KR102230320B1 - 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.In the present invention, on at least one surface of an iodine-based polarizing film having a transparent protective film on at least one surface of an iodine-based polarizer containing iodine and/or iodine ion, the following general formula (1):

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom.) A polarizing film having a pressure-sensitive adhesive layer, the polarizing film, characterized in that it has a pressure-sensitive adhesive layer formed of an acrylic pressure-sensitive adhesive composition containing at least one phosphoric acid-based compound selected from the group consisting of a multimer of the represented compound, and a (meth)acrylic polymer. And a laminate having a substrate having a transparent conductive layer bonded thereto, an image display device having the polarizing film and a liquid crystal panel having a transparent conductive layer bonded, and an image display device using the laminate as a touch panel.

Description

A polarizing film, a laminate, and an image display device with an adhesive layer formed thereon TECHNICAL FIELD

The present invention relates to a polarizing film in which an adhesive layer was formed. In addition, the present invention is a laminate in which the polarizing film on which the pressure-sensitive adhesive layer is formed and a substrate having a transparent conductive layer are bonded together, and an image display in which the polarizing film on which the pressure-sensitive adhesive layer is formed and a liquid crystal panel having a transparent conductive layer are bonded. A device and an image display device using the laminate as a touch panel.

Recently, a transparent conductive film such as an indium tin oxide (ITO) thin film has been widely used in various applications. For example, the transparent conductive film is formed on a side opposite to the side in contact with the liquid crystal layer of a transparent substrate constituting the liquid crystal cell of a liquid crystal display device using a liquid crystal cell such as an in-plane switching (IPS) method, and serves as an antistatic layer. It is known to do. In addition, the transparent conductive film in which the transparent conductive film is formed on a transparent resin film is used for an electrode substrate of a touch panel, and, for example, a liquid crystal display device or an image display device used in a mobile phone or a portable music player, and the touch panel are combined. Input devices to be used are widely spread.

As an input device used in combination with a touch panel and an image display device, a transparent conductive film in which a transparent conductive layer is formed on a transparent substrate made of a conventional glass plate or a transparent resin film is used on a liquid crystal display device. The outcell type installed on the upper side) has been widespread, but recently an on-cell type in which an electrode made of a transparent conductive film is formed on an upper glass substrate of a liquid crystal cell, or an electrode made of a transparent conductive film is placed inside the liquid crystal cell. Various configurations are known, such as an in-cell type. It is also known to realize a touch panel function by using an ITO layer as an antistatic layer of an image display device as a touch sensor and patterning it.

In a liquid crystal display device or an image display device using such a transparent conductive film, in recent years, there is a strong demand for weight reduction and thickness reduction, and it is also desired to reduce the thickness and weight of the polarizing film used in the liquid crystal display device or the like. As a method for reducing the thickness and weight of a polarizing film, for example, a single-sided protective polarizing film provided with a transparent protective film only on one side of a polarizer, and a method for producing a thin polarizing film in which the film thickness of the polarizer itself was reduced are known.

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

Japanese Patent No. 4751481 Specification Japanese Patent No. 491205 Specification

For example, in the case of using a transparent conductive film as an antistatic layer application, a polarizing film in which an adhesive layer is formed is usually laminated on a liquid crystal cell having the antistatic layer, and an antistatic layer made of a transparent conductive film and a polarizing film form an adhesive layer. It is bonded through. In addition, when a transparent conductive film is used as an electrode for a touch panel, depending on the configuration of the touch panel, a polarizing film in which an adhesive layer is formed is laminated on the transparent conductive film for electrodes, and an antistatic layer made of a transparent conductive film and polarized light The film may be bonded through the pressure-sensitive adhesive layer.

When the polarizing film is an iodine-based polarizing film, as described above, when the transparent conductive layer and the iodine-based polarizing film are bonded and subjected to a humidification endurance test (usually endurance test), the resistance value of the transparent conductive layer increases. There was a case. It has been found that such an increase in the resistance value is due to the iodine contained in the polarizer oozing into the pressure-sensitive adhesive layer and the transparent conductive layer corroding when the iodine reaches the transparent conductive layer.

For example, in the thin iodine polarizer having a thickness of 10 μm or less described in Patent Documents 1 and 2, it is necessary to increase the iodine concentration in the polarizer in order to have the same polarization characteristics as the conventional polarizer. When a polarizing film containing a high polarizer is bonded to a transparent conductive layer, it has been found that corrosion of the transparent conductive layer due to iodine is likely to occur. Moreover, even when an iodine-based polarizing film for single-sided protection was used, since the transparent conductive layer was directly bonded to the iodine-based polarizer via an adhesive layer, it was found that corrosion of the transparent conductive layer is liable to occur.

Accordingly, the present invention provides a polarizing film 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 laminated on the transparent conductive layer. It aims to do. In addition, the present invention is a laminate in which the polarizing film on which the pressure-sensitive adhesive layer is formed and a substrate having a transparent conductive layer are bonded, an image display device in which the polarizing film on which the pressure-sensitive adhesive layer is formed and a liquid crystal panel having a transparent conductive layer are bonded, the Another object of the present invention is to provide an image display device using a laminate as a touch panel.

The present inventors, as a result of earnestly examining in order to solve the above problems, found that the above object can be achieved by using a pressure-sensitive adhesive layer formed of an acrylic pressure-sensitive adhesive composition containing a phosphoric acid-based compound and a (meth)acrylic polymer. , Came to complete the present invention.

That is, the present invention is on at least one surface of an iodine polarizing film having a transparent protective film on at least one surface of an iodine polarizer containing iodine and/or iodine ions,

The following general formula (1):

[Formula 1]

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom.)

It has a pressure-sensitive adhesive layer formed of an acrylic pressure-sensitive adhesive composition containing at least one phosphoric acid-based compound selected from the group consisting of a compound represented by and a multimer of the compound represented by the general formula (1), and a (meth)acrylic polymer. It relates to a polarizing film in which the pressure-sensitive adhesive layer is formed. Here, the ``iodine polarizer containing iodine and/or iodine ions'' refers to an iodine polarizer containing iodine, an iodine polarizer containing iodine ions, and an iodine polarizer containing both iodine and iodine ions. In the invention, any can be preferably used.

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

Phosphoric acid, which is a hydrocarbon residue having 1 to 18 carbon atoms in which the phosphoric acid-based compound contains phosphoric acid, and one of R ¹ and R ^{2 in the general formula (1) is a hydrogen atom and the other may contain an oxygen atom. The monoester and R 1} and R ² in the general formula (1) contain at least one phosphate ester selected from the group consisting of a phosphate diester which is a hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom. It is preferably a mixture.

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

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

The iodine-based polarizing film is a one-sided protective polarizing film having a transparent protective film only on one side of the iodine-based polarizer, and the side of the one-sided protective polarizing film not having a transparent protective film and the pressure-sensitive adhesive layer are in contact. desirable.

It is preferable that the thickness of the iodine polarizer is 10 μm or less.

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

Moreover, it is preferable to use by bonding so that 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 substrate having a transparent conductive layer are in contact.

It is preferable that the amount of the phosphoric acid-based compound added is 0.001 to 4 parts by weight based on 100 parts by weight of the (meth)acrylic polymer.

It is preferable that the (meth)acrylic polymer contains an alkyl (meth)acrylate and a hydroxyl group-containing monomer as monomer units.

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

It is preferable that the weight average molecular weight of the (meth)acrylic polymer is 1.2 million to 3 million.

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

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

In addition, the present invention is characterized in that the polarizing film on which the pressure-sensitive adhesive layer is formed and a transparent conductive member having a transparent conductive layer are bonded so that 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 member are in contact with each other. It relates to a laminated body.

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

In the present invention, the pressure-sensitive adhesive layer of the polarizing film with the pressure-sensitive adhesive layer and a liquid crystal panel having a transparent conductive layer are bonded so that the pressure-sensitive adhesive layer of the polarizing film with the pressure-sensitive adhesive layer and the transparent conductive layer of the liquid crystal panel are in contact with each other. It relates to an image display device, characterized in that.

Further, the present invention relates to an image display device, wherein the laminate is used as a touch panel.

Although the polarizing film with the pressure-sensitive adhesive layer of the present invention uses an iodine polarizer, even when a transparent conductive layer is laminated on the pressure-sensitive adhesive layer of the polarizing film with the pressure-sensitive adhesive layer, corrosion of the transparent conductive layer can be suppressed, It is possible to suppress an increase in the surface resistance of the conductive layer. This is because the pressure-sensitive adhesive layer of the polarizing film with the pressure-sensitive adhesive layer of the present invention contains a phosphoric acid-based compound. Specifically, for example, when the phosphoric acid-based compound contains phosphoric acid, a passivation film is formed from phosphoric acid and metal ions in the transparent conductive layer on the surface of the transparent conductive layer, and as a result, iodine in the polarizer reaches the surface of the transparent conductive layer. It is thought that this is because it does not migrate, and corrosion of the transparent conductive layer is inhibited. In addition, when the phosphoric acid-based compound contains a phosphoric acid compound (e.g., phosphoric acid ester, etc.), the phosphoric acid compound is selectively adsorbed on the surface of the transparent conductive layer to form a film, and as a result, iodine in the polarizer is converted into a transparent conductive layer. It is thought that this is because it does not migrate to the surface, and corrosion of the transparent conductive layer is inhibited.

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

1. Polarizing film with adhesive layer

The polarizing film in which the pressure-sensitive adhesive layer of the present invention is formed is on 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/or iodine ions,

The following general formula (1):

[Formula 2]

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom.)

It has a pressure-sensitive adhesive layer formed of an acrylic pressure-sensitive adhesive composition containing at least one phosphoric acid-based compound selected from the group consisting of a compound represented by and a multimer of the 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 surface of an iodine-based polarizer containing iodine and/or iodine ions. In the present invention, even if it is a single-sided protective polarizing film having a transparent protective film on one side of the iodine-based polarizer, or a double-sided protective polarizing film having a transparent protective film on both sides of the iodine-based polarizer, when using a single-sided protective polarizing film, The effect of the present invention is remarkable. Moreover, even if it is a double-sided protective polarizing film, the effect of this invention is remarkable even when the thickness of the transparent protective film on the side in contact with an adhesive layer is thin (for example, 25 micrometers or less). In addition, when the polarizing film is a single-sided protective polarizing film, the pressure-sensitive adhesive layer can be directly formed on the surface of the polarizer on the side not having the transparent protective film.

As the iodine polarizer, any polarizer containing iodine and/or iodine ions can be used. For example, polyvinyl alcohol (PVA)-based films, partially formalized PVA-based films, and ethylene/vinyl acetate copolymers Examples of a hydrophilic polymer film such as a partially saponified film, uniaxially stretched by adsorbing iodine, are exemplified. Among these, a polarizer made of a PVA-based film and iodine is preferable. The thickness of these polarizers is not particularly limited, but is generally about 5 to 80 µm.

The polarizer obtained by uniaxially stretching a PVA-based film by dyeing it with iodine can be produced by, for example, dyeing by immersing PVA in an aqueous solution of iodine and stretching to 3 to 7 times the original length. If necessary, it may be immersed in an aqueous solution such as potassium iodide which may contain boric acid, zinc sulfate, or zinc chloride. Further, if necessary, before dyeing, the PVA-based film may be immersed in water and washed with water. By washing the PVA-based film with water, it is possible to wash the surface of the PVA-based film with an anti-blocking agent or contamination, and by swelling the PVA-based film, there is also an effect of preventing non-uniformity such as non-uniformity in dyeing. Stretching may be performed after dyeing with iodine, stretching may be performed while dyeing, or may be dyed with iodine after stretching. It can also be stretched in an aqueous solution such as boric acid or potassium iodide or in a water bath.

In addition, in the present invention, a thin iodine polarizer having a thickness of 10 µm or less can also be preferably used. Speaking from the viewpoint of thinning, the thickness is preferably 1 to 7 µm. Since such a thin iodine polarizer has little thickness unevenness, has excellent visibility, and has little dimensional change, it is preferable that it is excellent in durability, and further, the thickness as a polarizing film is also reduced in thickness.

As a thin polarizer, representatively, Japanese Patent Application Laid-Open No. 51-069644 or Japanese Patent Application Laid-Open No. 2000-338329, International Publication No. 2010/100917, International Publication No. 2010/100917, or Japanese Patent No. 4751481 B. The thin polarizing film described in Japanese Patent Application Laid-Open No. 2012-073563 is mentioned. These thin polarizing films can be obtained by a manufacturing method including a step of stretching a PVA-based resin layer and a resin substrate for stretching in a laminated state and a step of dyeing. With this manufacturing method, even if the PVA-based resin layer is thin, it is possible to extend without problems such as fracture due to stretching by being supported by the resin substrate for stretching.

The thin polarizing film can be stretched at a high magnification to improve polarization performance among manufacturing methods including a step of stretching and dyeing in a laminated state, so that the pamphlet of International Publication No. 2010/100917, International Publication No. 2010/100917 It is preferable that it is obtained by a manufacturing method including a step of stretching in an aqueous boric acid solution described in Unexamined Publication No. 2010/100917 pamphlet or Japanese Patent No. 4751481 specification or Japanese Unexamined Patent Publication No. 2012-073563, and in particular, Japanese Patent No. 4751481 specification or It is preferably obtained by a manufacturing method including a step of auxiliary aerial stretching before stretching in an aqueous boric acid solution described in Japanese Patent Application Laid-Open No. 2012-073563.

Moreover, the content of iodine and/or iodine ion (hereinafter, referred to as iodine content may be referred to as iodine content) of the iodine polarizer used in the present invention may be 1 to 14% by weight or 3 to 12% by weight in the polarizer. It may be, and it may be 4 to 7.5% by weight. The polarizing film with the pressure-sensitive adhesive layer of the present invention can suppress an increase in surface resistance of the transparent conductive layer laminated on the polarizing film with the pressure-sensitive adhesive layer even if the iodine content in the iodine-based polarizer is as large as the above range. This is because the phosphate-based compound contained in the pressure-sensitive adhesive layer forms a film on the surface of the transparent conductive layer, so that iodine contained in the iodine-based polarizing film does not migrate to the surface of the transparent conductive layer, resulting in corrosion of the transparent conductive layer. I think it is because it is hindered. Specifically, when the phosphoric acid-based compound contains phosphoric acid, the phosphoric acid forms a passivation film with metal ions in the transparent conductive layer on the surface of the transparent conductive layer, and the phosphoric acid-based compound is a phosphoric acid compound (e.g., phosphoric acid Ester, etc.), the phosphoric acid compound can be selectively adsorbed on the surface of the transparent conductive layer to form a film.

As a material for forming a transparent protective film formed on one side or both sides of the iodine polarizer, it is preferable to have excellent transparency, mechanical strength, thermal stability, moisture barrier properties, isotropic properties, and the like. For example, polyester polymers such as polyethylene terephthalate and polyethylene naphthalate, cellulose polymers such as diacetyl cellulose and triacetyl cellulose, acrylic polymers such as polymethyl methacrylate, polystyrene or acrylonitrile-styrene copolymer Styrene polymers, such as (AS resin), polycarbonate polymers, etc. are mentioned. In addition, polyethylene, polypropylene, polyolefin having a cyclo-based or norbornene structure, polyolefin-based polymers such as ethylene-propylene copolymers, vinyl chloride-based polymers, amide-based polymers such as nylon or aromatic polyamide, imide-based polymers, liquor Pone polymer, polyether sulfone polymer, polyether ether ketone polymer, polyphenylene sulfide polymer, vinyl alcohol polymer, vinylidene chloride polymer, vinyl butyral polymer, arylate polymer, polyoxymethylene polymer, Epoxy polymers, blends of the polymers, etc. are also exemplified as examples of polymers forming the transparent protective film. The transparent protective film can also be formed as a cured layer of a heat-curable, ultraviolet-curable resin such as acrylic, urethane, acrylic urethane, epoxy, and silicone.

The thickness of the protective film can be appropriately determined, but is generally about 1 to 500 µm in terms 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 a water-based adhesive or the like. Examples of the water-based adhesive include isocyanate-based adhesives, polyvinyl alcohol-based adhesives, gelatin-based adhesives, vinyl-based latex-based, water-based polyurethanes, and water-based polyesters. In addition to the above, examples of the adhesive between the polarizer and the transparent protective film include an ultraviolet curable adhesive and an electron beam curable adhesive. The adhesive for an electron beam-curable polarizing film shows preferable adhesiveness with respect to the said various transparent protective films. Moreover, a metal compound filler can be made to contain in the adhesive agent used by this invention.

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

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

(2) adhesive layer

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

The following general formula (1):

[Formula 3]

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom.)

It contains a phosphoric acid-based compound selected from the group consisting of a compound represented by and a multimer of the compound represented by the general formula (1), and a (meth)acrylic polymer.

As the phosphoric acid-based compound, as will be described later, phosphoric acid, phosphoric acid esters, or salts, dimers, and trimers thereof may be mentioned. These will be described in detail below.

In General Formula (1), R ¹ and R ² are each independently a hydrogen atom or a hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom. As a C1-C18 hydrocarbon residue which may contain an oxygen atom, a C1-C18 alkyl group, a C1-C18 alkenyl group, a C6-C18 aryl group, -(CH ₂ CH ₂ O) _n R ³ (R ³ is a C1-C18 alkyl group, a C1-C18 alkenyl group, or a C6-C18 aryl group, and n is an integer of 0-15.) etc. are mentioned. Moreover, the alkyl group and the alkenyl group may be linear or branched. Among these, as the C1-C18 hydrocarbon residue, a C1-C10 linear or branched alkyl group and a C6-C18 aryl group are preferable, and a C2-C6 linear or branched alkyl group is more desirable.

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

Moreover, in this invention, it is preferable that the compound represented by general formula (1) is an acidic phosphoric acid ester. Here, the acidic phosphoric acid ester is a case where ^{both R 1} and R ^{2 in the} general formula (1) are hydrocarbon residues having 1 to 18 carbon atoms which may contain an oxygen atom (diester product) or R ¹ , R ^{In the} case of a hydrocarbon residue having 1 to 18 carbon atoms in which one of 2 is a hydrogen atom and the other may contain an oxygen atom (monoester), for example, the following general formula (2):

[Formula 4]

(In the formula, R ¹ is the same as the 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 .)

The phosphate ester compound represented by is mentioned.

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 those similar to those 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 a hydrogen atom or a linear or branched C1-C10 It is more preferable that it is an alkyl group of, and it is more preferable that it is a hydrogen atom or a C2-C6 linear or branched alkyl group. As R ³ , a C1-C18 alkyl group, a C1-C18 alkenyl group, or a C6-C18 aryl group is mentioned, It is preferable that it is a C1-C18 alkyl group and a C6-C18 aryl group, A C1-C10 alkyl group is more preferable, and a C2-C6 alkyl group is more preferable. Moreover, n is an integer of 0-15, and it is preferable that it is an integer of 0-10. In addition, in the present invention, it _{is preferable from the viewpoint of preventing deterioration that does not contain a polyethylene oxide structure (CH 2} CH ₂ O) (that is, n = 0 in the formula (2)).

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

Further, in the present invention, two or more types of compounds represented by the general formula (2) may be mixed and used, or a mixture of the compound represented by the general formula (2) and the phosphoric acid may be used. 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 additionally added to the mixture of the monoester and the diester to be used. It is desirable to do it.

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

As a commercial item of the phosphate ester compound represented by the said general formula (2), "phosphanol SM-172" manufactured by Toho Chemical Industries, Ltd. (R ¹ = R ³ = C ₈ H ₁₇ of 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 of the general formula (2), n = 0, mono-di Mixture, acid value: 158 mgKOH/g), "phosphanol BH-650" (R ¹ = R ³ = C ₄ H ₉ of the general formula (2), n = 1, mono-di mixture, acid value: 388 mgKOH) /g), "phosphanol RS-410" (R ¹ = R ³ = C ₁₃ H ₂₇ of the general formula (2), n = 4, mono-di mixture, acid value: 105 mgKOH/g), "phosphanol ^{RS-610" (R 1} = C ₁₃ H ₂₇ , R ³ = C ₁₃ H ₂₇ , n = 6 of the general formula (2), mono-di mixture, acid value: 82 mgKOH/g), "phosphanol RS- ^{710" (R 1} = C ₁₃ H ₂₇ , R ³ = C ₁₃ H ₂₇ , n = 10 of the general formula (2), mono-di mixture, acid value: 62 mgKOH/g), "phosphanol ML-220" ^{(R 1} = R ³ = C ₁₂ H ₂₅ of the general formula (2), n = 2, mono-di mixture), ``phosphanol ML-200'' (R <sup>1</sup> = R <sup>3</sup> = C <sub>12 of the general formula (2)</sub> H <sub>25</sub> , n = 0, mono-di mixture), ``phosphanol ED-200'' (R ¹ = R ³ = C ₈ H ₁₇ , n = 1, mono-di mixture of general formula (2)), ``phos Phanol RL-210" (R <sup>1</sup> = R <sup>3</sup> = C <sub>18</sub> H <sub>37</sub> of the general formula (2), n = 2, mono-di mixture), ``phosphanol GF-339 (R ¹ = R of the general formula (2)) ³ = C ₆ H ₁₃ to C ₁₀ H ₂₁ mixture, n = 0, mono-di mixture), "phosphanol GF-199" (R ¹ = R ³ = C ₁₂ H ₂₅ , n of the general formula (2)) = 0, mono-di mixture), "phosphanol RL-310" (general ^{R 1} = R ³ = C ₁₈ H ₃₇ of formula (2), n = 3, mono-di mixture), ``phosphanol LP-700'' (R <sup>1</sup> = R <sup>3</sup> = C <sub>6</sub> H <sub>5 of the general formula (2)</sub> , n = 6, mono-di mixture), Daihachi Chemical Industries Co., Ltd. ``AP-1'' (R ¹ = R ³ = CH ₃ of general formula (2), n = 0, mono-di mixture, Acid value: 650 mgKOH/g or more), "AP-4" (R ¹ = R ³ = C ₄ H ₉ of the general formula (2), n = 0, mono-di mixture, acid value: 452 mgKOH/g) , "DP-4" (R ¹ = R ³ = C ₄ H ₉ , n = 0, mono-di mixture, acid value: 292 mgKOH/g of the general formula (2)), "MP-4" (general formula (2) of R ¹ = H, R ³ = C ₄ H ₉ , n = 0, mono-di mixture, acid value: 670 mgKOH/g), "AP-8" (R ¹ of general formula (2) = R ³ = C ₈ H ₁₇ , n = 0, mono-di mixture, acid value: 306 mgKOH/g), “AP-10” (R ^{1 in the} general formula (2) = R ³ = C ₁₀ H ₂₁ , n = 0, mono-di mixture, acid value: 263 mgKOH/g), "MP-10" (R ¹ = H, R ³ = C ₁₀ H ₂₁ of the general formula (2), n = 0, mono-di mixture , Acid value: 400 mgKOH/g), "JP-508" manufactured by Johoku Chemical Co., Ltd. (R ¹ = R ³ = C ₈ H ₁₇ of the general formula (2), n = 0, mono-di mixture, Acid value: 288 mgKOH/g), "JP-513" (R ¹ = R ³ = C ₁₃ H ₂₇ of the general formula (2), n = 0, mono-di mixture), "JP-524R" (general formula (2) of R ¹ = R ³ = C ₂₄ H ₄₉ , n = 0, mono-di mixture), ``DBP'' (R ¹ = R ³ = C ₄ H ₉ of the general formula (2), n = 0, Mono-D mixture, acid value: 266 mgKOH/g), "LB-58" (R ¹ = R ³ = C ₈ H ₁₇ of the general formula (2), n = 0, Diester, acid value: 173 mgKOH/g), Nikko Chemicals Co., Ltd. "Nikko DDP-2" (R ¹ = R ³ = C ₁₂ H ₂₅ to C ₁₅ H ₃₁ of the general formula (2)) Mixture, n = 2), mono-N-butyl phosphate manufactured by SIGMA-ALDRICH (O = P(OH) ₂ (OC ₄ H ₉ ^{), R 1} = H, R ³ = C ₄ H of the general formula (2) ₉ , n = 0, Product Nomber: CDS001281, monoester) and the like, and salts thereof. In addition, the said "mono-di mixture" is C1-C18 which may contain ^{monoester (R 1 = H of general formula (2)) and diester (R 1} = oxygen atom of general formula (2)). In the case of phosphanol SM-172, for example, in the case of phosphanol SM-172, a monoester (R ¹ = H, R ³ = C ₈ H ₁₇ , n = 0 of the general formula (2)) and, It shows that it is a mixture of ^{diester (R 1} = R ³ = C ₈ H ₁₇ , n = 0 of the general formula (2)). The mixing ratio of the monoester and diester of the said "mono-di mixture" can be calculated from the measurement result of ^{31 P-NMR.} About the measurement method, it is as described in an Example.

As the phosphoric acid-based compound used in the present invention, 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)), or a salt or multimer thereof may be used alone. Although it may be used or may be used in combination of two or more, from the viewpoint of the adsorption effect on the adherend (especially, a metal or metal oxide, or an adherend having a layer made of metal or metal oxide), And a mixture of two or more selected from the group consisting of phosphoric acid diesters, and containing phosphoric acid, and more preferably a mixture containing one or more phosphoric acid esters selected from the group consisting of phosphoric acid monoesters and phosphoric acid diesters. It is preferred, and it is particularly preferred that it is a mixture comprising a phosphoric acid monoester and phosphoric acid. In the present invention, one selected from the group consisting of phosphoric acid, phosphoric acid monoester, and phosphoric acid diester may be used alone, but when phosphoric acid is used alone, the pot life of the pressure-sensitive adhesive composition may be insufficient. Further, since phosphoric acid is a highly polar compound and has insufficient compatibility with an acrylic polymer, phosphoric acid bleeds out to the surface of the pressure-sensitive adhesive layer, and as a result, a problem may arise in terms of durability. In addition, when phosphoric acid is not used and only phosphoric acid esters (phosphoric acid monoesters and/or phosphoric acid diesters) are used, a problem may arise in durability under very severe conditions (eg, heat cycle test, etc.). In the present invention, it is most preferable to use a phosphoric acid-based compound containing phosphoric acid and a phosphoric acid monoester from the viewpoint of the balance of corrosion inhibition of the transparent conductive layer and durability under very severe conditions. Moreover, although the total amount of phosphoric acid and phosphoric acid monoester is not specifically limited, It is preferable that it is 80 weight% or more in 100 weight% of a phosphoric acid compound. Here, the phosphate 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 (general formula (2) In the case of ), R ¹ is a compound in which R 1 is a hydrogen atom), and the phosphate diester is a compound in which R ¹ and R ² in the general formula (1) are hydrocarbon residues having 1 to 18 carbon atoms which may contain an oxygen atom. (In the case of general formula (2), it is a compound which is a C1-C18 hydrocarbon residue which ^{R<1> may contain an oxygen atom).}

The adsorption effect on the adherend (especially metal or metal oxide) is considered to be related to the ``law of hard and soft acid groups'', defined by the HSAB rule, for the adherend and the phosphoric acid-based compound. It is thought that the adsorption effect is high by combining a soft base with a base and a soft acid, and a high deterioration prevention effect is obtained as a result. That is, for example, In of ITO corresponds to a hard acid defined by the HSAB rule, and a phosphoric acid-based compound becomes a soft base from a hard base in the order of phosphoric acid, a phosphate monoester, and a phosphate diester. It is considered that it can effectively adsorb to ITO, and as a result, a high deterioration prevention effect is obtained.

Moreover, when using a mixture of a monoester body and a diester body, it is preferable that it is a mixture containing a monoester body in a large amount. The mixing ratio (weight ratio) of the mixture of the monoester body and the diester body is preferably monoester body: diester body = 6:4 to 9:1, more preferably 7:3 to 9:1 . From the above reasons, it is preferable that the monoester body is contained in a large amount because the adsorption effect on the adherend is high.

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

Further, the acid value of the phosphoric acid compound used in the present invention is preferably 900 mgKOH/g or less, more preferably 50 to 800 mgKOH/g, and preferably 10 to 700 mgKOH/g. In addition, from the viewpoint of productive handling, the acid value of the phosphoric acid compound is preferably 400 mgKOH/g or less, more preferably 50 to 400 mgKOH/g, and more preferably 50 to 350 mgKOH/g. And it is particularly preferably 100 to 300 mgKOH/g. The phosphoric acid compound may act as a reaction catalyst for a crosslinking reaction depending on the kind of crosslinking agent described later (for example, an isocyanate crosslinking agent), and in that case, the pot life as an adhesive may be shortened. By setting the acid value of the phosphoric acid compound in the above range, it is possible to suppress the action as a reaction catalyst, which is preferable from the viewpoint of the pot life of the pressure-sensitive adhesive. Moreover, it is preferable from the viewpoint that an effect can be exhibited efficiently to add the phosphoric acid compound which has an acid value in the said range by the addition amount mentioned later.

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

The amount of the phosphoric acid-based compound added is preferably 0.001 to 4 parts by weight, more preferably 0.001 to 3 parts by weight, more preferably 0.001 to 2 parts by weight, based on 100 parts by weight of the (meth)acrylic polymer described later, It is particularly preferably 0.005 to 1 part by weight, more preferably 0.01 to 1 part by weight, and particularly preferably 0.02 to 0.2 part by weight. When the amount of the phosphoric acid compound is within the above range, an increase in the surface resistance value of the transparent conductive layer can be suppressed, and durability against heating and humidification can be improved, which is preferable. Further, in the present invention, as described above, phosphoric acid compounds such as phosphoric acid and phosphoric acid esters can be used in combination, but in that case, it can be added so that the total amount is within the above range.

In the present invention, it is transparent even if a transparent conductive layer is laminated on the pressure-sensitive adhesive layer surface of the polarizing film on which the pressure-sensitive adhesive layer is formed by using a polarizing film having a pressure-sensitive adhesive layer formed of an acrylic pressure-sensitive adhesive composition containing the phosphoric acid-based compound. It is possible to suppress an increase in the surface resistance of the conductive layer. When phosphoric acid is contained in the phosphoric acid-based compound, the phosphoric acid forms a passivation film with metal ions in the transparent conductive layer on the surface of the transparent conductive layer, and iodine in the polarizer does not migrate to the surface of the transparent conductive layer, as a result of which it is transparent. It is thought that this is because corrosion of the conductive layer is inhibited, and when the phosphoric acid compound contains a phosphoric acid compound (for example, phosphoric acid ester, etc.), the phosphoric acid compound is selectively adsorbed to the surface of the transparent conductive layer to form a film. Therefore, it is considered that 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.

Regarding the corrosion referred to herein, in the metal oxide, corrosion occurs in a mechanism different from that of generally known metal corrosion. In the case of a metal oxide such as ITO, since iodine derived from a polarizer permeates into the metal oxide layer and lowers the carrier mobility of the metal oxide, an increase in the resistance value occurs.

In the present invention, an excellent corrosion inhibitory effect can be exhibited against corrosion of a metal oxide as described above, and particularly, a more favorable effect can be exhibited with respect to a transparent conductive layer made of a metal oxide.

The (meth)acrylic 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 an alkyl (meth) acrylate and a hydroxyl polymer. It is preferable that it is obtained by polymerizing a monomer component containing an actual group-containing monomer. In addition, alkyl (meth)acrylate refers to an alkyl acrylate and/or an alkyl methacrylate, and has the same meaning as (meth) of this invention.

As the alkyl group related to the alkyl (meth)acrylate, various types of linear or branched chain can be used. Specific examples of the alkyl (meth) acrylate, for example, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t -Butyl (meth)acrylate, n-pentyl (meth)acrylate, isopentyl (meth)acrylate, isoamyl (meth)acrylate, n-hexyl (meth)acrylate, heptyl (meth)acrylate, 2 -Ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate , n-dodecyl(meth)acrylate, isomiristyl(meth)acrylate, n-tridecyl(meth)acrylate, tetradecyl(meth)acrylate, stearyl(meth)acrylate, octadecyl(meth)acrylate ) Acrylate, or dodecyl (meth) acrylate, etc. can be illustrated. These can be used alone or in combination. Among these, an alkyl (meth)acrylate having an alkyl group having 4 to 18 carbon atoms is preferred, a (meth)acrylate having an alkyl group having 4 to 10 carbon atoms is more preferred, and n-butyl (meth)acrylate, 2- Ethylhexyl (meth)acrylate is more preferred, and n-butyl (meth)acrylate is particularly preferred.

The alkyl (meth)acrylate is preferably 50 parts by weight or 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, It is more preferably 80 parts by weight or more, and particularly preferably 90 parts by weight or more.

In addition, as the hydroxyl group-containing monomer, one 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, and 6-hydroxyhexyl ( Meth)acrylate, 8-hydroxyoctyl(meth)acrylate, 10-hydroxydecyl(meth)acrylate, 12-hydroxylauryl(meth)acrylate, (4-hydroxymethylcyclohexyl)methyl( Meth)acrylate, etc. are mentioned, and these can be used individually by 1 type or in mixture of 2 or more types. Among these, 4-hydroxybutyl acrylate is preferable. In addition, in the case of using an isocyanate crosslinking agent as a crosslinking agent to be described later, it is preferable to use 4-hydroxybutyl acrylate as a hydroxyl group-containing monomer, since the crosslinking point with the isocyanate group of the isocyanate crosslinking agent can be efficiently secured. .

The hydroxyl group-containing monomer is preferably 10 parts by weight or less, more preferably 0.1 to 10 parts by weight, and still more 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 contain the alkyl (meth)acrylate having an alkyl group having 4 to 18 carbon atoms, optionally, the hydroxyl group-containing monomer, etc., but these monomers In addition, a carboxyl group-containing monomer, an aryl group-containing monomer, and other copolymerization monomers can be used as the monomer component.

As the carboxyl group-containing monomer, those having a polymerizable functional group having an unsaturated double bond such as a (meth)acryloyl group or a vinyl group, and having a carboxyl group can be used without particular limitation. Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and the like. 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 based on 100 parts by weight of the monomer component forming the (meth)acrylic polymer, and the addition amount that has little effect on the transparent conductive layer in particular From the viewpoint of, 6 parts by weight or less are more preferable, 2 parts by weight or less are more preferable, and 0.5 parts by weight or less are particularly preferable.

As the aryl group-containing monomer, one 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)acrylate aryl esters such as phenyl (meth)acrylate and benzyl (meth)acrylate.

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

Other copolymerization monomers are not particularly limited as long as they have 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 and boric (meth)acrylate. (Meth)acrylic acid alicyclic hydrocarbon esters such as nil and isobornyl (meth)acrylate; Vinyl esters such as vinyl acetate and vinyl propionate; For example, styrene-based monomers such as styrene; For example, epoxy group-containing monomers such as glycidyl (meth)acrylate and methylglycidyl (meth)acrylate; For example, alkoxy group-containing monomers such as methoxyethyl (meth)acrylate and ethoxyethyl (meth)acrylate; Cyano group-containing monomers, such as acrylonitrile and methacrylonitrile, for example; Functional monomers, such as 2-methacryloyloxyethyl isocyanate, for example; For example, olefin-based monomers such as ethylene, propylene, isoprene, butadiene, and isobutylene; For example, vinyl ether-based monomers such as vinyl ether; For example, halogen atom-containing monomers, such as vinyl chloride, etc. are mentioned.

Moreover, as a copolymerizable monomer, For example, Maleimide-type monomers, such as N-cyclohexyl maleimide, N-isopropyl maleimide, N-lauryl maleimide, and N-phenyl maleimide; For example, N-methyl itaconimide, N-ethyl itaconimide, N-butyl itaconimide, N-octyl itaconimide, N-2-ethylhexyl itaconimide, N-cyclo Itaconimide-based monomers such as hexyl itaconimide and N-lauryl itaconimide; For example, N-(meth)acryloyloxymethylenesuccinimide, N-(meth)acryloyl-6-oxyhexamethylenesuccinimide, N-(meth)acryloyl-8-oxyoctamethylene Succinimide-based monomers such as succinimide; For example, styrenesulfonic acid, allylsulfonic acid, 2-(meth)acrylamide-2-methylpropanesulfonic acid, (meth)acrylamidepropanesulfonic acid, sulfopropyl (meth)acrylate, (meth)acryloyloxynaphthalenesulfonic acid, etc. Sulfonic acid group-containing monomers are mentioned.

In addition, as a copolymerizable monomer, for example, glycol-based acrylic esters such as polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxyethylene glycol (meth)acrylate, and methoxypolypropylene glycol (meth)acrylate. Monomer; In addition, for example, a heterocyclic ring such as tetrahydrofurfuryl (meth)acrylate or fluorine (meth)acrylate, an acrylic acid ester-based monomer containing a halogen atom, and the like can be mentioned.

Further, a polyfunctional monomer can be used as the copolymerizable monomer. Examples of the polyfunctional monomer include compounds having two or more unsaturated double bonds such as a (meth)acryloyl group and a vinyl group. For example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetraethylene glycol di (meth) (Mono or poly) (mono or poly) alkyl such as (mono or poly) ethylene glycol di (meth) acrylate such as acrylate or (mono or poly) propylene glycol di (meth) acrylate such as propylene glycol di (meth) acrylate In addition to ene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, pentaerythritol di(meth)acrylate, trimethylolpropanetri(meth) Esterified products 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; And compounds having a reactive unsaturated double bond such as allyl (meth)acrylate and vinyl (meth)acrylate. In addition, as a polyfunctional monomer, polyester (meth)acrylic in which two or more unsaturated double bonds such as (meth)acryloyl group and vinyl group are added as the same functional group as the monomer component to a skeleton such as polyester, epoxy, urethane, etc. Rate, epoxy (meth)acrylate, urethane (meth)acrylate, and the like can also be used.

The ratio of the other copolymerization monomers is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, more preferably 15 parts by weight or less, based on 100 parts by weight of the monomer component forming the (meth)acrylic polymer. , 10 parts by weight or less is particularly preferred. If the ratio of the copolymerization monomer is too high, there is a concern that adhesive properties such as a decrease in adhesion 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 be deteriorated.

The weight average molecular weight of the (meth)acrylic polymer used in the present invention is preferably in the range of 1.2 million to 3 million, more preferably 1.2 million to 2.7 million, and still more preferably 1.2 million to 2.5 million. When the weight average molecular weight is less than 1.2 million, there are cases where it is not preferable from the viewpoint of heat resistance. Moreover, when the weight average molecular weight is less than 1.2 million, the low molecular weight component increases in the adhesive composition, and the said low molecular weight component bleeds out from the adhesive layer, and there existed a case where transparency was impaired. Further, the pressure-sensitive adhesive layer obtained by using a (meth)acrylic polymer having a weight average molecular weight of less than 1.2 million has inferior solvent resistance and mechanical properties in some cases. Moreover, when the weight average molecular weight is larger than 3 million, a large amount of diluting solvent is required in order to adjust the viscosity for coating, which is not preferable from the viewpoint of cost. Moreover, since the weight average molecular weight is in the said range, it is preferable also from a viewpoint of corrosion resistance and durability. The weight average molecular weight is measured by GPC (gel permeation chromatography) and refers to a value calculated in terms of polystyrene.

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

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

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

As a polymerization initiator, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-amidinopropane)dihydrochloride, 2,2'-azobis[2-(5 -Methyl-2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis(2-methylpropionamidine) 2 sulfate, 2,2'-azobis(N,N'- Dimethyleneisobutylamidine), 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]hydrate (trade name: VA-057, manufactured by Wako Pure Chemical Industries, Ltd.), etc. Azo initiator, potassium persulfate, persulfates such as ammonium persulfate, di(2-ethylhexyl)peroxydicarbonate, di(4-t-butylcyclohexyl)peroxydicarbonate, di-sec-butylperoxydicarbonate , t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, dilauroyl peroxide, di-n-octanoyl peroxide, 1,1,3,3- Tetramethylbutylperoxy-2-ethylhexanoate, di(4-methylbenzoyl)peroxide, dibenzoylperoxide, t-butylperoxyisobutylate, 1,1-di(t-hexylperoxy)cyclo Peroxide-based initiators such as hexane, t-butyl hydroperoxide, and hydrogen peroxide, redox initiators in which a peroxide and a reducing agent such as a combination of persulfate and sodium hydrogen sulfite, and a combination of peroxide and sodium ascorbate, and the like are mentioned. It is not limited to these.

The polymerization initiator may be used alone or in combination of two or more, but the content as a whole is about 0.005 to 1 part by weight based on 100 parts by weight of the monomer component forming the (meth)acrylic polymer. It is preferable to be.

As a chain transfer agent, for example, lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, thioglucholic acid 2-ethylhexyl, 2,3-dimercapto-1 -Propanol, etc. are mentioned. The chain transfer agent may be used alone or in combination of two or more, but the content as a whole is about 0.1 part by weight or less with respect to 100 parts by weight of the total amount of the monomer component.

Various silane coupling agents can be added to the acrylic pressure-sensitive adhesive composition used in the present invention in order to improve adhesion under high temperature and high humidity conditions. As the silane coupling agent, one having any suitable functional group can be used. As a functional group, a vinyl group, an epoxy group, an amino group, a mercapto group, a (meth)acryloxy group, an acetoacetyl group, an isocyanate group, a styryl group, a polysulfide group, etc. are mentioned, for example. Specifically, vinyl group-containing silane coupling agents such as vinyl triethoxysilane, vinyl tripropoxysilane, vinyl triisopropoxysilane, and vinyl tributoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc. Epoxy group-containing silane coupling agent of; γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)3-aminopropylmethyldimethoxysilane, γ-triethoxysilyl Amino group-containing silane coupling agents such as -N-(1,3-dimethylbutylidene)propylamine and N-phenyl-γ-aminopropyltrimethoxysilane; mercapto group-containing silane coupling agents such as γ-mercaptopropylmethyldimethoxysilane; styryl group-containing silane coupling agents such as p-styryl trimethoxysilane; (meth)acrylic group-containing silane coupling agents such as γ-acryloxypropyltrimethoxysilane and γ-methacryloxypropyltriethoxysilane; Isocyanate group-containing silane coupling agents, such as 3-isocyanate propyl triethoxysilane; Polysulfide group-containing silane coupling agents, such as bis(triethoxysilylpropyl) tetrasulfide, etc. are mentioned.

The silane coupling agent may be used alone or in combination of two or more, but the content as a whole is 1 part by weight or less based on 100 parts by weight of all monomer components constituting the (meth)acrylic polymer. It is preferable, it is more preferable that it is 0.01-1 weight part, it is more preferable that it is 0.02 to 0.8 weight part, and it is especially preferable that it is 0.05 to 0.7 weight part. When the blending amount of the silane coupling agent exceeds 1 part by weight, unreacted coupling agent components are generated, which is not preferable from the viewpoint of durability.

Further, 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 parts by weight with respect to 100 parts by weight of all the monomer components constituting the (meth)acrylic polymer.

Furthermore, it is preferable to add a crosslinking agent to the acrylic pressure-sensitive adhesive composition used in the present invention, since cohesive force relating to the durability of the pressure-sensitive adhesive can be imparted.

As a crosslinking agent, a polyfunctional compound is used, and an organic type crosslinking agent and a polyfunctional metal chelate are mentioned. 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 one in which a polyvalent metal atom is covalently bonded or coordinated with an organic compound. Examples of polyvalent metal reactors include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, and Ti. have. An atom in the organic compound to be covalently bonded or coordinated may be an oxygen atom, and examples of the organic compound include an alkyl ester, an alcohol compound, a carboxylic acid compound, an ether compound, and a ketone compound. These crosslinking agents can be used alone or in combination of two or more. Among these, a peroxide-based crosslinking agent and an isocyanate-based crosslinking agent are preferable, and it is more preferable to use them in combination.

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

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

More specifically, for example, lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, and alicyclic isocyanates such as isophorone diisocyanate, 2,4- Aromatic diisocyanates such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, and polymethylene polyphenyl isocyanate, trimethylolpropane/tolylene diisocyanate terpolymer adduct (trade name: coronate L, Nippon Polyurethane Industrial Co., Ltd.), trimethylolpropane/hexamethylene diisocyanate trimer adduct (trade name: Coronate HL, Nippon Polyurethane Industrial Co., Ltd.), isocyanurate of hexamethylene diisocyanate ( Product name: Isocyanate adducts such as Coronate HX, Nippon Polyurethane Industrial Co., Ltd.), trimethylolpropane adduct of xylylene diisocyanate (trade name: D110N, manufactured by Mitsui Chemicals Co., Ltd.), trimethyl of hexamethylene diisocyanate Allpropane adduct (trade name: D160N, manufactured by Mitsui Chemicals Co., Ltd.); Polyether polyisocyanate, polyester polyisocyanate, and adducts of these and various polyols, isocyanurate bonds, biuret bonds, and polyisocyanates polyfunctionalized by allophanate bonds. Among these, it is preferable to use an aliphatic isocyanate because the reaction rate is high.

As the peroxide-based crosslinking agent, various peroxides are used. As peroxides, di(2-ethylhexyl)peroxydicarbonate, di(4-t-butylcyclohexyl)peroxydicarbonate, di-sec-butylperoxydicarbonate, t-butylperoxyneodecanoate, t- Hexylperoxypivalate, t-butylperoxypivalate, dilauroyl peroxide, di-n-octanoyl peroxide, 1,1,3,3-tetramethylbutylperoxyisobutyrate, 1,1, 3,3-tetramethylbutylperoxy2-ethylhexanoate, di(4-methylbenzoyl)peroxide, dibenzoyl peroxide, t-butylperoxyisobutylate, etc. are mentioned. Among these, di(4-t-butylcyclohexyl)peroxydicarbonate, dilauroyl peroxide, and dibenzoyl peroxide, which are particularly excellent in crosslinking reaction efficiency, are preferably used.

The blending ratio of the crosslinking agent in the acrylic pressure-sensitive adhesive composition is not particularly limited, but is usually blended in 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, and more preferably about 0.01 to 5 parts by weight. In particular, in the case of using a peroxide-based crosslinking agent, about 0.05 to 1 part by weight is preferable, and more preferably 0.06 to 0.5 part by weight, based on 100 parts by weight of the (meth)acrylic polymer (solid content).

Moreover, by adding an ionic compound to the acrylic pressure-sensitive adhesive composition used by this invention, it is preferable from a viewpoint of antistatic film at the time of a process operation.

As the ionic compound, an alkali metal salt and/or an organic cation-anion salt can be preferably used. As the alkali metal salt, an organic salt and an inorganic salt of an alkali metal can be used. In addition, the "organic cation-anion salt" as used in the present invention is an organic salt, and indicates that the cation portion is composed of an organic substance, and the anion portion may be an organic substance or an inorganic substance. "Organic cation-anion salt" is also referred to as an ionic liquid or an ionic solid.

<Alkaline metal salt>

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

The anionic portion of the alkali metal salt may be composed of an organic substance or an inorganic substance. 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) ∼ (7),

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

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

_{^{(6): - O 3 S}} (CF 2) l SO 3 - ( However, l is an integer of 1 to 10),

_{(7): (C p F} 2p + 1 SO 2) N - (C q F 2q + 1 SO 2) ( However, p, q is an integer of 1 to 10),

What is indicated by is used. In particular, the anionic moiety containing a fluorine atom is preferably used because an ionic compound having good ion dissociation properties can be obtained. Anion portion constituting the inorganic salts ^{are, 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 - or the like is used. Anionic portion _{is, (CF 3 SO 2) 2} N -, (C 2 F 5 SO 2) 2 N - wherein the general formula (4), (alkylsulfonyl perfluoroalkyl) represented by such imide preferred, In particular, (trifluoromethanesulfonyl)imide represented by _{(CF 3} SO ₂ ) ₂ N ^{-is preferable.}

Examples of the alkali metal organic salt include sodium acetate, sodium alginate, sodium lignin sulfonate, sodium toluene sulfonate, lithium hexafluorophosphate (LiPF ₆ ), LiCF ₃ SO ₃ , Li(CF ₃ SO ₂ ) ₂ N, Li(CF ₃ SO ₂ ) ₂ N, Li(C ₂ F ₅ SO ₂ ) ₂ N, Li(C ₄ F ₉ SO ₂ ) ₂ N, Li(CF ₃ SO ₂ ) ₃ C, KO ₃ S(CF ₂ ) ₃ SO ₃ K, LiO ₃ S(CF ₂ ) ₃ SO ₃ K, etc., among these, lithium hexafluorophosphate (LiPF ₆ ), LiCF ₃ SO ₃ , Li(CF ₃ SO ₂ ) ₂ N , Li(C ₂ F ₅ SO ₂ ) ₂ N, Li(C ₄ F ₉ SO ₂ ) ₂ N, Li(CF ₃ SO ₂ ) ₃ C, etc. are preferred, and Li(CF ₃ SO ₂ ) ₂ N, Li Fluorine-containing lithium imide salts such as (C ₂ F ₅ SO ₂ ) ₂ N, Li (C ₄ F ₉ SO ₂ ) ₂ N are more preferable, and lithium hexafluorophosphate (LiPF ₆ ), lithium bistrifluoro Methanesulfonylimide (LiTFSI, Li(CF ₃ SO ₂ ) ₂ N) is particularly preferred.

Moreover, lithium perchlorate and lithium iodide are mentioned as an inorganic salt of an alkali metal.

<Organic cation-anion salt>

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

Anionic ingredients, for example ^{Cl -, Br -, I -} , AlCl 4 -, Al 2 Cl 7 -, BF 4 -, PF 6 -, ClO 4 -, NO 3 -, CH 3 COO -, CF _{^{3 COO -, 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 - ( where, n is an integer of 1 to 10),

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

_{^{(6): - O 3 S}} (CF 2) l SO 3 - ( However, l is an integer of 1 to 10),

_{(7): (C p F} 2p + 1 SO 2) N - (C q F 2q + 1 SO 2) ( However, p, q is an integer of 1 to 10),

What is indicated by is used. Among these, in particular, an anionic component containing a fluorine atom is preferably used because an ionic compound having good ion dissociation properties can be obtained.

As a specific example of the organic cation-anion salt, a compound composed of a combination of the cation component and an anion component is appropriately selected and used. For example, 1-butylpyridinium tetrafluoroborate, 1-butylpyridinium hexafluorophosphate, 1-butyl-3-methylpyridinium tetrafluoroborate, 1-butyl-3-methylpyridinium trifluoro Methanesulfonate, 1-butyl-3-methylpyridinium bis(trifluoromethanesulfonyl)imide, 1-butyl-3-methylpyridiniumbis(pentafluoroethanesulfonyl)imide, 1-hexylpy Ridinium tetrafluoroborate, 2-methyl-1-pyrroline tetrafluoroborate, 1-ethyl-2-phenylindoletetrafluoroborate, 1,2-dimethylindoletetrafluoroborate, 1-ethylcarbazoletetra Fluoroborate, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium trifluoroacetate, 1-ethyl- 3-methylimidazolium heptafluorobutyrate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium perfluorobutanesulfonate, 1-ethyl- 3-methylimidazolium dicyanamide, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-ethyl-3-methylimidazolium bis(pentafluoroethanesulfonyl) )Imide, 1-ethyl-3-methylimidazolium tris(trifluoromethanesulfonyl)methide, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimida Zoliumhexafluorophosphate, 1-butyl-3-methylimidazolium trifluoroacetate, 1-butyl-3-methylimidazolium heptafluorobutylate, 1-butyl-3-methylimidazolium trifluoro Methanesulfonate, 1-butyl-3-methylimidazolium perfluorobutanesulfonate, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-hexyl-3-methyl Imidazolium bromide, 1-hexyl-3-methylimidazolium chloride, 1-hexyl-3-methylimidazolium tetrafluoroborate, 1-hexyl-3-methylimidazolium hexafluorophosphate, 1-hexyl -3-methylimidazolium trifluoromethanesulfonate, 1-octyl-3-methylimidazolium tetrafluoroborate, 1-octyl-3-methylimidazolium hexafluorophosphate, 1-hexyl-2, 3-dimethylimidazolium tetrafluoroborate, 1,2-dimethyl-3-propylimidazolium bis (trifluorome) Tansulfonyl) imide, 1-methylpyrazolium tetrafluoroborate, 3-methylpyrazolium tetrafluoroborate, tetrahexylammonium bis(trifluoromethanesulfonyl)imide, diallyldimethylammonium tetrafluoroborate, Diallyldimethylammonium trifluoromethanesulfonate, diallyldimethylammonium bis(trifluoromethanesulfonyl)imide, diallyldimethylammoniumbis(pentafluoroethanesulfonyl)imide, N,N-diethyl- N-methyl-N-(2-methoxyethyl)ammonium tetrafluoroborate, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium trifluoromethanesulfonate, N,N -Diethyl-N-methyl-N-(2-methoxyethyl)ammoniumbis(trifluoromethanesulfonyl)imide, N,N-diethyl-N-methyl-N-(2-methoxyethyl) Ammonium bis(pentafluoroethanesulfonyl)imide, glycidyltrimethylammonium trifluoromethanesulfonate, glycidyltrimethylammonium bis(trifluoromethanesulfonyl)imide, glycidyltrimethylammonium bis(penta Fluoroethanesulfonyl)imide, 1-butylpyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-butyl-3-methylpyridinium (trifluoromethanesulfonyl) trifluoroacetamide , 1-ethyl-3-methylimidazolium (trifluoromethanesulfonyl) trifluoroacetamide, N,N-diethyl-N-methyl-N-(2-methoxyethyl) ammonium (trifluoro Methanesulfonyl) trifluoroacetamide, diallyldimethylammonium (trifluoromethanesulfonyl) trifluoroacetamide, glycidyltrimethylammonium (trifluoromethanesulfonyl) trifluoroacetamide, N,N -Dimethyl-N-ethyl-N-propylammoniumbis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-ethyl-N-butylammoniumbis(trifluoromethanesulfonyl)imide, N ,N-dimethyl-N-ethyl-N-pentylammoniumbis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-ethyl-N-hexylammoniumbis(trifluoromethanesulfonyl)imide , N,N-dimethyl-N-ethyl-N-heptylammoniumbis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-ethyl-N-nonylammoniumbis(trifluoromethanesulfonyl) Imide, N,N-dimethyl-N,N-dipropylammoniumbis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-propyl-N-butylammoniumbis(triflu Oromethanesulfonyl)imide, N,N-dimethyl-N-propyl-N-pentylammoniumbis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-propyl-N-hexylammoniumbis( Trifluoromethanesulfonyl)imide, N,N-dimethyl-N-propyl-N-heptylammoniumbis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-butyl-N-hexylammonium Bis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-butyl-N-heptylammoniumbis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-pentyl-N- Hexyl ammonium bis (trifluoromethanesulfonyl) imide, N,N-dimethyl-N,N-dihexyl ammonium bis (trifluoromethanesulfonyl) imide, trimethylheptyl ammonium bis (trifluoromethanesulfonyl )Imide, N,N-diethyl-N-methyl-N-propylammoniumbis(trifluoromethanesulfonyl)imide, N,N-diethyl-N-methyl-N-pentylammoniumbis(trifluoro Romethanesulfonyl)imide, N,N-diethyl-N-methyl-N-heptylammoniumbis(trifluoromethanesulfonyl)imide, N,N-diethyl-N-propyl-N-pentylammonium Bis(trifluoromethanesulfonyl)imide, triethylpropylammonium bis(trifluoromethanesulfonyl)imide, triethylpentylammonium bis(trifluoromethanesulfonyl)imide, triethylheptylammonium bis( Trifluoromethanesulfonyl)imide, N,N-dipropyl-N-methyl-N-ethylammoniumbis(trifluoromethanesulfonyl)imide, N,N-dipropyl-N-methyl-N- Pentylammonium bis(trifluoromethanesulfonyl)imide, N,N-dipropyl-N-butyl-N-hexylammonium bis(trifluoromethanesulfonyl)imide, N,N-dipropyl-N, N-dihexylammonium bis(trifluoromethanesulfonyl)imide, N,N-dibutyl-N-methyl-N-pentylammonium bis(trifluoromethanesulfonyl)imide, N,N-dibutyl -N-methyl-N-hexylammoniumbis(trifluoromethanesulfonyl)imide, trioctylmethylammoniumbis(trifluoromethanesulfonyl)imide, N-methyl-N-ethyl-N-propyl-N -Pentyl ammonium bis(trifluoromethanesulfonyl)imide, 1-butyl-3-methylpyridin-1-ium trifluoromethanesulfonate, etc. are mentioned. As these commercial items, "CIL-314" (manufactured by Nippon Carit Co., Ltd.), "ILA2-1" (manufactured by Koei Chemical Industries, Ltd.), etc. can be used, for example.

Further, for example, 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, triethylbutylammonium bis(trifluoromethanesulfonyl)imide, tetrabutylammonium bis(trifluoromethanesulfonyl)imide, tetrahexylammonium bis(trifluoromethane Sulfonyl) imide, etc. are mentioned.

Further, for example, 1-dimethylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-ethylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1 -Propylpyrrolidiniumbis(trifluoromethanesulfonyl)imide, 1-methyl-1-butylpyrrolidiniumbis(trifluoromethanesulfonyl)imide, 1-methyl-1-pentylpyrrolidiniumbis (Trifluoromethanesulfonyl)imide, 1-methyl-1-hexylpyrrolidiniumbis(trifluoromethanesulfonyl)imide, 1-methyl-1-heptylpyrrolidiniumbis(trifluoromethanesulphate) Fonyl)imide, 1-ethyl-1-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-ethyl-1-butylpyrrolidiniumbis(trifluoromethanesulfonyl)imide, 1 -Ethyl-1-pentylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-hexylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-hep Tylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1,1-dipropylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-propyl-1-butylpyrrolidinium bis (trifluoro Romethanesulfonyl)imide, 1,1-dibutylpyrrolidiniumbis(trifluoromethanesulfonyl)imide, 1-propylpiperidiniumbis(trifluoromethanesulfonyl)imide, 1-pentyl Piperidinium bis (trifluoromethanesulfonyl) imide, 1,1-dimethylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-ethylpiperidinium bis (trifluoro Methanesulfonyl)imide, 1-methyl-1-propylpiperidiniumbis(trifluoromethanesulfonyl)imide, 1-methyl-1-butylpiperidiniumbis(trifluoromethanesulfonyl)imide , 1-methyl-1-pentylpiperidinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-hexylpiperidiniumbis(trifluoromethanesulfonyl)imide, 1-methyl-1 -Heptylpiperidiniumbis(trifluoromethanesulfonyl)imide, 1-ethyl-1-propylpiperidiniumbis(trifluoromethanesulfonyl)imide, 1-ethyl-1-butylpiperidiniumbis (Trifluoromethanesulfonyl)imide, 1-ethyl-1-pentylpiperidiniumbis(trifluoromethanesulfonyl)imide, 1-ethyl-1-hexylpiperidiniumbis(trifluoromethanesulphate) Fonyl)imide, 1-ethyl-1-heptylpiperidiniumbis(trifluoromethanesulfonyl)imide, 1,1-dipropylpiperidiniumbis(t Lifluoromethanesulfonyl)imide, 1-propyl-1-butylpiperidiniumbis(trifluoromethanesulfonyl)imide, 1,1-dibutylpiperidiniumbis(trifluoromethanesulfonyl) Imide, 1,1-dimethylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-ethylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1 -Propylpyrrolidiniumbis(pentafluoroethanesulfonyl)imide, 1-methyl-1-butylpyrrolidiniumbis(pentafluoroethanesulfonyl)imide, 1-methyl-1-pentylpyrrolidiniumbis (Pentafluoroethanesulfonyl) imide, 1-methyl-1-hexylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-heptylpyrrolidinium bis (pentafluoroethanesol Fonyl)imide, 1-ethyl-1-propylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-butylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1 -Ethyl-1-pentylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-hexylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1- hep Tylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1,1-dipropylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-propyl-1-butylpyrrolidinium bis (pentafluoro Loethanesulfonyl)imide, 1,1-dibutylpyrrolidiniumbis(pentafluoroethanesulfonyl)imide, 1-propylpiperidiniumbis(pentafluoroethanesulfonyl)imide, 1-pentyl Piperidiniumbis(pentafluoroethanesulfonyl)imide, 1,1-dimethylpiperidiniumbis(pentafluoroethanesulfonyl)imide, 1-methyl-1-ethylpiperidiniumbis(pentafluoro Ethanesulfonyl)imide, 1-methyl-1-propylpiperidiniumbis(pentafluoroethanesulfonyl)imide, 1-methyl-1-butylpiperidiniumbis(pentafluoroethanesulfonyl)imide , 1-methyl-1-pentylpiperidiniumbis(pentafluoroethanesulfonyl)imide, 1-methyl-1-hexylpiperidiniumbis(pentafluoroethanesulfonyl)imide, 1-methyl-1 Heptylpiperidiniumbis(pentafluoroethanesulfonyl)imide, 1-ethyl-1-propylpiperidiniumbis(pentafluoroethanesulfonyl)imide, 1-ethyl-1-heptylpiperidiniumbis( Pentafluoroethanesulfonyl)imide, 1-ethyl-1-pentylpiperidiniumbis(pentafluoroethanesulfonyl)imide, 1-ethyl-1-hexylpipe Ridiniumbis(pentafluoroethanesulfonyl)imide, 1-ethyl-1-heptylpiperidiniumbis(pentafluoroethanesulfonyl)imide, 1-propyl-1-butylpiperidiniumbis(pentafluoro Loethanesulfonyl)imide, 1,1-dipropylpiperidiniumbis(pentafluoroethanesulfonyl)imide, 1,1-dibutylpiperidiniumbis(pentafluoroethanesulfonyl)imide, etc. Can be mentioned.

In addition, instead of the cation component of the compound, trimethylsulfonium cation, triethylsulfonium cation, tributylsulfonium cation, trihexylsulfonium cation, diethylmethylsulfonium cation, dibutylethylsulfonium And compounds using phonium cation, dimethyldecylsulfonium cation, tetramethylphosphonium cation, tetraethylphosphonium cation, tetrabutylphosphonium cation, and tetrahexylphosphonium cation.

In addition, in place of the bis(trifluoromethanesulfonyl)imide, bis(pentafluorosulfonyl)imide, bis(heptafluoropropanesulfonyl)imide, bis(nonafluorobutanesulfonyl)imide De, trifluoromethanesulfonylnonafluorobutanesulfonylimide, heptafluoropropanesulfonyltrifluoromethanesulfonylimide, pentafluoroethanesulfonylnonafluorobutanesulfonylimide, cyclo-hexa And compounds using fluoropropane-1,3-bis(sulfonyl)imide anion and the like.

Moreover, as an ionic compound, besides the said alkali metal salt and an organic cation-anion salt, inorganic salts, such as ammonium chloride, aluminum chloride, copper chloride, ferrous chloride, ferric chloride, and ammonium sulfate, are mentioned. These ionic compounds may be used alone or in combination of a plurality.

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

Furthermore, in the acrylic pressure-sensitive adhesive composition used in the present invention, if necessary, a viscosity modifier, a peel modifier, a tackifier, a plasticizer, a softener, a glass fiber, a glass beads, a filler made of a metal powder, other inorganic powder, etc., a pigment, Colorants (pigments, dyes, etc.), pH adjusters (acids or bases), antioxidants, ultraviolet absorbers, and the like, and various additives may be appropriately used within a range not departing from the object of the present invention. These additives can also be blended as an emulsion.

(3) a polarizing film with an adhesive layer formed thereon

The polarizing film with 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, and the acrylic pressure-sensitive adhesive composition is applied on various substrates, dried with a dryer such as a heat oven, and evaporated to form a pressure-sensitive adhesive layer, and the iodine-based polarizing film A method of transferring the pressure-sensitive adhesive layer may be used, or the acrylic pressure-sensitive adhesive composition may be directly applied onto the iodine-based polarizing film to form a pressure-sensitive adhesive layer.

It does not specifically limit as said base material, For example, various base materials, such as a release film and a transparent resin film base material, are mentioned.

Various methods are used as the coating method to the substrate or the polarizing film. Specifically, for example, fountain coater, roll coat, kiss roll coat, gravure coat, reverse coat, roll brush, spray coat, deep roll coat, bar coat, knife coat, air knife coat, curtain coat, lip coat, die Methods, such as an extrusion coating method using a coater or the like, are mentioned.

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

The thickness (after drying) of the pressure-sensitive adhesive layer is, for example, preferably 5 to 100 µm, more preferably 10 to 60 µm, and still more preferably 12 to 40 µm. When the thickness of the pressure-sensitive adhesive layer is less than 10 µm, adhesion to the adherend tends to be insufficient, and durability under 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 exceeds 100 µm, the acrylic pressure-sensitive adhesive composition cannot be sufficiently completely dried during application and drying when forming the pressure-sensitive adhesive layer, and air bubbles remain, or the thickness of the pressure-sensitive adhesive layer remains on the surface of the pressure-sensitive adhesive layer. There is a tendency that non-uniformity occurs or causes an appearance problem to be easily present.

As a constituent material of the release film, for example, resin films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films, porous materials such as paper, fabric, and nonwoven fabric, nets, foam sheets, metal foils, and laminates thereof Suitable thin-leaf bodies such as a sieve are mentioned, but a resin film is preferably used from the viewpoint of excellent surface smoothness.

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

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

Although it does not specifically limit as said transparent resin film base material, Various resin films which have transparency are used. The said resin film is formed by one layer of film. For example, as the material, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, acetate resins, polyethersulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (Meth)acrylic resins, polyvinyl chloride resins, polyvinylidene chloride resins, polystyrene resins, polyvinyl alcohol resins, polyarylate resins, polyphenylene sulfide resins, and the like. Among these, polyester resins, polyimide resins, and polyethersulfone resins are particularly preferable.

It is preferable that the thickness of the film substrate is 15 to 200 µm.

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

Examples of the polymers include polyurethane resins, polyester resins, acrylic resins, polyether resins, cellulose resins, polyvinyl alcohol resins, polyvinylpyrrolidone, and polystyrene resins. . Among these, polyurethane resins, polyester resins, and acrylic resins are particularly preferred. A crosslinking agent can be appropriately blended into these resins. One or two or more of these other binder components can be suitably used according to the purpose.

When the anchor layer is formed of a water-dispersible material, a water-dispersion polymer is used. Examples of water-dispersible polymers are those obtained by emulsifying various resins such as polyurethane and polyester using an emulsifier, or those obtained by introducing a water-dispersible anionic group, a cation group, or a nonionic group into the resin to be self-emulsified. And the like.

In addition, an antistatic agent can be contained in the anchor agent. The antistatic agent is not particularly limited as long as it is a material capable of imparting conductivity, and examples thereof include ionic surfactants, conductive polymers, metal oxides, carbon black, and carbon nanomaterials. Among these, conductive polymers are Preferably, it is a water-dispersible conductive polymer more preferably.

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

The blending amount of the antistatic agent is, for example, 70 parts by weight or less, preferably 50 parts by weight or less, based on 100 parts by weight of the polymers used in the anchor agent. From the viewpoint of the antistatic effect, it is preferable to set it as 10 parts by weight or more, and further to 20 parts by weight or more.

In addition, various additives may be blended with the anchor agent for the purpose of suppressing deterioration of the pressure-sensitive adhesive layer or polarizer that occurs when contacting the anchor coat layer, and various additives for the purpose of imparting a function to the anchor coat layer. I can. For example, antioxidants, deterioration inhibitors, ultraviolet absorbers, optical brighteners, and the like can be added.

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

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

Moreover, when the adhesive layer of the polarizing film in which the adhesive layer of this invention was formed is exposed, you may protect the adhesive layer with a release film (separator) until it is provided for practical use. As a release film, the thing mentioned above is mentioned. When a release film is used as a base material in the production of the pressure-sensitive adhesive layer, the release film can be used as a release film of the pressure-sensitive adhesive layer of the polarizing film on which the pressure-sensitive adhesive layer is formed by bonding the pressure-sensitive adhesive layer on the release film and an iodine-based polarizing film. Yes, it is possible to simplify the process.

2. Laminate

In the laminate of the present invention, the polarizing film on which the pressure-sensitive adhesive layer is formed and a member having a transparent conductive layer are pasted so that 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 member having the transparent conductive layer are in contact with each other. It is characterized by a combination.

The polarizing film on which the pressure-sensitive adhesive layer is formed may be the one described above.

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

As the transparent substrate, any one having transparency may be used, and for example, a resin film or a substrate made of glass or the like (for example, a sheet-like, film-like, plate-like substrate, etc.) can be exemplified, and a resin film is particularly preferred. . The thickness of the transparent substrate is not particularly limited, but is preferably about 10 to 200 µm, and more preferably about 15 to 150 µm.

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

In addition, the transparent substrate is subjected to etching or primer treatment such as sputtering, corona discharge, flame, ultraviolet irradiation, electron beam irradiation, chemical conversion, oxidation, etc. to the surface in advance, and the transparent conductive layer formed thereon is applied to the transparent substrate. You may try to improve the adhesion. Further, before forming the transparent conductive layer, if necessary, it may be subjected to vibration suppression and cleaning by solvent cleaning or ultrasonic cleaning.

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

Moreover, as said ITO, crystalline ITO and amorphous (amorphous) ITO are mentioned. Crystalline ITO can be obtained by applying a high temperature during sputtering or by further heating amorphous ITO. Since the above-described deterioration by iodine occurs remarkably in amorphous ITO, the polarizing film in which the pressure-sensitive adhesive layer of the present invention is formed is particularly effective in amorphous ITO.

The thickness of the transparent conductive layer is not particularly limited, but it is preferably 7 nm or more, more preferably 10 nm or more, more preferably 12 to 60 nm, and furthermore 15 to 45 nm. It is preferable, and it is more preferable to set it as 18 to 45 nm, and it is especially preferable to set it as 20 to 30 nm. When 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 there is a tendency that the change in the electric resistance value of the transparent conductive layer increases. On the other hand, when it exceeds 60 nm, the productivity of the transparent conductive layer decreases, the cost increases, and the optical properties tend to decrease.

The method for forming the transparent conductive layer is not particularly limited, and a conventionally known method may be employed. Specifically, a vacuum evaporation method, a sputtering method, and an ion plating method can be illustrated, for example. Moreover, it is also possible to adopt an appropriate method according to the required film thickness.

The thickness of the substrate having the transparent conductive layer is 15 to 200 µm. In addition, from the viewpoint of thinning, it is preferably 15 to 150 µm, and more preferably 15 to 50 µm. When the substrate having the transparent conductive layer is used in a resistive film method, a thickness of, for example, 100 to 200 µm is mentioned. In addition, when used in the electrostatic capacity method, a thickness of, for example, 15 to 100 µm is preferable, and in particular, a thickness of 15 to 50 µm is more preferable, and a thickness of 20 to 50 µm is more preferable in accordance with the recent additional thinning demand. Do.

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

In addition, as a member having a transparent conductive layer and a liquid crystal cell, a liquid crystal cell including a configuration of a substrate (eg, glass substrate, etc.)/liquid crystal layer/substrate used in image display devices such as various liquid crystal display devices. What has a transparent conductive layer on the side which does not contact with the liquid crystal layer of the said board|substrate is mentioned. Moreover, when forming a color filter substrate on a liquid crystal cell, you may have a transparent conductive layer on the said 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 is an image display device (liquid crystal display device, organic EL (electroluminescence) display device, PDP (plasma display panel), electronic paper, etc.) provided with an input device (touch panel, etc.), input device It can be preferably used in the manufacture of a base material (member) constituting devices such as (touch panel, etc.) or a base material (member) used in these devices, but it can be particularly preferably used in the production of an optical base material for a touch panel. . In addition, it can be used regardless of a method such as a touch panel such as a resistive film method or a capacitive 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 optical devices is not particularly limited as long as it has optical properties, but, for example, an image display device (liquid crystal display device, organic EL (electroluminescence) display device, PDP (plasma display panel), electronic paper, etc.) ), a base material (member) constituting devices such as an input device (touch panel, etc.), or a base material (member) used in these devices.

In addition, as described above, the polarizing film with the pressure-sensitive adhesive layer of the present invention can suppress corrosion of the transparent conductive layer even when a transparent conductive layer is laminated on the pressure-sensitive adhesive layer of the polarizing film with the pressure-sensitive adhesive layer, as described above, and is transparent. It is possible to suppress an increase in the surface resistance of the conductive layer. Therefore, as long as the pressure-sensitive adhesive layer of the polarizing film on which the pressure-sensitive adhesive layer is formed is an image display device having a configuration in contact with the transparent conductive layer, the polarizing film with the pressure-sensitive adhesive layer of the present invention can be preferably used. For example, a liquid crystal panel having a polarizing film with a pressure-sensitive adhesive layer of the present invention and a transparent conductive layer is bonded so that the pressure-sensitive adhesive layer of the polarizing film with the pressure-sensitive adhesive layer and the transparent conductive layer of the liquid crystal panel are in contact with each other, and an image display device It can be done with.

More specifically, an image display device in which a transparent conductive layer is used as an antistatic layer, and an image display device in which a transparent conductive layer is used as an electrode in a touch panel can be mentioned. As an image display device using a transparent conductive layer as an antistatic layer application, specifically, as shown in FIG. 1, for example, polarizing film (1)/adhesive layer (2)/antistatic layer (3)/glass substrate (4)/liquid crystal layer (5)/driving electrode (6)/glass substrate (4)/adhesive layer (2)/polarizing film (1), and the antistatic layer (3) and drive electrode (6) An image display device formed from this transparent conductive layer can be mentioned. As the polarizing films 1 and 2 in which the pressure-sensitive adhesive layer on the upper side (viewer side) of the image display device was formed, a polarizing film provided with the pressure-sensitive adhesive layer of the present invention can be used. In addition, as an image display device using a transparent conductive layer as an electrode for a touch panel, for example, a polarizing film (1)/adhesive layer (2)/an antistatic layer and sensor layer (7)/glass substrate (4)/ Structure of liquid crystal layer 5/driving electrode and sensor layer 8/glass substrate 4/adhesive layer 2/polarizing film 1 (in-cell touch panel, Fig. 2) or polarizing film 1 /Adhesive layer (2)/Antistatic layer and sensor layer (7)/Sensor layer (9)/Glass substrate (4)/Liquid crystal layer (5)/Drive electrode (6)/Glass substrate (4)/Adhesive layer (2) )/Polarizing film 1 configuration (on-cell touch panel, Fig. 3), and an antistatic layer and sensor layer 7, sensor layer 9, and driving electrode 6 formed of a transparent conductive layer Can be mentioned. As the polarizing films 1 and 2 in which the pressure-sensitive adhesive layer on the upper side (viewer side) of the image display device was formed, a polarizing film with the pressure-sensitive adhesive layer of the present invention can be used.

Example

Hereinafter, the present invention will be described in detail using Examples, but the present invention is not limited to the following Examples unless the gist of the present invention is exceeded. In addition, in each example, both parts and% are based on weight.

<Iodine content in polarizer>

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

1) Fluorescent X-ray intensity was measured for a plurality of polarizers containing a predetermined amount of potassium iodide, and a relational expression between iodine content and fluorescent X-ray intensity was derived.

2) Fluorescent X-rays of an iodine polarizer having an unknown iodine content were measured, and the amount of iodine was calculated from the numerical value using the above relational formula.

Production Example 1 (Preparation of polarizing film (1))

A stretched laminate was produced from a laminate in which a 9 µm-thick polyvinyl alcohol (PVA) layer was formed on an amorphous PET substrate by air-assisted stretching at a stretching temperature of 130°C. Next, the stretched laminate was immersed in a dyeing solution containing 0.1 parts by weight of iodine and 0.7 parts by weight of potassium iodide for 60 seconds with respect to 100 parts by weight of water, thereby producing a colored laminate. In addition, an optical film laminate comprising a 4 µm-thick PVA layer was formed integrally with the amorphous PET substrate so that the colored laminate was stretched in water with boric acid at a stretching temperature of 65°C so that the total draw ratio was 5.94 times. By such two-stage stretching, the PVA molecules of the PVA layer formed on the amorphous PET substrate are oriented at a high degree, and iodine adsorbed by dyeing constitutes a highly functional polarizing layer in which the iodine adsorbed by dyeing is oriented at a high order in one direction as a polyiodine ion complex. An optical film laminate including a PVA layer having a thickness of 4 µm could be produced. Further, while applying a PVA-based adhesive to the surface of the polarizing layer of the optical film laminate, after bonding the saponified 40 μm thick acrylic resin film (transparent protective film 1), the amorphous PET substrate was peeled off. , A polarizing film having a transparent protective film was produced only on one side using a thin iodine polarizer. Hereinafter, this is called polarizing film (1). The iodine content of the polarizing film 1 was 5.1% by weight.

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

Polarization having a transparent protective film only on one side using a thin iodine polarizer as in Production Example 1 except that the dyeing time was changed from 60 seconds to 120 seconds (Production Example 2) and 180 seconds (Production Example 3). The 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 (Preparation of polarizing film 4)

A polyvinyl alcohol film having a thickness of 80 µm was stretched to three times while dyeing for 1 minute in an iodine solution having a concentration of 30°C and 0.3% between rolls having different speed ratios. Thereafter, the total draw ratio was extended to 6 times while immersed for 0.5 minutes in an aqueous solution containing boric acid at 60°C and 4% concentration and potassium iodide at 10% concentration. Next, after washing by immersing for 10 seconds in an aqueous solution containing potassium iodide at 30°C and 1.5% concentration, it was dried at 50°C for 4 minutes to obtain a polarizer having a thickness of 25 μm and an iodine content of 2.3% by weight. On one side of the polarizer, an acrylic resin film (transparent protective film (1)) having a thickness of 40 μm was bonded to each other with a polyvinyl alcohol-based adhesive to prepare a polarizing film. Hereinafter, this is called polarizing film (4). The iodine content of the polarizing film 4 was 2.3 weight%.

Production Example 5 (Preparation of polarizing film 5)

In Production Example 1, after peeling off the amorphous PET substrate, a 25 μm-thick norbornene-based film (transparent protective film (2)) was bonded to the other side with a polyvinyl alcohol-based adhesive to prepare a polarizing film. . Hereinafter, this is called thin polarizing film (5). The iodine content of the polarizing film 5 was 5.1% by weight.

Production Example 6 (Preparation of polarizing film 6)

On both sides of the polarizer having an iodine content of 2.3% by weight obtained by Production Example 4, an acrylic resin film (transparent protective film (1)) having a thickness of 40 µm and a norbornene-based film (transparent protective film (2)) having a thickness of 25 µm were prepared. It was bonded together with a polyvinyl alcohol-based adhesive to prepare a polarizing film. Hereinafter, this is called polarizing film (6). The iodine content of the polarizing film 6 was 2.3 weight%.

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

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

In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirring device, 99 parts of butyl acrylate, 1 part of 4-hydroxybutyl acrylate, and as an initiator, 2,2'-azobisisobutyronitrile ( AIBN) was added 1 part with ethyl acetate with respect to 100 parts of a monomer (solid content), and it was made to react at 60 degreeC for 7 hours in a nitrogen gas stream. Thereafter, ethyl acetate was added to the reaction solution to obtain a solution containing an acrylic polymer (A-1) with a weight average molecular weight of 1.6 million (solid content concentration 30% by weight).

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

In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirring device, 99 parts of butyl acrylate, 1 part of 2-hydroxyethyl acrylate, and 1 part of AIBN as an initiator per 100 parts of the monomer (solid content) were added. It was added together with ethyl acetate, and it was made to react at 60 degreeC under a nitrogen gas stream for 7 hours. Thereafter, ethyl acetate was added to the reaction solution to obtain a solution containing an acrylic polymer (A-2) with a weight average molecular weight of 1.6 million (solid content concentration 30% by weight).

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

To a reaction vessel equipped with a cooling tube, a nitrogen inlet tube, a thermometer and a stirring device, 100 parts of butyl acrylate, and 1 part of AIBN as an initiator, per 100 parts of the monomer (solid content) were added together with ethyl acetate, and under a nitrogen gas stream. And reacted at 60° C. for 7 hours. Thereafter, ethyl acetate was added to the reaction solution to obtain a solution containing an acrylic polymer (A-3) with a weight average molecular weight of 1.6 million (solid content concentration 30% by weight).

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

In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirring device, 98.6 parts of butyl acrylate, 1 part of 4-hydroxybutyl acrylate, 0.4 parts of acrylic acid, and 100 parts of AIBN as a monomer (solid content) as an initiator To this, 1 part was added together with ethyl acetate, and it was made to react at 60 degreeC for 7 hours in a nitrogen gas stream. Thereafter, ethyl acetate was added to the reaction solution to obtain a solution containing an acrylic polymer (A-4) having a weight average molecular weight of 1.6 million (solid content concentration 30% by weight).

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

In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirring device, 95 parts of butyl acrylate, 1 part of 4-hydroxybutyl acrylate, 4 parts of acrylic acid, and 100 parts of AIBN as a monomer (solid content) as an initiator 1 part was added together with ethyl acetate, and it was made to react at 60 degreeC for 7 hours in a nitrogen gas stream. Thereafter, ethyl acetate was added to the reaction solution to obtain a solution containing an acrylic polymer (A-5) with a weight average molecular weight of 1.55 million (solid content concentration 30% by weight).

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

In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirring device, 91 parts of butyl acrylate, 1 part of 2-hydroxyethyl acrylate, 8 parts of acrylic acid, and 100 parts of AIBN as a monomer (solid content) as an initiator About 0.75 parts was added together with ethyl acetate, and it was made to react at 60 degreeC for 9 hours in a nitrogen gas stream. Thereafter, ethyl acetate was added to the reaction solution to obtain a solution containing an acrylic polymer (A-6) with a weight average molecular weight of 1.9 million (solid content concentration 30% by weight).

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

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

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

In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirring device, 84.9 parts of butyl acrylate, 0.1 parts of 4-hydroxybutyl acrylate, 5 parts of acrylic acid, 10 parts of benzyl acrylate, and AIBN as an initiator were used. With respect to 100 parts of monomer (solid content), 1 part was added together with ethyl acetate, and it was made to react at 60 degreeC for 7 hours in a nitrogen gas stream. Thereafter, ethyl acetate was added to the reaction solution to obtain a solution containing an acrylic polymer (A-8) having a weight average molecular weight of 1.8 million (solid content concentration 30% by weight).

Moreover, the weight average molecular weight of the acrylic polymer obtained in Production Examples 7-14 was measured by the following measuring method.

<Measurement of weight average molecular weight (Mw) of acrylic polymer>

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

Equipment: manufactured by Tosoh Corporation, HLC-8220GPC

column :

Sample column: manufactured by Tosoh Corporation, TSKguardcolumn Super HZ-H (1 piece) + TSKgel Super HZM-H (2 pieces)

Reference column: Tosoh Corporation, TSKgel Super H-RC (1 pc.)

Flow: 0.6 ml/min

Injection volume: 10 µl

Column temperature: 40 °C

Eluent: THF

Concentration of injected sample: 0.2% by weight

Detector: differential refractometer

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

Example 1

(Adjustment of acrylic pressure-sensitive adhesive composition)

Per 100 parts of solid content of the solution containing the acrylic polymer (A-1) obtained in Production Example 7 (solid content concentration 30% by weight), as a crosslinking agent, trimethylolpropane xylylene diisocyanate (trade name: Takenate D110N, Mitsui Chemical Co., Ltd.) Manufacturing) 0.1 parts, dibenzoyl peroxide 0.3 parts, phosphanol SM-172 (trade name, manufactured by Toho Chemical Industries, Ltd.) as a phosphoric acid compound, 0.03 parts, and γ-glycidoxypropyl as a silane coupling agent 0.075 parts of trimethoxysilane (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.), as a phenolic antioxidant, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4) -Hydroxyphenyl) propionate (IRGANAOX 1010, manufactured by BASF Japan Co., Ltd.) 0.3 parts were blended to obtain an acrylic pressure-sensitive adhesive composition.

(Preparation of a polarizing film with an 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 release agent with a fountain coater, and dried in an air circulation constant temperature oven at 155° C. for 2 minutes, and a thickness of 20 on the surface of the substrate. A pressure-sensitive adhesive layer of µm was formed. Next, the separator in which the pressure-sensitive adhesive layer was formed was attached to the surface of the polarizing film 1 which does not have a protective film, and the polarizing film with the pressure-sensitive adhesive layer was produced.

Examples 2 to 5

Except having changed the addition amount of the phosphoric acid compound from 0.03 parts to the number of copies shown in Table 3, it carried out similarly to Example 1, and produced the polarizing film with the adhesive layer formed.

Example 6

Phosphanol SM-172 (trade name, manufactured by Toho Chemical Industries Co., Ltd.) 0.03 parts, except having changed to phosphanol RS-410 (manufactured by Toho Chemical Industries, Ltd.) 0.1 parts, in the same manner as in Example 1, the pressure-sensitive adhesive layer This formed polarizing film was produced.

Example 7

In the same manner as in Example 1, except that 0.03 parts of phosphanol SM-172 (trade name, manufactured by Toho Chemical Industries, Ltd.) was changed to 0.1 parts of phosphanol RS-710 (manufactured by Toho Chemical Industries, Ltd.), the pressure-sensitive adhesive layer This formed polarizing film was produced.

Example 8

A polarizing film with a pressure-sensitive adhesive layer formed in the same manner as in Example 1, except that 0.03 parts of phosphanol SM-172 (trade name, manufactured by Toho Chemical Industries, Ltd.) was changed to 0.05 parts of DBP (manufactured by Johoku Chemical Co., Ltd.) Was produced.

Example 9

Phosphanol SM-172 (trade name, manufactured by Toho Chemical Industries Co., Ltd.) 0.03 parts, except for changing to 0.03 parts of phosphoric acid (reagent limited express) (Wako Pure Chemical Industries Co., Ltd. product), in the same manner as in Example 1, a pressure-sensitive adhesive A layered polarizing film was produced.

Examples 10-14

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

Examples 15-17

In the (production of the polarizing film with an adhesive layer) of Example 1, except having changed the polarizing film (1) to the polarizing films (2), (3), (4), it was carried out in the same manner as in Example 1, A polarizing film with an adhesive layer was prepared.

Example 18

(Adjustment of acrylic pressure-sensitive adhesive composition)

Per 100 parts of solid content of the solution containing the acrylic polymer (A-1) obtained in Production Example 7 (solid content concentration 30% by weight), as a crosslinking agent, trimethylolpropane xylylene diisocyanate (trade name: Takenate D110N, Mitsui Chemical Co., Ltd.) Manufacturing) 0.1 parts, dibenzoyl peroxide 0.3 parts, phosphanol SM-172 (trade name, manufactured by Toho Chemical Industries, Ltd.) as a phosphoric acid compound, 0.03 parts, and γ-glycidoxypropyl as a silane coupling agent 0.075 parts of trimethoxysilane (trade name: KBM-403, manufactured by Shin-Etsu Chemical Industries, Ltd.) and 0.5 parts of lithium bistrifluoromethanesulfonylimide (manufactured by Morita Chemical Industries, Ltd.) as an ionic compound , As a phenolic antioxidant, 0.3 parts of pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (IRGANAOX 1010, manufactured by BASF Japan Co., Ltd.) , An acrylic pressure-sensitive adhesive composition was obtained.

(Preparation of a polarizing film with an adhesive layer)

Except having used the said acrylic adhesive composition, it carried out similarly to Example 1, and produced the polarizing film with the adhesive layer formed.

Example 19

0.5 parts of lithium bistrifluoromethanesulfonylimide (manufactured by Morita Chemical Co., Ltd.), 1-methyl-1-ethylpyrrolidinium bis(trifluoromethanesulfonyl)imide (Kishida Chemical Co., Ltd.) Production) Except having changed to 0.5 part, it carried out similarly to Example 18, and produced the polarizing film with the adhesive layer formed.

Example 20

The solution containing the acrylic polymer (A-1) obtained in Production Example 7 was changed to the acrylic acid ester copolymer (A-8) obtained in Production Example 14, and phosphanol SM-172 (trade name, Toho Chemical Industries Co., Ltd. ) Manufacturing) 0.03 part of phosphoric acid (reagent limited grade) (made by Wako Pure Chemical Industries, Ltd.) was carried out similarly to Example 1 except having changed to 0.05 part, and the polarizing film with the adhesive layer was produced.

Example 21

Except having changed the addition amount of phosphoric acid (reagent limited grade) (made by Wako Pure Chemical Industries, Ltd.) from 0.05 part to 0.1 part, it carried out similarly to Example 20, and produced the polarizing film in which the adhesive layer was formed.

Example 22

Phosphanol SM-172 (trade name, manufactured by Toho Chemical Industries Co., Ltd.) 0.03 parts, MP-4 (brand name, acid value: 670 mgKOH/g, Daihachi Chemical Industries Co., Ltd.) 0.01 parts, except that the change was carried out. In the same manner as in Example 1, a polarizing film with an adhesive layer was produced.

Example 23

A polarizing film with a pressure-sensitive adhesive layer formed in the same manner as in Example 22, except that the addition amount of MP-4 (brand name, acid value: 670 mgKOH/g, manufactured by Daihachi Chemical Industries, Ltd.) was changed from 0.01 parts to 0.06 parts. Was produced.

Example 24

The solution containing the acrylic polymer (A-1) obtained in Production Example 7 was changed to the acrylic acid ester copolymer (A-8) obtained in Production Example 14, and phosphanol SM-172 (trade name, Toho Chemical Industries Co., Ltd. ) Manufacturing) 0.03 parts of MP-4 (brand name, acid value: 670 mgKOH/g, manufactured by Daihachi Chemical Industries Co., Ltd.) was changed to 0.1 parts, in the same manner as in Example 1, and a polarizing film with a pressure-sensitive adhesive layer formed thereon Was produced.

Examples 25 and 26

In the same manner as in Example 24, except that the addition amount of MP-4 (brand name, acid value: 670 mgKOH/g, manufactured by Daihachi Chemical Industries, Ltd.) was changed from 0.1 parts to 0.8 parts and 3 parts, the pressure-sensitive adhesive layer This formed polarizing film was produced.

Example 27

The solution containing the acrylic polymer (A-1) obtained in Production Example 7 was changed to the acrylic acid ester copolymer (A-8) obtained in Production Example 14, and phosphanol SM-172 (trade name, Toho Chemical Industries Co., Ltd. ) Manufacturing) 0.03 parts, MP-4 (trade name, acid value: 670 mgKOH/g, manufactured by Daihachi Chemical Industries, Ltd.) 0.04 parts and phosphoric acid (reagent limited grade) (manufactured by Wako Pure Chemical Industries, Ltd.) 0.01 parts of a mixture Except having changed to, it carried out similarly to Example 1, and produced the polarizing film in which the adhesive layer was formed.

Example 28

The solution containing the acrylic polymer (A-1) obtained in Production Example 7 was changed to the acrylic acid ester copolymer (A-8) obtained in Production Example 14, and phosphanol SM-172 (trade name, Toho Chemical Industries Co., Ltd. ) Manufacturing) 0.03 parts of phosphanol SM-172 (trade name, manufactured by Toho Chemical Industries Co., Ltd.) 0.04 parts and phosphoric acid (reagent limited express) (manufactured by Wako Pure Chemical Industries, Ltd.) 0.01 parts, except that the mixture was changed. In the same manner as in Example 1, a polarizing film with an adhesive layer was produced.

Examples 29-34

A polarizing film with an adhesive layer was produced in the same manner as in Example 1, except that the type of the solution containing the obtained acrylic polymer and the type and amount of the phosphoric acid compound were changed to the type and number of copies shown in Table 3.

Comparative Example 1

In the same manner as in Example 1, except that the solution containing the acrylic polymer (A-1) was changed to the solution containing the acrylic polymer (A-2) obtained in Production Example 8, and no phosphate ester was used. , To prepare a polarizing film in which the pressure-sensitive adhesive layer was formed.

Comparative Example 2

In the same manner as in Example 1, except that the solution containing the acrylic polymer (A-1) was changed to the solution containing the acrylic polymer (A-3) obtained in Production Example 9, and no phosphate ester was used. , To prepare a polarizing film in which the pressure-sensitive adhesive layer was formed.

Comparative Example 3

In the same manner as in Example 1, except that the solution containing the acrylic polymer (A-1) was changed to the solution containing the acrylic polymer (A-5) obtained in Production Example 11, and no phosphate ester was used. , To prepare a polarizing film in which the pressure-sensitive adhesive layer was formed.

Comparative Example 4

In the same manner as in Example 1, except that the solution containing the acrylic polymer (A-1) was changed to the solution containing the acrylic polymer (A-7) obtained in Production Example 13, and no phosphate ester was used. , To prepare a polarizing film in which the pressure-sensitive adhesive layer was formed.

Examples 35, 36

Except having changed the polarizing film (1) to the polarizing films (5) and (6) in (production of the polarizing film with an adhesive layer) of Example 1, it carried out similarly to Example 1, and the adhesive layer was formed A polarizing film was produced. In addition, the pressure-sensitive adhesive layer was laminated on the protective film (2) side.

Example 37

Except having changed the polarizing film 1 to the polarizing film 5 in (production of the polarizing film with an adhesive layer) of Example 24, it carried out similarly to Example 24, and produced the polarizing film with the adhesive layer formed I did. In addition, the pressure-sensitive adhesive layer was laminated on the protective film (2) side.

Comparative Example 5

Except having changed the polarizing film (1) to the polarizing film (5) in Example 1 (adjustment of an acrylic pressure-sensitive adhesive composition) without using a phosphate ester (production of a polarizing film with an adhesive layer), it is carried out In the same manner as in Example 1, a polarizing film with an adhesive layer was produced. In addition, the pressure-sensitive adhesive layer was laminated on the protective film (2) side.

Comparative Example 6

In Example 1 (Adjustment of the acrylic pressure-sensitive adhesive composition), the solution containing the acrylic polymer (A-1) was changed to the solution containing the acrylic polymer (A-3) obtained in Production Example 9, and the phosphate ester was further changed to In the same manner as in Example 1, except for changing the polarizing film 1 to the polarizing film 6 in (production of a polarizing film with an adhesive layer) without using, a polarizing film with an adhesive layer was produced. I did. In addition, the pressure-sensitive adhesive layer was laminated on the protective film (2) side.

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

(Analysis method)

The composition of the phosphoric acid-based compound used in Examples and Comparative Examples was ^{calculated based on the measurement result of 31} P-NMR (Acetone-d6, room temperature). After calculating mol% from the integral value of the peak obtained by measurement, the content ratio (weight%) was calculated from the alkyl chain of the alcohol component of the ester.

( ³¹ P-NMR measurement conditions)

Measuring device: Bruker Biospin, AVANCEIII-400

Observation frequency: 160 ㎒ ( ³¹ P)

Flip angle: 30°

Measurement solvent: Acetone-d6 (heavy acetone)

Measurement temperature: room temperature

Chemical shift standard: P=(OCH ₃ ) ₃ in Acetone-d6 ( ³¹ P; 140 ppm external standard)

In Table 2, the phosphate 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 In the case of formula (2), R ¹ is a compound in which R 1 is a hydrogen atom), and the phosphate diester is a hydrocarbon having 1 to 18 carbon atoms in which ^{R 1} and R ^{2 in the general formula (1) may contain an oxygen atom.} It is a compound which is a residue (in the case of general formula (2), a compound which is a C1-C18 hydrocarbon residue which ^{R<1> may contain an oxygen atom).} For example, in the case of phosphanol SM-172, "monoester" is a compound in which R ¹ = H, R ³ = C ₈ H ₁₇ , n = 0 of the general formula (2), and "diester" is general ^{A compound in which R 1} =R ³ =C ₈ H ₁₇ of formula (2) and n = 0 is shown.

<corrosion resistance test>

A conductive film with an ITO layer formed on its surface (trade name: Elecrista (P400L), manufactured by Nitto Electric Co., Ltd.) was cut into 15 mm × 15 mm, and at the center of this conductive film, samples obtained in Examples and Comparative Examples After cutting and bonding to 8 mm × 8 mm, the sample was autoclaved at 50° C. and 5 atm for 15 minutes, as a measurement sample for corrosion resistance. The resistance value of the obtained measurement sample was measured using a measuring apparatus described later, and this was set as the "initial resistance value".

Thereafter, the measurement sample was put in an environment at a temperature of 60° C. and a humidity of 90% for 500 hours, and then the resistance value was measured as “the resistance value after moist heat”. In addition, the resistance value was measured using HL5500PC manufactured by Accent Optical Technologies. From the "initial resistance value" and "resistance value after moist heat" measured as described above, the resistance value change rate (%) was calculated by the following equation, and evaluated according to the following evaluation criteria.

(Evaluation standard)

◎: The resistance value change rate is less than 150% (the increase in the resistance value due to moist heat is small (corrosion resistance is good))

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

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

X: The resistance value change rate is 400% or more (the increase in the resistance value due to moist heat is large (corrosion resistance defect))

<Durability test of adhesive (peel and foam)>

The separator film of the polarizing film sample with the pressure-sensitive adhesive layer obtained in Examples and Comparative Examples was peeled off, bonded to the ITO surface of the alkali-free glass and the glass with the amorphous ITO described below, and then autoclaved at 50° C., 5 atm, and 15 minutes. After performing the treatment, it was put into a heating oven at 80°C and 100°C, and a thermo-hygrostat at 60°C/90%RH and 85°C/85%RH. Peeling and foaming of the polarizing film after 500 hours were observed visually, and evaluated according to the following evaluation criteria. Moreover, after carrying out the environment of 85 degreeC and -40 degreeC for 300 cycles in 1 cycle and 1 hour (heat shock test (HS test)), peeling and foaming of a polarizing film were observed visually, and it evaluated by the following evaluation criteria.

◎: No peeling or foaming was observed at all.

○: Peeling or foaming to a degree that cannot be confirmed with the naked eye was observed.

△: Small peeling or foaming that can be seen with the naked eye was observed.

X: Clear peeling or foaming was observed.

(Method of manufacturing amorphous ITO-formed glass)

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

The abbreviations in the table are as follows, respectively.

(Phosphate compound)

B-1: Phosphanol SM-172, acid value: 219 mgKOH/g, Mono-D mixture, manufactured by Toho Chemical Industries, Ltd.

B-2: Phosphanol RS-410, acid value: 105 mgKOH/g, Mono-D mixture, manufactured by Toho Chemical Industries, Ltd.

B-3: Phosphanol RS-710, acid value: 62 mgKOH/g, Mono-D mixture, manufactured by Toho Chemical Industries, Ltd.

B-4: DBP, acid value: 266 mgKOH/g, Mono-D mixture, manufactured by Johoku Chemical Co., Ltd.

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

B-6: MP-4, acid value: 670 mgKOH/g, Mono-D mixture, manufactured by Daihachi Chemical Industries, Ltd.

B-7: Mono-N-butyl phosphate (O=P(OH) ₂ (OC ₄ H ₉ ), Product Nomber: CDS001281), manufactured by SIGMA-ALDRICH

(Crosslinking agent)

Peroxide type: dibenzoyl peroxide

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

(Ionic compound)

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

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

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

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

Claims (22)

A polarizing film in which a pressure-sensitive adhesive layer having a pressure-sensitive adhesive layer is formed on 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/or iodine ions,
The iodine-based polarizing film is a one-sided protective polarizing film having a transparent protective film only on one side of the iodine-based polarizing film, and the side of the one-sided protective polarizing film which does not have a transparent protective film and the pressure-sensitive adhesive layer are in contact,
The polarizing film with the pressure-sensitive adhesive layer is used by bonding the pressure-sensitive adhesive layer of the polarizing film with the pressure-sensitive adhesive layer and the transparent conductive layer of a member having a transparent conductive layer in contact with each other,
The pressure-sensitive adhesive layer is the following general formula (1):
[Formula 1]

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom.)
A pressure-sensitive adhesive layer, characterized in that it is formed of an acrylic pressure-sensitive adhesive composition containing at least one phosphoric acid-based compound selected from the group consisting of a compound represented by and a multimer of the compound represented by the general formula (1), and a (meth)acrylic polymer. Formed polarizing film. The method of claim 1,
A polarizing film with a pressure-sensitive adhesive layer, wherein the content of iodine and/or iodine ions in the iodine polarizer is 1 to 14% by weight. The method of claim 2,
A polarizing film with an adhesive layer, wherein the content of iodine and/or iodine ions in the iodine polarizer is 3 to 12% by weight. The method of claim 1,
Phosphoric acid mono, which is a hydrocarbon residue having 1 to 18 carbon atoms in which the phosphoric acid-based compound contains phosphoric acid, and one of R ¹ and R ^{2 in the general formula (1) may contain a hydrogen atom and the other may contain an oxygen atom.} Ester, and a mixture containing at least one phosphate ester selected from the group consisting of phosphate diesters, which are hydrocarbon residues having 1 to 18 carbon atoms, wherein ^{R 1} and R ² in the general formula (1) may contain an oxygen atom. A polarizing film having an adhesive layer, characterized in that. The method of claim 4,
The polarizing film with a pressure-sensitive adhesive layer, characterized in that the phosphoric acid-based compound is a mixture containing phosphoric acid and phosphoric acid monoester. The method of claim 1,
The polarizing film with a pressure-sensitive adhesive layer, wherein the hydrocarbon residue having 1 to 18 carbon atoms is a linear or branched alkyl group having 1 to 10 carbon atoms. delete The method of claim 1,
The polarizing film with an adhesive layer, characterized in that the thickness of the iodine-based polarizer is 10 μm or less. The method of claim 1,
A polarizing film with a pressure-sensitive adhesive layer, characterized in that the total thickness of the iodine-based polarizing film is 80 μm or less. delete The method of claim 1,
The amount of the phosphoric acid-based compound added is 0.001 to 4 parts by weight based on 100 parts by weight of the (meth)acrylic polymer. The method of claim 1,
The polarizing film with a pressure-sensitive adhesive layer, wherein the (meth)acrylic polymer contains, as a monomer unit, an alkyl (meth)acrylate and a hydroxyl group-containing monomer. The method of claim 12,
A polarizing film with a pressure-sensitive adhesive layer, characterized in that the hydroxyl group-containing monomer is 4-hydroxybutyl acrylate. The method of claim 1,
A polarizing film with a pressure-sensitive adhesive layer, characterized in that the weight average molecular weight of the (meth)acrylic polymer is 1.2 million to 3 million. The method of claim 1,
The polarizing film with an adhesive layer, wherein the acrylic pressure-sensitive adhesive composition further contains a crosslinking agent. The method of claim 15,
The crosslinking agent is at least one type of crosslinking agent selected from the group consisting of a peroxide crosslinking agent and an isocyanate crosslinking agent. The method of claim 1,
The polarizing film with a pressure-sensitive adhesive layer, wherein the acrylic pressure-sensitive adhesive composition further contains an ionic compound. A lamination, characterized in that the polarizing film with the pressure-sensitive adhesive layer according to claim 1 and a transparent conductive member having a transparent conductive layer are bonded together so that the pressure-sensitive adhesive layer of the polarizing film with the pressure-sensitive adhesive layer and the transparent conductive layer of the substrate are in contact with each other. sieve. The method of claim 18,
A laminate, characterized in that the transparent conductive layer is formed of indium tin oxide. The method of claim 19,
The laminate, characterized in that the indium tin oxide is an amorphous indium tin oxide. A liquid crystal panel having an adhesive layer of a polarizing film in which the adhesive layer according to any one of claims 1 to 6, 8, 9, and 11 to 17 was formed, and a transparent conductive layer, An image display device, characterized in that 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 crystal panel are bonded to each other so as to contact each other. An image display device, wherein the laminate according to any one of claims 18 to 20 is used as a touch panel.

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