer of 1 to 10)

(6): ^- O ₃ S (CF ₂ ) ₁ SO ₃ ^- (wherein 1 is an integer of 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 of 1 to 10)

And the like are used. Particularly, the anion moiety containing a fluorine atom is preferably used since an ionic compound having a good ion dissociation property can be obtained. The anion forming the inorganic salt includes Cl ^- , Br ^- , I ^- , AlCl ₄ ^- , Al ₂ Cl ₇ ^- , BF ₄ ^- , PF ₆ ^- , ClO ₄ ^- , NO ₃ ^- , AsF ₆ ^- , SbF ₆ ^- , NbF ₆ ^- , TaF ₆ ^- , (CN) ₂ N ^- and the like. An anion is preferably a (perfluoroalkylsulfonyl) imide represented by the above general formula (4) such as (CF ₃ SO ₂ ) ₂ N ^- or (C ₂ F ₅ SO ₂ ) ₂ N ^- Particularly, (trifluoromethanesulfonyl) imide represented by (CF ₃ SO ₂ ) ₂ N ^- is preferable.

Specific examples of the organic salts of alkali metals include sodium acetate, sodium alginate, sodium ligninsulfonate, sodium toluenesulfonate, lithium hexafluorophosphate (LiPF ₆ ), LiCF ₃ SO ₃ , Li (CF ₃ SO ₂ ) ₂ N, _{Li (CF 3 SO 2) 2} N, Li (C 2 F 5 SO 2) 2 N, Li (C 4 F 9 SO 2) 2 N, Li (CF 3 SO 2) 3 C, KO 3 S (CF 2 ) ₃ SO ₃ K and LiO ₃ S (CF ₂ ) ₃ SO ₃ K, among which 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. are _{preferred, Li (CF 3 SO 2)} 2 N, Li (C ₂ F ₅ SO ₂ ) ₂ N and Li (C ₄ F ₉ SO ₂ ) ₂ N, and more preferred are fluorine-containing lithium imide salts such as lithium hexafluorophosphate (LiPF ₆ ), lithium bistrifluoro the methanesulfonyl imide _{(LiTFSI, Li (CF 3 SO} 2) 2 N) is particularly preferred.

Examples of inorganic salts of alkali metals include lithium perchlorate and lithium iodide.

&Lt; Organocathion-Anion Salt &gt;

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 pyridinium cation, piperidinium cation, pyrrolidinium cation, cation having pyrroline skeleton, cation having pyrrole skeleton, imidazolium cation, tetrahydropyrimidine Pyrazolium cation, pyrazolinium cation, tetraalkylammonium cation, trialkylsulfonium cation, tetraalkylphosphonium cation, and the like can be given.

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 ^{- _{3 COO -, CH 3 SO 3}} -, CF 3 SO 3 -, (CF 3 SO 2) 3 C -, AsF 6 -, SbF 6 -, NbF 6 -, TaF 6 -, (CN) 2 N -, C ^{_{4 F 9 SO 3 -, C}} 3 F 7 COO -, ((CF 3 SO 2) (CF 3 CO) N -, - O 3 S (CF 2) 3 SO 3 - or the following formula (4) to ( 7),

(4): _???????? (C _n F _{2n + 1} SO ₂ ) ₂ N ^- wherein n is an integer of 1 to 10,

(5): CF ₂ (C _m F _{2 m} SO ₂ ) ₂ N ^- (wherein m is an integer of 1 to 10)

(6): ^- O ₃ S (CF ₂ ) ₁ SO ₃ ^- (wherein 1 is an integer of 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 of 1 to 10)

And the like are used. Among these, anionic components containing a fluorine atom are preferably used because an ionic compound having good ion dissociability is obtained.

As a specific example of the organic cation-anion salt, a compound comprising a combination of the cationic component and the anion component is appropriately selected and used. For example, 1-butylpyridinium tetrafluoroborate, 1-butylpyridinium hexafluorophosphate, 1-butyl-3-methylpyridinium tetrafluoroborate, 1-butyl- Butyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imide, 1-butyl-3-methylpyridinium bis (pentafluoroethanesulfonyl) imide, 1- Methyl-1-pyrrolin tetrafluoroborate, 1-ethyl-2-phenylindole tetrafluoroborate, 1,2-dimethyl indole tetrafluoroborate, 1-ethylcarbazole tetra Ethyl-3-methylimidazolium trifluoroacetate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium trifluoroacetate, 3-methylimidazolium heptafluorobutyrate, 1-ethyl-3-methylimidazolium trifluoro Ethyl-3-methylimidazolium bis (trifluoromethyl) imidazolium, 1-ethyl-3-methylimidazolium perfluorobutanesulfonate, Ethyl-3-methylimidazolium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-3-methylimidazolium tris (trifluoromethanesulfonyl) imide Butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium trifluoroacetate, Methylimidazolium heptafluorobutyrate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium perfluorobutanesulfonate, 1-butyl- 3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-hexyl-3-methylimidazolium bromide, 1-hexyl-3-methylimidazolium chloride, 1- 3-methylimidazolium tetrafluoroborate, 1-hexyl-3-methylimidazolium hexafluorophosphate, 1-hexyl-3-methylimidazolium trifluoromethanesulfonate, 1-octyl- 3-methylimidazolium hexafluorophosphate, 1-hexyl-2,3-dimethylimidazolium tetrafluoroborate, 1,2-dimethyl-3-propyl (Trifluoromethanesulfonyl) imide, 1-methylpyrazolium tetrafluoroborate, 3-methylpyrazolium tetrafluoroborate, tetrahexylammonium bis (trifluoromethanesulfonyl) imide, di Allyl dimethyl ammonium tetrafluoroborate, diallyldimethyl ammonium trifluoromethanesulfonate, diallyldimethyl ammonium bis (trifluoromethanesulfonyl) imide, diallyldimethyl ammonium bis (pentafluoroethanesulfonyl) imide , N, N-diethyl-N-methyl-N- (2- N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium trifluoromethanesulfonate, N, (Trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (pentafluoroethanesulfonyl) Glycidyltrimethylammonium bis (pentafluoroethanesulfonyl) imide, glycidyltrimethylammonium bis (trifluoromethanesulfonyl) imide, glycidyltrimethylammonium bis (pentafluoroethanesulfonyl) imide, Butylpyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-butyl-3-methylpyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-ethyl- N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium (trifluoromethanesulfonyl) trifluoroacetamide, tri (Trifluoromethanesulfonyl) trifluoroacetamide, N, N-dimethyl-N- (trifluoromethanesulfonyl) trifluoroacetamide, diallyldimethylammonium (trifluoromethanesulfonyl) trifluoroacetamide, glycidyltrimethylammonium N-dimethyl-N-ethyl-N-butylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl- (Trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-hexylammonium bis (Trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-nonylammonium bis (trifluoromethanesulfonyl) (Trifluoromethanesulfonyl) imide, N, N-dimethyl-N-propyl-N-butylammonium bis (trifluoromethanesulfonyl) , N-dimethyl-N- N, N-dimethyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl- N, N-dimethyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl- Dimethyl-N-butyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl- N-dimethyl-N, N-dihexylammonium bis (trifluoromethanesulfonyl) imide, trimethylheptylammonium bis (trifluoromethanesulfonyl) imide, N, -Propylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, Methyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl- N-propyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, triethylpropylammonium bis (trifluoromethanesulfonyl) imide, triethylpentylammonium bis (trifluoromethanesulfonyl) imide (Trifluoromethanesulfonyl) imide, N, N-dipropyl-N-methyl-N-ethylammonium bis (trifluoromethanesulfonyl) imide, (Trifluoromethanesulfonyl) imide, N, N-dipropyl-N-butyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N N, N-diethylamino-bis (trifluoromethanesulfonyl) imide, N, N-dibutyl- N, N-dibutyl-N-methyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, trioctylmethylammonium bis (trifluoromethanesulfonyl) -Ethyl-N-propyl-N-pentyl Monyum (methanesulfonyl trifluoromethyl) bis-imide, 1-butyl-3-methyl-pyridin-1-ium trifluoromethanesulfonate. As commercial products thereof, for example, "CIL-314" (manufactured by Nippon Carryt Co., Ltd.) and "ILA2-1" (manufactured by Koei Kagaku Kogyo Co., Ltd.) can be used.

Further, examples thereof include tetramethylammonium bis (trifluoromethanesulfonyl) imide, trimethylethylammonium bis (trifluoromethanesulfonyl) imide, trimethylbutylammonium bis (trifluoromethanesulfonyl) imide, Trimethylpentylammonium bis (trifluoromethanesulfonyl) imide, trimethylheptylammonium bis (trifluoromethanesulfonyl) imide, trimethyloctylammonium bis (trifluoromethanesulfonyl) imide, tetraethylammonium bis (Trifluoromethanesulfonyl) imide, triethylbenzylammonium bis (trifluoromethanesulfonyl) imide, tetrabutylammonium bis (trifluoromethanesulfonyl) imide, tetrahexylammonium bis Sulfonyl) imide, and the like.

Further, for example, 1-dimethylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-ethylpyrrolidinium bis (trifluoromethanesulfonyl) imide, -Propylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-butylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-pentylpyrrolidinium bis Methyl-1-hexylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-heptylpyrrolidinium bis (trifluoromethanesulfonyl) imide, Ethyl-1-butylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-propylpyrrolidinium bis (trifluoromethanesulfonyl) Ethyl-1-pentylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-heptene Tilpyrrolidinium bis (trifluoro Propyl-1-butylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1,1-dipropylpyrrolidinium bis (trifluoromethanesulfonyl) imide, (Trifluoromethanesulfonyl) imide, 1-propylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-pentylpiperidinium bis (trifluoromethanesulfonyl) imide, (Trifluoromethanesulfonyl) imide, 1-methyl-1-ethylpiperidinium bis (trifluoromethanesulfonyl) imide, 1,1-dimethylpiperidinium bis Methyl-1-propylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-butylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl- Methyl-1-hexylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-heptylpiperidinium bis (trifluoromethanesulfonyl) imide, Fluoromethane Ethyl-1-butylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-propylpiperidinium bis (trifluoromethanesulfonyl) 1-pentylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-hexylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl- Propyl-1-butylpiperidinium bis (trifluoromethanesulfonyl) imide, 1,1-dipropylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-dimethylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1,1-dibutylpiperidinium bis (trifluoromethanesulfonyl) imide, Methyl-1-ethylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-propylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, Pyrrolidinium bis (pentafluoro Methyl-1-pentylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-hexylpyrrolidinium bis (pentafluoroethanesulfonyl) imide (Pentafluoroethanesulfonyl) imide, 1-ethyl-1-propylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-heptylpyrrolidinium bis -Butylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-pentylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-hexylpyrrolidinium bis (Pentafluoroethanesulfonyl) imide, 1-ethyl-1-heptylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1,1-dipropylpyrrolidinium bis (pentafluoroethanesulfonyl) Imide, 1-propyl-1-butylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1,1-dibutylpyrrolidinium bis (pentafluoroethanesulfonyl) Piperidinium bis (pentafluoro (Pentafluoroethanesulfonyl) imide, 1,1-dimethylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1 (Pentafluoroethanesulfonyl) imide, 1-methyl-1-propylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-butylpiperidinium bis Methyl-1-pentylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-hexylpiperidinium bis (pentafluoroethanesulfonyl) imide, Methyl-1-heptylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-propylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1- Ethyl-1-heptylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-pentylpiperidinium bis (pentafluoroethanesulfonyl) imide, Peridinium bis (pentafluoro Ethyl-1-heptylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-propyl-1-butylpiperidinium bis (pentafluoroethanesulfonyl) imide , 1,1-dipropylpiperidinium bis (pentafluoroethanesulfonyl) imide, and 1,1-dibutylpiperidinium bis (pentafluoroethanesulfonyl) imide.

In place of the cation component of the above-mentioned compound, there may be mentioned, for example, trimethylsulfonium cation, triethylsulfonium cation, tributylsulfonium cation, trihexylsulfonium cation, diethylmethylsulfonium cation, dibutylethyl sulphate Tetramethylphosphonium cation, tetramethylphosphonium cation, tetramethylphosphonium cation, tetramethylphosphonium cation, tetramethylphosphonium cation, tetramethylphosphonium cation, tetramethylphosphonium cation, tetramethylphosphonium cation, tetramethylphosphonium cation, tetramethylphosphonium cation and tetrahexylphosphonium cation.

In place of the bis (trifluoromethanesulfonyl) imide, bis (pentafluorosulfonyl) imide, bis (heptafluoropropanesulfonyl) imide, bis (nonafluorobutanesulfonyl) imide Heptafluoropropanesulfonyl trifluoromethanesulfonylimide, pentafluoroethanesulfonylonafluorobutanesulfonylimide, cyclohexane sulfonylimide, heptafluoropropanesulfonyl trifluoromethanesulfonylimide, pentafluoroethanesulfonyl nonafluorobutanesulfonylimide, cyclohexane Fluoropropane-1,3-bis (sulfonyl) imide anion, and the like.

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

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

Further, the acrylic pressure-sensitive adhesive composition used in the present invention may further contain additives such as a viscosity modifier, a release modifier, a tackifier, a plasticizer, a softener, a glass fiber, a glass bead, a metal powder, A pH adjuster (acid or base), an antioxidant, an ultraviolet absorber and the like may be suitably used as long as they do not deviate from the object of the present invention. These additives may also be formulated as emulsions.

(3) Polarizing film on which a pressure-sensitive adhesive layer is formed

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

The method of forming the pressure-sensitive adhesive layer is not particularly limited, but the acrylic pressure-sensitive adhesive composition may be coated on various substrates and dried by a dryer such as a heat oven to volatilize the solvent or the like to form a pressure- Or the pressure sensitive adhesive layer may be formed by applying the acrylic pressure sensitive adhesive composition directly onto the iodine polarizing film.

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

As the coating method for the substrate or the polarizing film, various methods are used. Specific examples thereof include fountain coaters, roll coats, kiss roll coats, gravure coats, reverse coats, roll brushes, spray coats, dip roll coats, bar coats, knife coats, air knife coats, curtain coats, And extrusion coating method using a coater or the like.

The drying conditions (temperature and time) are not particularly limited and can be appropriately set according to the composition, concentration, etc. of the acrylic pressure-sensitive adhesive composition. For example, the drying condition (temperature and time) is from 80 to 170 캜, preferably from 90 to 200 캜, Minute, preferably 2 to 30 minutes.

The thickness of the pressure-sensitive adhesive layer (after drying) is preferably 5 to 100 占 퐉, more preferably 10 to 60 占 퐉, and more preferably 12 to 40 占 퐉. If the thickness of the pressure-sensitive adhesive layer is less than 10 mu m, adhesion to an adherend becomes insufficient and durability at high temperature and high temperature and high humidity tends to be insufficient. On the other hand, when the thickness of the pressure-sensitive adhesive layer is more than 100 占 퐉, it is impossible to completely dry the pressure-sensitive adhesive layer sufficiently when the acrylic pressure-sensitive adhesive composition is applied and dried at the time of forming the pressure-sensitive adhesive layer, There is a tendency that nonuniformity occurs and the appearance problem becomes easier to present.

Examples of the constituent material of the release film include a resin film such as polyethylene, polypropylene, polyethylene terephthalate and polyester film, a porous material such as paper, cloth, nonwoven fabric, net, foam sheet, metal foil, And the like, but a resin film is preferably used because of its excellent surface smoothness.

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, a polyethylene terephthalate film, a polybutylene terephthalate Film, a polyurethane film, an ethylene-vinyl acetate copolymer film, and the like.

The thickness of the release film is usually 5 to 200 占 퐉, preferably 5 to 100 占 퐉. If necessary, the releasing film may be subjected to an antistatic treatment such as releasing treatment with a silicone, fluorine, long chain alkyl or fatty acid amide releasing agent, silica powder or the like, a coating type, a kneading type, a deposition type or the like . Particularly, the releasability from the pressure-sensitive adhesive layer can be further improved by suitably carrying out the surface treatment of the release film, such as silicone treatment, long-chain alkyl treatment or fluorine treatment.

The transparent resin film base material is not particularly limited, but various resin films having transparency are used. The resin film is formed of a single-layer film. For example, as the material thereof, a polyester resin such as polyethylene terephthalate and polyethylene naphthalate, an acetate resin, a polyether sulfone resin, a polycarbonate resin, a polyamide resin, a polyimide resin, a polyolefin resin, (Meth) acrylic resins, polyvinyl chloride resins, polyvinylidene chloride resins, polystyrene resins, polyvinyl alcohol resins, polyarylate resins, and polyphenylene sulfide resins. Of these, particularly preferred are polyester resins, polyimide resins and polyether sulfone resins.

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

Further, an anchor layer may be provided between the iodine-based polarizing film and the pressure-sensitive adhesive layer. The material for forming the anchor layer is not particularly limited, and examples thereof include various polymers, metal oxide sol, silica sol, and the like. Of these, polymers are particularly preferably used. The polymer may be used in any of the solvent-soluble type, water-dispersible type, and water-soluble type.

Examples of the polymers include polyurethane resins, polyester resins, acrylic resins, polyether resins, cellulose resins, polyvinyl alcohol resins, polyvinyl pyrrolidone, and polystyrene resins . Among these, a polyurethane resin, a polyester resin and an acrylic resin are particularly preferable. A crosslinking agent may be appropriately added to these resins. These other binder components may be used singly or in combination of two or more in accordance with their use.

When the anchor layer is formed of an aqueous dispersion type material, an aqueous dispersion type polymer is used. Examples of the water-dispersible polymer include those obtained by emulsifying various resins such as polyurethane and polyester with an emulsifier, and those obtained by self-emulsification by introducing a water-dispersible anion, cation, or nonionic group into the resin And the like.

The anchor agent may contain an antistatic agent. The antistatic agent is not particularly limited as long as it is a material capable of imparting conductivity. Examples of the antistatic agent include an ionic surfactant, a conductive polymer, a metal oxide, a carbon black, and a carbon nano material. Among them, And more preferably a water dispersible conductive polymer.

Examples of the water-soluble conductive polymer include polyaniline sulfonic acid (weight average molecular weight 150000 in terms of polystyrene conversion, manufactured by Mitsubishi Rayon Co., Ltd.), and water-dispersible conductive polymers include polythiophene conductive polymers (Denatron series ) And the like.

The blending amount of the antistatic agent is 70 parts by weight or less, preferably 50 parts by weight or less, based on 100 parts by weight of the polymers used in the anchor. From the standpoint of antistatic effect, it is preferable that the amount is 10 parts by weight or more, and more preferably 20 parts by weight or more.

Various additives may be added to the anchor agent for the purpose of suppressing deterioration of the pressure-sensitive adhesive layer or the polarizer produced when the anchor coat layer is brought into contact with the anchor coat layer, and various additives may be added for the purpose of imparting functions to the anchor coat layer . For example, antioxidants, deterioration inhibitors, ultraviolet absorbers, fluorescent whitening agents, and the like can be added.

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

The method for forming the anchor layer is not particularly limited and can be carried out by a generally known method. In forming the anchor layer, the iodine-based polarizing film may be subjected to activation treatment. Various methods can be employed for the activation treatment, and for example, corona treatment, low-pressure UV treatment, plasma treatment, or the like can be employed.

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

When the pressure-sensitive adhesive layer of the polarizing film on which the pressure-sensitive adhesive layer of the present invention is formed is exposed, the pressure-sensitive adhesive layer may be protected with a release film (separator) until it is provided for practical use. Examples of the release film include those described above. When a release film is used as the base material in the production of the pressure-sensitive adhesive layer, the releasing film can be used as a releasing film of a pressure-sensitive adhesive layer of a polarizing film on which a pressure-sensitive adhesive layer is formed by bonding an adhesive layer on the release film to an iodine- Therefore, it is possible to simplify the process.

2. Laminate

The laminate of the present invention is a laminate comprising a polarizing film on which the pressure-sensitive adhesive layer is formed and a member having a transparent conductive layer so that the pressure-sensitive adhesive layer of the polarizing film on which the pressure-sensitive adhesive layer is formed is in contact with the transparent conductive layer of the member having the transparent conductive layer .

As the polarizing film on which the pressure-sensitive adhesive layer is formed, the above-described polarizing film may be used.

The member having the transparent conductive layer is not particularly limited and a well-known member can be used. Examples of the member having the transparent conductive layer on the transparent substrate such as a transparent film and the member having the transparent conductive layer and the liquid crystal cell .

The transparent substrate may be a transparent substrate such as a resin film or a substrate made of glass or the like (for example, a sheet-like, film-like, or plate-like substrate), and a resin film is particularly preferable . The thickness of the transparent base material is not particularly limited, but is preferably about 10 to 200 占 퐉, more preferably about 15 to 150 占 퐉.

The material of the resin film is not particularly limited, but various plastic materials having transparency can be cited. For example, as the material thereof, a polyester resin such as polyethylene terephthalate and polyethylene naphthalate, an acetate resin, a polyether sulfone resin, a polycarbonate resin, a polyamide resin, a polyimide resin, a polyolefin resin, (Meth) acrylic resins, polyvinyl chloride resins, polyvinylidene chloride resins, polystyrene resins, polyvinyl alcohol resins, polyarylate resins and polyphenylene sulfide resins. Of these, particularly preferred are polyester resins, polyimide resins and polyether sulfone resins.

The surface of the transparent substrate is subjected to an etching treatment or a priming treatment such as sputtering, corona discharge, a flame, an ultraviolet ray irradiation, an electron beam irradiation, a chemical conversion or an oxidation in advance to form a transparent conductive layer The adhesion may be improved. Before forming the transparent conductive layer, it may be damped and cleaned by solvent cleaning, ultrasonic cleaning or the like, if necessary.

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

Examples of the ITO include crystalline ITO and noncrystalline (amorphous) ITO. The crystalline ITO can be obtained by applying a high temperature during sputtering or by further heating amorphous ITO. Since the deterioration due to iodine occurs remarkably in amorphous ITO, the polarizing film on which the pressure-sensitive adhesive layer of the present invention is formed 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, more preferably 12 to 60 nm, and more preferably 15 to 45 nm More preferably 18 to 45 nm, and particularly preferably 20 to 30 nm. If the thickness of the transparent conductive layer is less than 7 nm, deterioration of the transparent conductive layer due to iodine tends to occur, and the change in electrical resistance value of the transparent conductive layer tends to increase. On the other hand, when it exceeds 60 nm, the productivity of the transparent conductive layer deteriorates, the cost increases, and the optical characteristics also tend to decrease.

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

The thickness of the substrate having the transparent conductive layer is 15 to 200 탆. From the viewpoint of thinning, it is preferably 15 to 150 占 퐉, more preferably 15 to 50 占 퐉. When the substrate having the transparent conductive layer is used in a resistive film method, for example, a thickness of 100 to 200 mu m can be mentioned. When used in a capacitive method, for example, a thickness of 15 to 100 mu m is preferable, and more preferably 15 to 50 mu m, more preferably 20 to 50 mu m, more preferably 20 to 50 mu m, Do.

An undercoat layer, an oligomer-preventing layer, and the like can be formed between the transparent conductive layer and the transparent substrate, if necessary.

Examples of the member having the transparent conductive layer and the liquid crystal cell include a liquid crystal cell including a substrate (for example, a glass substrate or the like) / liquid crystal layer / substrate used for an image display device such as various liquid crystal display devices And a transparent conductive layer on the side not in contact with the liquid crystal layer of the substrate. When a color filter substrate is formed on a liquid crystal cell, a transparent conductive layer may be provided on the color filter. The method of forming the transparent conductive layer on the substrate of the liquid crystal cell is the same as described above.

3. Image display device

The laminate of the present invention can be applied to an image display apparatus (a liquid crystal display apparatus, an organic EL (electroluminescence) display apparatus, a PDP (plasma display panel), an electronic paper, etc.) (Member) constituting a device such as a touch panel (a touch panel or the like) or a substrate (member) used in these devices, but it can be preferably used in the production of an optical substrate for a touch panel . In addition, it can be used regardless of the touch panel method such as the resistance film method or the capacitance method.

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

The polarizing film having the pressure-sensitive adhesive layer of the present invention can suppress corrosion of the transparent conductive layer even when the transparent conductive layer is laminated on the pressure-sensitive adhesive layer of the polarizing film on which the pressure-sensitive adhesive layer is formed as described above, The increase in the surface resistance of the conductive layer can be suppressed. Therefore, if the pressure-sensitive adhesive layer of the polarizing film on which the pressure-sensitive adhesive layer is formed is in contact with the transparent conductive layer, the polarizing film on which the pressure-sensitive adhesive layer of the present invention is formed can be preferably used. For example, a liquid crystal panel having a polarizing film on which a pressure-sensitive adhesive layer of the present invention is formed and a transparent conductive layer is attached to the pressure-sensitive adhesive layer of the polarizing film on which the pressure-sensitive adhesive layer is formed and the transparent conductive layer of the liquid- .

More specifically, an image display device using a transparent conductive layer as an antistatic layer application and an image display device using a transparent conductive layer as an electrode of a touch panel can be given. 1, the polarizing film 1 / the pressure-sensitive adhesive layer 2 / the antistatic layer 3 / the glass substrate 1, The driving electrode 6, the glass substrate 4, the pressure sensitive adhesive layer 2, and the polarizing film 1, and the antistatic layer 3, the driving electrode 6, And an image display device formed of the transparent conductive layer. A polarizing film on which the pressure-sensitive adhesive layer of the present invention is formed can be used as the polarizing films (1, 2) on which the pressure-sensitive adhesive layer on the image side (viewing side) of the image display device is formed. The polarizing film 1 / the pressure-sensitive adhesive layer 2 / the antistatic layer and the sensor layer 7 / the glass substrate 4 / the antistatic layer / (In-cell type touch panel, Fig. 2) of the liquid crystal layer 5, the driving electrode and sensor layer 8, the glass substrate 4, the pressure-sensitive adhesive layer 2 and the polarizing film 1, / Adhesive layer 2 / antistatic layer and sensor layer 7 / sensor layer 9 / glass substrate 4 / liquid crystal layer 5 / driving electrode 6 / glass substrate 4 / pressure-sensitive adhesive layer 2 In which an antistatic layer and a sensor layer 7, a sensor layer 9 and a driving electrode 6 are formed of a transparent conductive layer, and the polarizing film 1 (on-cell type touch panel; . A polarizing film on which the pressure-sensitive adhesive layer of the present invention is formed can be used as the polarizing films (1, 2) on which the pressure-sensitive adhesive layer on the image side (viewing side) of the image display device is formed.

Example

Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to the following examples unless the gist of the present invention is exceeded. In the examples, all parts and percentages are by weight.

&Lt; Iodine Content in Polarizer &gt;

The content of iodine (content of iodine and / or iodine ion) in the polarizer was measured according to the following procedure.

1) A fluorescent X-ray intensity of a plurality of polarizers containing a predetermined amount of potassium iodide was measured to derive a relational expression between the iodine content and the fluorescent X-ray intensity.

2) Fluorescent X-ray of an iodine-based polarizer having an unknown iodine content was measured, and from this value, the iodine amount was calculated using the above-mentioned relational expression.

Production Example 1 (Production of polarizing film (1)

A stretched laminate was produced by air-assisted stretching at a stretching temperature of 130 DEG C on a laminate having a 9 mu m-thick polyvinyl alcohol (PVA) layer formed on an amorphous PET substrate. Next, the drawn laminate was immersed in a dyeing solution containing 0.1 part by weight of iodine and 0.7 part by weight of potassium iodide for 100 seconds with respect to 100 parts by weight of water to obtain a colored laminate. Further, the colored layered product was stretched in boric acid aqueous solution having a stretching temperature of 65 占 폚 to produce an optical film laminate including a PVA layer having a thickness of 4 占 퐉 which was integrally stretched with an amorphous PET substrate so that the total draw ratio was 5.94. By such two-step stretching, the PVA molecules of the PVA layer formed on the amorphous PET substrate are oriented at a high degree, and the iodine adsorbed by dyeing constitutes a highly functional polarizing layer oriented in one direction as a polyiodide ion complex, An optical film laminate including a PVA layer having a thickness of 4 占 퐉 could be produced. Further, a saponified 40 탆 thick acrylic resin film (transparent protective film (1)) was applied while applying a PVA adhesive to the surface of the polarizing layer of the optical film laminate, and then the amorphous PET substrate was peeled off , And a polarizing film having a transparent protective film only on one side using a thin iodine polarizer was produced. Hereinafter, this is referred to as a polarizing film (1). The iodine content of the polarizing film (1) was 5.1% by weight.

Production Examples 2 and 3 (Production of polarizing films (2) and (3)) [

Polarization with a transparent protective film only on one side using a thin iodine polarizer was carried out in the same manner as in Production Example 1 except that the dyeing time was changed from 60 seconds to 120 seconds (Production Example 2) and 180 seconds (Production Example 3) A film was produced. Hereinafter, these are referred to as polarizing films (2) and (3). The iodine content of the polarizing films (2) and (3) was 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 탆 was stretched to 3 times while dyeing in an iodine solution of 0.3% concentration at 30 캜 for 1 minute between rolls having different velocity ratios. Thereafter, the substrate was immersed in an aqueous solution containing boric acid at a concentration of 4% at 60 DEG C and potassium iodide at a concentration of 10% for 0.5 minute, and then stretched to a total draw ratio of 6 times. Subsequently, the substrate was washed by immersing in an aqueous solution containing potassium iodide at a concentration of 1.5% at 30 DEG C for 10 seconds and then dried at 50 DEG C for 4 minutes to obtain a polarizer having a thickness of 25 mu m and an iodine content of 2.3 wt%. An acrylic resin film (transparent protective film (1)) having a thickness of 40 占 퐉 was laminated on one surface of the polarizer with a polyvinyl alcohol-based adhesive to prepare a polarizing film. Hereinafter, this is referred to as a polarizing film 4. The iodine content of the polarizing film (4) was 2.3% by weight.

Production Example 5 (Production of polarizing film (5)) [

In Production Example 1, after the amorphous PET substrate was peeled off, a norbornene-based film (transparent protective film (2)) with a thickness of 25 탆 was laminated on the other side with a polyvinyl alcohol-based adhesive to prepare a polarizing film . Hereinafter, this is referred to as a thin polarizing film 5. The iodine content of the polarizing film 5 was 5.1% by weight.

Production Example 6 (Production of polarizing film (6)

An acrylic resin film (transparent protective film 1) having a thickness of 40 占 퐉 and a norbornene-based film (transparent protective film 2) having a thickness of 25 占 퐉 were placed on both surfaces of a polarizer having an iodine content of 2.3% by weight obtained in Production Example 4 And they were laminated with a polyvinyl alcohol-based adhesive to prepare a polarizing film. Hereinafter, this is referred to as a polarizing film 6. The iodine content of the polarizing film 6 was 2.3% by weight.

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

Production Example 7 (Preparation of solution containing acrylic polymer (A-1)) [

In a reaction vessel equipped with a condenser, a nitrogen inlet tube, a thermometer and a stirrer, 99 parts of butyl acrylate, 1 part of 4-hydroxybutyl acrylate, and 1 part of 2,2'-azobisisobutyronitrile ( AIBN) was added together with ethyl acetate in an amount of 1 part per 100 parts of the monomer (solid content), and the mixture was reacted at 60 DEG C for 7 hours under a nitrogen gas stream. Thereafter, ethyl acetate was added to the reaction solution to obtain a solution (solid content concentration: 30% by weight) containing an acrylic polymer (A-1) having a weight average molecular weight of 1,600,000.

Production Example 8 (Preparation of solution containing acrylic polymer (A-2)

In a reaction vessel equipped with a cooling tube, a nitrogen inlet tube, a thermometer and a stirrer, 99 parts of butyl acrylate, 1 part of 2-hydroxyethyl acrylate, and 1 part of AIBN as a initiator per 100 parts of the monomer (solid content) Ethyl acetate and the mixture was reacted at 60 DEG C for 7 hours in a nitrogen gas stream. Thereafter, ethyl acetate was added to the reaction solution to obtain a solution (solid content concentration: 30% by weight) containing an acrylic polymer (A-2) having a weight average molecular weight of 1,600,000.

Production Example 9 (Preparation of solution containing acrylic polymer (A-3)) [

100 parts of butyl acrylate and 1 part of 100 parts of AIBN as an initiator were added together with ethyl acetate to a reaction vessel equipped with a condenser, a nitrogen inlet tube, a thermometer and a stirrer, , And reacted at 60 DEG C for 7 hours. Thereafter, ethyl acetate was added to the reaction solution to obtain a solution (solid content concentration: 30% by weight) containing an acrylic polymer (A-3) having a weight average molecular weight of 1,600,000.

Production Example 10 (Production of a solution containing an acrylic polymer (A-4)

98.6 parts of butyl acrylate, 1 part of 4-hydroxybutyl acrylate, 0.4 part of acrylic acid, and 100 parts of a monomer (solid content) as an initiator were placed in a reaction vessel equipped with a thermometer, a condenser, Was added together with ethyl acetate, and the reaction was carried out at 60 占 폚 for 7 hours under a nitrogen gas stream. Thereafter, ethyl acetate was added to the reaction solution to obtain a solution (solid content concentration: 30% by weight) containing an acrylic polymer (A-4) having a weight average molecular weight of 1,600,000.

Production Example 11 (Preparation of solution containing acrylic polymer (A-5)) [

95 parts of butyl acrylate, 1 part of 4-hydroxybutyl acrylate, 4 parts of acrylic acid, and 100 parts of a monomer (solid content) as an initiator were placed in a reaction vessel equipped with a thermometer, a condenser, Was added together with ethyl acetate, and the reaction was carried out at 60 占 폚 for 7 hours under a nitrogen gas stream. Thereafter, ethyl acetate was added to the reaction solution to obtain a solution (solid content concentration: 30% by weight) containing an acrylic polymer (A-5) having a weight average molecular weight of 1,55,000.

Production Example 12 (Preparation of solution containing acrylic polymer (A-6)

A reactor was charged with 91 parts of butyl acrylate, 1 part of 2-hydroxyethyl acrylate, 8 parts of acrylic acid, and 100 parts of AIBN as a monomer (solid content) as an initiator in a reaction vessel equipped with a condenser, a nitrogen inlet tube, Was added together with ethyl acetate, and the mixture was reacted at 60 占 폚 for 9 hours under a nitrogen gas stream. Thereafter, ethyl acetate was added to the reaction solution to obtain a solution (solid content concentration: 30% by weight) containing an acrylic polymer (A-6) having a weight average molecular weight of 1,190,000.

Production Example 13 (Production of a solution containing an acrylic polymer (A-7)

In a reaction vessel equipped with a condenser, a nitrogen inlet tube, a thermometer and a stirrer, 99 parts of butyl acrylate, 1 part of 4-hydroxybutyl acrylate, and 1.5 parts of AIBN per 100 parts of the monomer (solid content) Ethyl acetate and the mixture was reacted at 60 DEG C for 7 hours in a nitrogen gas stream. Thereafter, ethyl acetate was added to the reaction solution to obtain a solution (solid content concentration: 30% by weight) containing an acrylic polymer (A-7) having a weight average molecular weight of 90,000.

Production Example 14 (Production of a solution containing an acrylic polymer (A-8)) [

A reaction vessel equipped with a condenser, a nitrogen inlet tube, a thermometer and a stirrer was charged with 84.9 parts of butyl acrylate, 0.1 part of 4-hydroxybutyl acrylate, 5 parts of acrylic acid, 10 parts of benzyl acrylate and 10 parts of AIBN One part of the monomer (solid content) was added together with ethyl acetate, and the mixture was reacted at 60 DEG C for 7 hours in a nitrogen gas stream. Thereafter, ethyl acetate was added to the reaction solution to obtain a solution (solid content concentration: 30% by weight) containing an acrylic polymer (A-8) having a weight average molecular weight of 1,800,000.

The weight average molecular weights of the acrylic polymers obtained in Production Examples 7 to 14 were measured by the following measuring methods.

&Lt; Measurement of weight average molecular weight (Mw) of acrylic polymer &

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

Device: manufactured by Toso Co., Ltd., HLC-8220GPC

column :

Sample column: TSKguardcolumn Super HZ-H (1 piece) + TSKgel Super HZM-H (2 pieces)

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

Flow rate: 0.6 ml / min

Injection volume: 10 μl

Column temperature: 40 DEG C

Eluent: THF

Injection sample concentration: 0.2 wt%

Detector: differential refractometer

The weight average molecular weight was calculated by polystyrene conversion.

Example 1

(Adjustment of acrylic pressure-sensitive adhesive composition)

(Trade name: Takenate D110N, manufactured by Mitsui Chemicals, Inc.) was used as a crosslinking agent per 100 parts of the solid content of the solution (solid concentration 30% by weight) containing the acrylic polymer (A-1) , 0.3 part of dibenzoyl peroxide, 0.03 part of Phosphanol SM-172 (trade name, manufactured by Toho Chemical Industry Co., Ltd.) as a phosphoric acid compound, 0.03 part of? -Glycidoxypropyl 0.075 part of trimethoxysilane (trade name: KBM-403, Shin-Etsu Chemical Co., Ltd.) as a phenol-based antioxidant and 0.075 part of pentaerythritol tetrakis [3- (3,5- -Hydroxyphenyl) propionate (IRGANAOX 1010, manufactured by BASF Japan K.K.) were blended to obtain an acrylic pressure-sensitive adhesive composition.

(Production of a polarizing film having a pressure-sensitive adhesive layer)

The acrylic pressure-sensitive adhesive composition was uniformly coated on the surface of a polyethylene terephthalate film (substrate) treated with a silicone-based releasing agent with a fountain coater and dried in an air circulating thermostat oven at 155 캜 for 2 minutes to form a pressure- Mu m of a pressure-sensitive adhesive layer was formed. Then, a separator having a pressure-sensitive adhesive layer formed thereon was adhered to the surface of the polarizing film 1 having no protective film to prepare a polarizing film having a pressure-sensitive adhesive layer.

Examples 2 to 5

A polarizing film having a pressure-sensitive adhesive layer was prepared in the same manner as in Example 1 except that the amount of the phosphoric acid compound added was changed from 0.03 part to the number of parts shown in Table 3. [

Example 6

Except that 0.03 part of Phosphanol SM-172 (trade name, manufactured by Toho Chemical Industry Co., Ltd.) was changed to 0.1 part of Phosphanol RS-410 (Toho Chemical Industry Co., Ltd.) A polarizing film was formed.

Example 7

Except that 0.03 part of Phosphanol SM-172 (trade name, manufactured by Toho Chemical Industry Co., Ltd.) was changed to 0.1 part of Phosphanol RS-710 (Toho Chemical Industry Co., Ltd.) A polarizing film was formed.

Example 8

Except that 0.03 part of Phosphanol SM-172 (trade name, manufactured by Toho Chemical Industry Co., Ltd.) was changed to 0.05 part of DBP (manufactured by Joho Chemical Co., Ltd.) Respectively.

Example 9

Except that 0.03 part of Phosphanol SM-172 (trade name, manufactured by Toho Chemical Industry Co., Ltd.) was changed to 0.03 part of phosphoric acid (reagent grade) (manufactured by Wako Pure Chemical Industries, Ltd.) Thereby forming a polarizing film having a layer formed thereon.

Examples 10-14

Except that the solution containing the acrylic polymer (A-1) obtained in Preparation Example 7 was changed to a solution containing the acrylic polymer (A-2) to (A-6) obtained in Production Examples 8 to 12, respectively, In the same manner as in Example 1, a polarizing film having a pressure-sensitive adhesive layer was produced.

Examples 15 to 17

Except that polarizing films (1) were changed to polarizing films (2), (3) and (4) in Example 1 (preparation of polarizing film with pressure-sensitive adhesive layer) A polarizing film having a pressure-sensitive adhesive layer formed thereon was produced.

Example 18

(Adjustment of acrylic pressure-sensitive adhesive composition)

(Trade name: Takenate D110N, manufactured by Mitsui Chemicals, Inc.) was used as a crosslinking agent per 100 parts of the solid content of the solution (solid concentration 30% by weight) containing the acrylic polymer (A-1) , 0.3 part of dibenzoyl peroxide, 0.03 part of Phosphanol SM-172 (trade name, manufactured by Toho Chemical Industry Co., Ltd.) as a phosphoric acid compound, 0.03 part of? -Glycidoxypropyl 0.075 part of trimethoxysilane (trade name: KBM-403, Shin-Etsu Chemical Co., Ltd.) and 0.5 part of lithium bistrifluoromethane sulfonylimide (manufactured by Morita Chemical Industry Co., Ltd.) , And 0.3 part of pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (IRGANAOX 1010, manufactured by BASF Japan Ltd.) To obtain an acrylic pressure-sensitive adhesive composition.

(Production of a polarizing film having a pressure-sensitive adhesive layer)

A polarizing film having a pressure-sensitive adhesive layer was prepared in the same manner as in Example 1 except that the acrylic pressure-sensitive adhesive composition was used.

Example 19

0.5 part of lithium bistrifluoromethanesulfonylimide (manufactured by MORITA CHEMICAL INDUSTRIES, LTD.) Was added to 1-methyl-1-ethylpyrrolidinium bis (trifluoromethanesulfonyl) imide (Kishida Chemical Co., Ltd.) was prepared in the same manner as in Example 18 except that the pressure-sensitive adhesive layer was changed to 0.5 part.

Example 20

The solution containing the acrylic polymer (A-1) obtained in Production Example 7 was changed to the acrylic ester copolymer (A-8) obtained in Production Example 14 and further treated with Phosphanol SM-172 (trade name, ) Was changed to 0.05 part of phosphoric acid (reagent grade) (manufactured by Wako Pure Chemical Industries, Ltd.) to prepare a polarizing film having a pressure-sensitive adhesive layer.

Example 21

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

Example 22

Except that 0.03 part of Phosphanol SM-172 (trade name, manufactured by Toho Chemical Industry Co., Ltd.) was changed to 0.01 part of MP-4 (trade name, acid value: 670 mgKOH / g, manufactured by Daihachi Chemical Industry Co., Ltd.) A polarizing film on which a pressure-sensitive adhesive layer was formed was prepared in the same manner as in Example 1.

Example 23

Except that the addition amount of MP-4 (trade name, acid value: 670 mgKOH / g, manufactured by Daihachi Chemical Industry Co., Ltd.) was changed from 0.01 part to 0.06 part, Respectively.

Example 24

The solution containing the acrylic polymer (A-1) obtained in Production Example 7 was changed to the acrylic ester copolymer (A-8) obtained in Production Example 14 and further treated with Phosphanol SM-172 (trade name, ) Was changed to 0.1 part of MP-4 (trade name, acid value: 670 mgKOH / g, manufactured by Daihachi Chemical Industry Co., Ltd.) Respectively.

Examples 25 and 26

Except that the addition amount of MP-4 (trade name, acid value: 670 mgKOH / g, manufactured by Daihachi Chemical Industry Co., Ltd.) was changed from 0.1 part to 0.8 part and 3 parts, A polarizing film was formed.

Example 27

The solution containing the acrylic polymer (A-1) obtained in Production Example 7 was changed to the acrylic ester copolymer (A-8) obtained in Production Example 14 and further treated with Phosphanol SM-172 (trade name, ), 0.03 part of MP-4 (trade name, acid value: 670 mgKOH / g, manufactured by Daihachi Chemical Industry Co., Ltd.) and 0.01 part of phosphoric acid (reagent grade) (Wako Pure Chemical Industries, Ltd.) , A polarizing film in which a pressure-sensitive adhesive layer was formed was prepared in the same manner as in Example 1. [

Example 28

The solution containing the acrylic polymer (A-1) obtained in Production Example 7 was changed to the acrylic ester copolymer (A-8) obtained in Production Example 14 and further treated with Phosphanol SM-172 (trade name, ) Was changed to a mixture of 0.04 parts of Phosphanol SM-172 (trade name, manufactured by Toho Chemical Industry Co., Ltd.) and 0.01 part of phosphoric acid (reagent grade) (manufactured by Wako Pure Chemical Industries, Ltd.) A polarizing film on which a pressure-sensitive adhesive layer was formed was prepared in the same manner as in Example 1.

Examples 29 to 34

A polarizing film on which a pressure-sensitive adhesive layer was formed was prepared in the same manner as in Example 1 except that the kind of the acrylic polymer-containing solution, the kind of the phosphoric acid compound, and the amount thereof were changed to the kinds and amounts shown in Table 3.

Comparative Example 1

The procedure of Example 1 was repeated except that the solution containing the acrylic polymer (A-1) was changed to a solution containing the acrylic polymer (A-2) obtained in Production Example 8 and no phosphate ester was used To prepare a polarizing film having a pressure-sensitive adhesive layer.

Comparative Example 2

The procedure of Example 1 was repeated except that the solution containing the acrylic polymer (A-1) was changed to a solution containing the acrylic polymer (A-3) obtained in Production Example 9 and no phosphate ester was used To prepare a polarizing film having a pressure-sensitive adhesive layer.

Comparative Example 3

The procedure of Example 1 was repeated except that the solution containing the acrylic polymer (A-1) was changed to a solution containing the acrylic polymer (A-5) obtained in Production Example 11 and no phosphate ester was used To prepare a polarizing film having a pressure-sensitive adhesive layer.

Comparative Example 4

The procedure of Example 1 was repeated except that the solution containing the acrylic polymer (A-1) was changed to a solution containing the acrylic polymer (A-7) obtained in Preparation Example 13 and no phosphate ester was used To prepare a polarizing film having a pressure-sensitive adhesive layer.

Examples 35 and 36

A pressure-sensitive adhesive layer was formed in the same manner as in Example 1, except that the polarizing film (1) was changed to the polarizing films (5) and (6) in the production of the polarizing film To prepare a polarizing film. Further, the pressure-sensitive adhesive layer was laminated on the protective film 2 side.

Example 37

A polarizing film in which a pressure-sensitive adhesive layer was formed 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 Respectively. Further, the pressure-sensitive adhesive layer was laminated on the protective film 2 side.

Comparative Example 5

Except that the polarizing film (1) was changed to the polarizing film (5) in Example 1 (preparation of a polarizing film having a pressure-sensitive adhesive layer) without using phosphate ester in the preparation of the acrylic pressure-sensitive adhesive composition A polarizing film on which a pressure-sensitive adhesive layer was formed was prepared in the same manner as in Example 1. Further, the pressure-sensitive adhesive layer was laminated on the protective film 2 side.

Comparative Example 6

A solution containing the acrylic polymer (A-1) was changed to a solution containing the acrylic polymer (A-3) obtained in Production Example 9, and a phosphate ester was added to the solution containing the acrylic polymer A polarizing film on which a pressure-sensitive adhesive layer was formed was produced in the same manner as in Example 1 except that the polarizing film (1) was changed to the polarizing film (6) in the production of the polarizing film Respectively. Further, the pressure-sensitive adhesive layer was laminated on the protective film 2 side.

Phosphoric acid compounds used in Examples and Comparative Examples were analyzed as follows. The results are shown in Table 2.

(Analysis method)

The composition of the phosphate compound used in Examples and Comparative Examples was calculated based on the measurement results of ³¹ P-NMR (Acetone-d6, room temperature). The mol% was calculated from the integrated value of the peaks obtained by the measurement, and then the content ratio (% by weight) of the alcohol component of the ester with respect to the alkyl chain was calculated.

( ³¹ P-NMR measurement conditions)

Measuring devices: Bruker Biospin, AVANCEIII-400

Observation frequency: 160 ㎒ ( ³¹ P)

Flip angle: 30 °

Measurement solvent: Acetone-d6 (medium acetone)

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 is a compound which is a hydrocarbon residue having 1 to 18 carbon atoms, in which either one of R ¹ and R ² in the general formula (1) is a hydrogen atom and the other may contain an oxygen atom Is a compound in which R ¹ is a hydrogen atom in the case of Formula (2)), and the phosphoric acid diester is a compound in which R ¹ and R ² in the general formula (1) are hydrocarbons having 1 to 18 carbon atoms (In the case of formula (2), a compound wherein R ¹ is a hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom). For example, in the case of phosphapone SM-172, the "monoester" is a compound in which R ¹ = H, R ³ = C ₈ H ₁₇ and n = 0 in the general formula (2) Represents a compound wherein R ¹ = R ³ = C ₈ H ₁₇ , n = 0 in the formula (2).

<Corrosion resistance test>

A conductive film (trade name: P400L, manufactured by Nitto Denko Co., Ltd.) having an ITO layer formed on its surface was cut into 15 mm x 15 mm, and the samples obtained in Examples and Comparative Examples Was cut and cut into 8 mm x 8 mm and then autoclaved at 50 DEG C and 5 atm for 15 minutes to obtain a measurement sample of corrosion resistance. The resistance value of the measurement sample thus obtained was measured using a measuring device described later, and this was regarded as an &quot; initial resistance value &quot;.

Thereafter, the sample for measurement was placed in an environment at a temperature of 60 DEG C and a humidity of 90% for 500 hours, and the resistance value was measured as &quot; resistance value after wet heat &quot;. The resistance value was measured using HL5500PC manufactured by Accent Optical Technologies. The resistance value change ratio (%) was calculated from the "initial resistance value" and the "resistance value after wet heat" measured as described above according to the following equation, and evaluated according to the following evaluation criteria.

(Evaluation standard)

?: Less than 150% of resistance value change rate (resistance value rise due to humid heat is small (corrosion resistance is good))

?: The change rate of the resistance value is 150% or more and less than 300%

DELTA: Change rate of the resistance value is 300% or more and less than 400%

X: Change rate of resistance value is 400% or more (increase in resistance value due to humid heat is large (corrosion resistance failure))

&Lt; Durability test of pressure-sensitive adhesive (peeling and foaming) &gt;

The separator film of the polarizing film sample in which the pressure-sensitive adhesive layer obtained in the Examples and Comparative Examples were formed was peeled off and bonded to the ITO side of the glass with no alkali glass and the following amorphous ITO formed thereon. The resultant was placed in an autoclave After the treatment, the mixture was placed in a heating oven at 80 캜 and 100 캜 and a constant temperature and humidity chamber at 60 캜 / 90% RH and 85 캜 / 85% RH. The peeling and foaming of the polarizing film after 500 hours were visually observed and evaluated according to the following evaluation criteria. The polarizing film peeling and foaming of the polarizing film after observing the environment at 85 캜 and -40 캜 for 300 cycles of 1 cycle for 1 hour (heat shock test (HS test)) were visually observed and evaluated by the following evaluation criteria.

◎: No peeling or foaming was observed at all.

○: The peeling or foaming was observed to the extent that it could not be confirmed by the naked eye.

?: Small peeling or foaming that can be confirmed with naked eyes was observed.

X: Apparent peeling or foaming was observed.

(Production 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 ITO thin film without crystallization. The Sn ratio of the crystalline ITO thin film was 3% by weight. The Sn ratio of the ITO thin film was calculated from the weight of Sn atom / (weight of Sn atom + weight of In atom).

The abbreviations in the tables are as follows.

(Phosphoric acid compound)

B-1: phosphapol SM-172, acid value: 219 mgKOH / g, mono-di mixture, manufactured by Toho Chemical Industry Co.,

B-2: phosphanol RS-410, acid value: 105 mgKOH / g, mono-di mixture, manufactured by Toho Chemical Industry Co.,

B-3: phosphanol RS-710, acid value: 62 mgKOH / g, mono-di mixture, manufactured by Toho Chemical Industry Co.,

B-4: DBP, acid value: 266 mgKOH / g, mono-di mixture, manufactured by Joho Chemical Co.,

B-5: Phosphoric acid (reagent grade), manufactured by Wako Pure Chemical Industries, Ltd.

B-6: MP-4, acid value: 670 mgKOH / g, mono-di mixture, manufactured by Daihachi Chemical Industry Co.,

B-7: mono -N- butyl phosphate _{(O = P (OH) 2} (OC 4 H 9), Product Nomber: CDS001281), SIGMA-ALDRICH prepared

(Crosslinking agent)

Peroxide system: dibenzoyl peroxide

Isocyanate type: trimethylolpropane xylylene diisocyanate (trade name: Takenate D110N) (manufactured by Mitsui Chemicals)

(Ionic compound)

E-1: Lithium bistrifluoromethanesulfonylimide (manufactured by Morita Chemical Industry Co., Ltd.)

E-2: 1-Methyl-1-ethylpyrrolidinium bis (trifluoromethanesulfonyl) imide (Kishida Chemical Co., Ltd.)

The iodine content in Tables 3 and 5 is the content (% by weight) of iodine and / or iodide ion in the polarizer.

1: polarizing film
2: Pressure-sensitive adhesive layer
3: antistatic layer
4: glass substrate
5: liquid crystal layer
6: driving electrode
7: Antistatic layer and sensor layer
8: Driving electrode and sensor layer
9: Sensor layer

Claims (22)

(I) at least one side of an iodine-based polarizing film having a transparent protective film on at least one side of an iodine-based polarizer containing iodine and /
[Chemical 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.)
, And a pressure sensitive adhesive layer formed of an acrylic pressure sensitive adhesive composition containing at least one phosphoric acid compound selected from the group consisting of a compound represented by the general formula (1) and a (meth) acrylic polymer, Sensitive adhesive layer is formed. The method according to claim 1,
Wherein the content of iodine and / or iodide ion in the iodine-based polarizer is 1 to 14% by weight. 3. The method of claim 2,
Wherein a content of iodine and / or iodide ion in the iodine-based polarizer is 3 to 12% by weight. 4. The method according to any one of claims 1 to 3,
Wherein the phosphate compound comprises phosphoric acid and is a hydrocarbon residue having 1 to 18 carbon atoms which may be an oxygen atom in either one of R ¹ and R ² of the general formula (1) Ester, and a phosphoric acid diester which is a hydrocarbon residue having 1 to 18 carbon atoms, in which R ¹ and R ² in the general formula (1) may contain an oxygen atom, And a pressure-sensitive adhesive layer formed on the pressure-sensitive adhesive layer. 5. The method of claim 4,
Wherein the phosphoric acid compound is a mixture comprising phosphoric acid and phosphoric acid monoester. 6. The method 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. 7. The method according to any one of claims 1 to 6,
Wherein the iodine polarizing film is a single polarizing protective polarizing film having a transparent protective film on only one side of the iodine polarizer and a surface of the single polarizing protective polarizing film not having a transparent protective film, Wherein the pressure-sensitive adhesive layer is formed on the polarizing film. 8. The method according to any one of claims 1 to 7,
Wherein the thickness of the iodine polarizer is 10 占 퐉 or less. 9. The method according to any one of claims 1 to 8,
Wherein the total thickness of the iodine-based polarizing film is 80 占 퐉 or less. 10. The method according to any one of claims 1 to 9,
A pressure-sensitive adhesive sheet comprising the pressure-sensitive adhesive layer of a polarizing film according to any one of claims 1 to 9, and a transparent conductive layer of a member having a transparent conductive layer, film. 11. The method according to any one of claims 1 to 10,
Wherein the phosphoric acid compound is added in an amount of 0.001 to 4 parts by weight based on 100 parts by weight of the (meth) acryl-based polymer. 12. The method according to any one of claims 1 to 11,
Wherein the (meth) acryl-based polymer comprises, as a monomer unit, an alkyl (meth) acrylate and a monomer containing a hydroxyl group. 13. The method of claim 12,
And the hydroxyl group-containing monomer is 4-hydroxybutyl acrylate. 14. The method according to any one of claims 1 to 13,
Wherein the weight average molecular weight of the (meth) acrylic polymer is from 1.2 million to 3 million. 15. The method according to any one of claims 1 to 14,
Wherein the acrylic pressure sensitive adhesive composition further comprises a crosslinking agent. 16. The method of claim 15,
Wherein the cross-linking agent is at least one cross-linking agent selected from the group consisting of a peroxide-based cross-linking agent and an isocyanate-based cross-linking agent. 17. The method according to any one of claims 1 to 16,
Wherein the acrylic pressure sensitive adhesive composition further comprises an ionic compound. A polarizing film on which a pressure-sensitive adhesive layer according to any one of claims 1 to 17 is formed and a transparent electroconductive member having a transparent electroconductive layer are laminated to a pressure-sensitive adhesive layer of a polarizing film on which the pressure- To form a laminate. 19. The method of claim 18,
Wherein the transparent conductive layer is formed of indium tin oxide. 20. The method of claim 19,
Wherein the indium tin oxide is amorphous indium tin oxide. A liquid crystal display device comprising a pressure sensitive adhesive layer of a polarizing film on which a pressure sensitive adhesive layer according to any one of claims 1 to 17 is formed and a liquid crystal panel having a transparent conductive layer are laminated on a pressure sensitive adhesive layer of a polarizing film on which the pressure sensitive adhesive layer is formed, Layer are in contact with each other. An image display apparatus characterized by using the laminate according to any one of claims 18 to 20 as a touch panel.

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