JP2021009231A - Polarization film, manufacturing method of the same, optical film and image display device - Google Patents

Abstract

To provide a polarization film which has no spot-like voids and no partial swelling on a transparent protective film surface.SOLUTION: In a polarization film, a transparent protective film is provided through an adhesive layer on at least one surface of a polarizer, one surface of the transparent protective film is the surface having a convex portion, the adhesive layer is provided on the surface having the convex portion of the transparent protective film, and the thickness of the adhesive layer is equal to or greater than 1.6 μm.SELECTED DRAWING: None

Description

The present invention relates to a method for producing a polarizing film in which a transparent protective film is provided on at least one surface of a polarizing element via an adhesive layer. The polarizing film can form an image display device such as a liquid crystal display (LCD), an organic EL display device, a CRT, or a PDP as an optical film obtained by itself or in a laminated manner.

Liquid crystal display devices are rapidly expanding into the market for watches, mobile phones, PDAs, laptop computers, monitors for personal computers, DVD players, TVs, and the like. The liquid crystal display device visualizes the polarization state due to switching of the liquid crystal, and a polarizer is used because of the display principle. In particular, applications such as TVs are required to have higher brightness, higher contrast, and a wider viewing angle, and polarizing films are also required to have higher transmittance, higher degree of polarization, and higher color reproducibility.

As the polarizer, since it has high transmittance and high degree of polarization, for example, an iodine-based polarizer having a stretched structure in which iodine is adsorbed on polyvinyl alcohol (hereinafter, simply referred to as “PVA”) is the most widely used. It is used. Generally, a polarizing film is used in which a transparent protective film is bonded to both sides of a polarizing element by a so-called water-based adhesive in which a polyvinyl alcohol-based material is dissolved in water (Patent Documents 1 and 2 below). As the transparent protective film, triacetyl cellulose having high moisture permeability or the like is used. When the water-based adhesive is used (so-called wet lamination), a drying step is required after the polarizer and the transparent protective film are bonded together.

On the other hand, instead of the water-based adhesive, an active energy ray-curable adhesive has been proposed. When a polarizing film is produced using an active energy ray-curable adhesive, a drying step is not required, so that the productivity of the polarizing film can be improved. For example, the present inventors have proposed a radical polymerization type active energy ray-curable adhesive using an N-substituted amide-based monomer as a curable component (Patent Document 3 below).

Japanese Unexamined Patent Publication No. 2001-296427 JP-A-2007-256569 Japanese Unexamined Patent Publication No. 2012-052000

However, in a conventional polarizing film obtained by bonding a polarizing element and a transparent protective film with an adhesive layer, there are cases where spot-like white spot defects occur or the surface of the transparent protective film is partially swollen. ..

An object of the present invention is to solve the above problems and to provide a polarizing film having no spot-like white spot defects and no partial swelling on the surface of the transparent protective film.

The above problem can be solved by the following configuration.

That is, the present invention is a polarizing film in which a transparent protective film is provided on at least one surface of the polarizing element via an adhesive layer.
One surface of the transparent protective film is a surface having a convex portion.
The adhesive layer is provided on the surface of the transparent protective film having a convex portion.
The present invention relates to a polarizing film, characterized in that the thickness of the adhesive layer is 1.6 μm or more.

As one aspect of the transparent protective film, the surface having the convex portion of the transparent protective film is a support peeling surface from which the film-forming support has been peeled off, and the convex portion is the surface of the film-forming support. It was formed due to the recess.

The transparent protective film is preferably a cellulosic resin film.

The thickness of the transparent protective film is preferably 30 μm or less.

The polarizing film preferably has an easy-adhesion layer that is a part of the adhesive layer on the bonding surface of the polarizer.

で表される化合物（ただし、Ｘは反応性基を含む官能基であり、Ｒ^１およびＲ^２はそれぞれ独立に、水素原子、置換基を有してもよい、脂肪族炭化水素基、アリール基、またはヘテロ環基を表す）及び／又は構造式中にＭ−Ｏ結合（Ｍはケイ素、チタン、アルミニウム、またはジルコニウムであり、Ｏは酸素原子である）を有する有機金属化合物を含有することが好ましい。なお、本発明においては、前記一般式（１）で表される化合物を「ホウ素含有化合物」ともいう。 The easy-adhesion composition, which is the material for forming the easy-adhesion layer, has the following general formula (1):

Compound represented by (where X is a functional group containing a reactive group, and R ¹ and R ² may independently have a hydrogen atom and a substituent, an aliphatic hydrocarbon group and an aryl group, respectively. , Or a heterocyclic group) and / or may contain an organometallic compound having an MO bond (M is silicon, titanium, aluminum, or zirconium, O is an oxygen atom) in the structural formula. preferable. In the present invention, the compound represented by the general formula (1) is also referred to as a "boron-containing compound".

で表される化合物（ただし、Ｙは有機基であり、Ｘ、Ｒ^１およびＲ^２は前記と同じ）であることが好ましい。 The compound represented by the general formula (1) is the following general formula (1').

It is preferable that the compound is represented by (where Y is an organic group and X, R ¹ and R ² are the same as described above).

The reactive groups of the compound represented by the general formula (1) are α, β-unsaturated carbonyl group, vinyl group, vinyl ether group, epoxy group, oxetane group, amino group, aldehyde group, mercapto group, and halogen. It is preferably at least one reactive group selected from the group consisting of groups.

The easy-adhesion composition preferably contains a polymerizable compound X having an SP value of 21.0 (MJ / m ³ ) ^1/2 or more and 26.0 (MJ / m ³ ) ^1/2 or less.

Further, the present invention is a method for manufacturing a polarizing film in which a transparent protective film is provided on at least one surface of a polarizing element via an adhesive layer.
One surface of the transparent protective film is a surface having a convex portion.
A coating step of applying the adhesive composition to the surface of the transparent protective film having a convex portion,
The polarizer and the transparent protective film are attached via a bonding step of bonding the polarizing element and the transparent protective film, and the adhesive layer having a thickness of 1.6 μm or more obtained by curing the adhesive composition. The present invention relates to a method for producing a polarizing film, which comprises a bonding step of bonding.

As one aspect of the transparent protective film, the surface having the convex portion of the transparent protective film is a support peeling surface from which the film-forming support has been peeled off, and the convex portion is the surface of the film-forming support. It was formed due to the recess.

The viscosity of the adhesive composition at the time of coating is preferably 0.5 to 100 mPa · s.

で表される化合物（ただし、Ｘは反応性基を含む官能基であり、Ｒ^１およびＲ^２はそれぞれ独立に、水素原子、置換基を有してもよい、脂肪族炭化水素基、アリール基、またはヘテロ環基を表す）及び／又は構造式中にＭ−Ｏ結合（Ｍはケイ素、チタン、アルミニウム、またはジルコニウムであり、Ｏは酸素原子である）を有する有機金属化合物を含有する易接着組成物を塗工する塗工工程を含むことが好ましい。 The method for producing the polarizing film is described in the following general formula (1): on the bonding surface of the polarizing element.

Compound represented by (where X is a functional group containing a reactive group, and R ¹ and R ² may independently have a hydrogen atom and a substituent, an aliphatic hydrocarbon group and an aryl group, respectively. , Or a heterocyclic group) and / or easy adhesion containing an organometallic compound having an MO bond (M is silicon, titanium, aluminum, or zirconium and O is an oxygen atom) in the structural formula. It is preferable to include a coating step of coating the composition.

The easy-adhesion composition preferably contains a polymerizable compound X having an SP value of 21.0 (MJ / m ³ ) ^1/2 or more and 26.0 (MJ / m ³ ) ^1/2 or less.

The present invention also relates to an optical film having the polarizing film.

The present invention also relates to the polarizing film or an image display device having the optical film.

The present inventor has investigated the causes of spot-like white spot defects and partial swelling on the surface of a transparent protective film in a conventional polarizing film. Then, it was considered that the above problem was caused by the following causes.

Conventionally, when a polarizing element and a transparent protective film are bonded together with an adhesive layer to produce a polarizing film, the surface of the transparent protective film on which the adhesive layer is provided is not particularly specified, and the adhesive layer is a transparent protective film. It was provided on any surface of.

When a minute convex portion is formed on the surface of the transparent protective film for some reason in the manufacturing process of the transparent protective film, and an adhesive layer is formed on the surface of the transparent protective film having the convex portion, the convex portion is formed. Since it becomes difficult for the adhesive layer to be formed on the surface, it is considered that a white spot defect occurs at the convex portion. Further, when the bonding surface of the polarizer and the surface having the convex portion of the transparent protective film are bonded via the adhesive composition, the bonding surface of the polarizing element and the convex portion come into contact with each other, and pressure is applied to the convex portion. Is hung. As a result, it is considered that the transparent protective film around the convex portion is pushed outward by the convex portion under pressure and deformed, and the surface of the transparent protective film is partially bulged.

Even when the adhesive layer is provided on the surface of the transparent protective film having a convex portion, the present inventor sets the thickness of the adhesive layer to 1.6 μm or more to cause spot-like white spot defects and transparency. It has been found that a polarizing film having no partial swelling on the surface of the protective film can be obtained. It is considered that by setting the thickness of the adhesive layer to 1.6 μm or more, the convex portion on the surface of the transparent protective film is completely covered with the adhesive layer, so that the occurrence of white spot defects is suppressed. Further, by making the thickness of the adhesive layer 1.6 μm or more, the pressure applied to the convex portion at the time of bonding is relaxed by the adhesive composition, and the convex portion makes it difficult for the transparent protective film around the convex portion to be pushed outward. Therefore, it is considered that partial swelling is less likely to occur on the surface of the transparent protective film.

The following causes can be considered as one of the causes for forming the convex portion on the surface of the transparent protective film.

For a transparent protective film such as a triacetyl cellulose film, a polymer solution in which a polymer is dissolved in a solvent is usually applied onto a support for film formation to form a coating film, and the film is formed while volatilizing the solvent from the formed coating film. It is produced by a so-called solution casting film forming method in which the produced film is then peeled off from the film-forming support.

In the process of manufacturing the transparent protective film, the side of the transparent protective film from which the film-forming support has been peeled off due to minute scratches and recesses such as pinholes existing on the surface of the film-forming support. It is considered that a convex portion is formed on the surface (support peeling surface).

As a method of solving the problem of spot-like white spot defects or partial swelling on the surface of the transparent protective film, a method of providing an adhesive layer on a surface (air side surface) of the transparent protective film that is not the support peeling surface. Can be considered. However, on the air side of the transparent protective film, a specific curable component in the adhesive composition easily penetrates into the film, and if the curable component permeates excessively into the film, a fragile layer is formed in the adhesive layer. It has been found that it may be formed, which may reduce the adhesive strength. Therefore, the method of providing the adhesive layer on the air side surface of the transparent protective film limits the design of the adhesive composition. When the adhesive layer is provided on the peeling surface side of the support of the transparent protective film, by setting the thickness of the adhesive layer to 1.6 μm or more as described above, the spot-like white spot defects and the surface of the transparent protective film are formed. A polarizing film without partial swelling can be obtained.

Further, the present inventor has found that problems such as spot-like white spot defects and partial swelling on the surface of the transparent protective film are likely to occur when a cellulose-based resin film is used. Therefore, the present invention is particularly effective when a cellulosic resin film is used.

Further, the present inventor has found that the problem of partial swelling on the surface of the transparent protective film tends to occur when the thickness of the transparent protective film is 30 μm or less. Therefore, the present invention is particularly effective when a transparent protective film having a thickness of 30 μm or less is used.

Further, when the bonding surface of the polarizing element and the surface having the convex portion of the transparent protective film are bonded to each other via the adhesive composition, air bubbles are likely to be mixed between the bonding surface of the polarizing element and the convex portion. There was a problem. The present inventor provides polarization by providing an easy-adhesive composition layer (the easy-adhesive composition layer becomes an easy-adhesive layer that is a part of the adhesive layer after curing) on the bonding surface of the polarizer. It was found that air bubbles are less likely to be mixed between the bonding surface of the child and the convex portion.

The easy-adhesion composition, which is a material for forming the easy-adhesion layer, preferably contains the boron-containing compound. The boron-containing compound can react with a functional group such as a hydroxyl group contained in a polarizer. This makes it possible to improve the adhesiveness between the polarizer and the adhesive layer, and as a result, has the effect of improving the water resistance of the polarizing film. Here, when the water content of the polarizer is low, for example, when the moisture content of the polarizer is 15% by mass or less, the boron-containing compound and the functional group contained in the polarizer cannot sufficiently react, and the effect is sufficient. May not be obtained. However, even when the water content of the polarizer is low, by blending water in the easy-adhesion composition, the reactivity of the boron-containing compound with the functional group contained in the polarizer is enhanced, and thereby adhesion to the polarizer. The adhesiveness with the agent layer can be improved. As a result, even when the moisture content of the polarizing element is low, it is possible to achieve both improvement in the water resistance of the polarizing film and improvement in the coatability of the easy-adhesion composition.

Further, the easy-adhesion composition preferably contains the organometallic compound. The organometallic compound becomes an active metal species due to the intervention of water, and as a result, the organometallic compound can form a strong bond with the polarizer. However, since the organometallic compound has a plurality of reaction points, the organometallic compound that has reacted with the polarizer still has unreacted points. Then, the organometallic compound can form a strong bond with the curable component in the adhesive composition coated on the bonded surface of the transparent protective film. As described above, since the organometallic compound can form a strong bond with both the polarizer and the adhesive layer, the water resistance between the polarizer and the adhesive layer is dramatically improved.

Further, the easy-adhesion composition preferably contains a polymerizable compound X having an SP value of 21.0 (MJ / m ³ ) ^1/2 or more and 26.0 (MJ / m ³ ) ^1/2 or less. .. Since the SP value of the polymerizable compound X is close to the SP value of a transparent protective film such as an unkenken triacetyl cellulose film and an acrylic film, the polymerizable compound X improves the adhesiveness between the adhesive layer and the transparent protective film. Contribute. Since the polymerizable compound X is a raw material for the adhesive layer, it is usually blended in the adhesive composition. As described above, the polymerizable compound X is preferably added in a large amount to the adhesive composition because it contributes to the improvement of the adhesiveness between the adhesive layer and the transparent protective film. However, when a large amount of the polymerizable compound X is blended in the adhesive composition, the polymerizable compound X easily permeates into the transparent protective film. When the polymerizable compound X is excessively permeated into the transparent protective film, a fragile layer is formed in the adhesive layer, thereby reducing the adhesive strength. As a result, the adhesiveness between the adhesive layer and the transparent protective film is reduced. By blending the polymerizable compound X in the easy-adhesive composition, not only can the excessive permeation of the polymerizable compound X into the transparent protective film be suppressed, but also the polymerizable compound in the easy-adhesive composition can be suppressed. The X and the curable component in the adhesive composition react with each other to integrate the easy-adhesive layer and the adhesive layer (make the easy-adhesive layer a part of the adhesive layer). Thereby, the adhesive force between the polarizer and the adhesive layer can be improved without lowering the adhesiveness between the adhesive layer and the transparent protective film.

Further, when the adhesive composition is applied to the surface of the transparent protective film having the convex portion, there is a problem that air bubbles are likely to be mixed around the convex portion. The present inventor has found that by adjusting the viscosity of the adhesive composition at the time of coating to 0.5 to 100 mPa · s, it becomes difficult for air bubbles to be mixed around the convex portion.

In the polarizing film of the present invention, a transparent protective film is provided on at least one surface of the polarizing element via an adhesive layer, and one surface of the transparent protective film is a surface having a convex portion. The adhesive layer is provided on the surface of the transparent protective film having a convex portion, and the thickness of the adhesive layer is 1.6 μm or more.

Hereinafter, the polarizing film of the present invention will be described in detail.
<Polarizer>
In the present invention, from the viewpoint of improving optical durability in a harsh environment under high temperature and high humidity, it is preferable to use a thin polarizing element having a thickness of 3 μm or more and 15 μm or less, more preferably 12 μm or less, and further. It is preferably 10 μm or less, and particularly preferably 8 μm or less. Such a thin polarizing element has less uneven thickness, excellent visibility, and less dimensional change, so that it has excellent durability against thermal shock.

The thin polarizer generally has a low water content, and specifically, the water content is often 15% by mass or less. While such a thin polarizer having a low water content has the above-mentioned effects, it has low reactivity with a boron-containing compound or an organic metal compound contained in the easy-adhesion composition used in the present invention, and adheres to the polarizer. The effect of improving the adhesiveness with the agent layer may not be sufficient. Therefore, in the polarizing film of the present invention, when a polarizing element having a water content of 15% by mass or less is used, the easy-adhesion composition preferably contains water, and specifically, the total amount of the easy-adhesion composition is 100. In terms of mass%, the water content is preferably 5 to 90% by mass, more preferably 30 to 80% by mass.

As the polarizer, one using a polyvinyl alcohol-based resin is used. As the polarizer, for example, a hydrophilic polymer film such as a polyvinyl alcohol-based film, a partially formalized polyvinyl alcohol-based film, an ethylene-vinyl acetate copolymerization system partially saponified film, and a bicolor property of iodine or a bicolor dye are used. Examples thereof include a uniaxially stretched film by adsorbing a substance, a polyene-based oriented film such as a dehydrated product of polyvinyl alcohol and a dehydrogenated product of polyvinyl chloride. Among these, a polarizer made of a polyvinyl alcohol-based film and a dichroic substance such as iodine is preferable.

A polarizer obtained by dyeing a polyvinyl alcohol-based film with iodine and uniaxially stretching it can be produced, for example, by dyeing polyvinyl alcohol by immersing it in an aqueous solution of iodine and stretching it 3 to 7 times its original length. If necessary, boric acid, zinc sulfate, zinc chloride and the like may be contained, or the mixture may be immersed in an aqueous solution such as potassium iodide. Further, if necessary, the polyvinyl alcohol-based film may be immersed in water and washed with water before dyeing. In addition to being able to clean the surface of the polyvinyl alcohol film and blocking inhibitors by washing the polyvinyl alcohol film with water, it also has the effect of preventing non-uniformity such as uneven dyeing by swelling the polyvinyl alcohol film. is there. Stretching may be performed after dyeing with iodine, stretching while dyeing, or stretching and then dyeing with iodine. It can be stretched even in an aqueous solution such as boric acid or potassium iodide or in a water bath.

It is preferable that the polarizer contains boric acid from the viewpoint of stretching stability and humidification reliability. Further, the boric acid content contained in the polarizer is preferably 22% by mass or less, more preferably 20% by mass or less, based on the total amount of the polarizer, from the viewpoint of suppressing the occurrence of through cracks. From the viewpoint of stretching stability and humidification reliability, the boric acid content with respect to the total amount of the polarizer is preferably 10% by mass or more, and more preferably 12% by mass or more.

As a thin polarizer, typically
Japanese Patent No. 4751486,
Japanese Patent No. 4751481
Patent No. 4815544,
Japanese Patent No. 5048120,
International Publication No. 2014/07759 Pamphlet,
International Publication No. 2014/077636 Pamphlet,
And the like, or the thin polarizing element obtained from the manufacturing method described in these.

The thin polarizer is patented in Patent No. 4751486, in that it can be stretched at a high magnification and the polarization performance can be improved even in a manufacturing method including a step of stretching in a laminated state and a step of dyeing. Those obtained by a production method including a step of stretching in an aqueous boric acid solution as described in Japanese Patent No. 4751481 and Japanese Patent No. 4815544 are preferable, and particularly described in Japanese Patent No. 4751481 and Japanese Patent No. 4815544. It is preferably obtained by a production method including a step of auxiliary stretching in the air before stretching in a certain boric acid aqueous solution. These thin polarizers can be obtained by a production method including a step of stretching a polyvinyl alcohol-based resin (hereinafter, also referred to as PVA-based resin) layer and a resin base material 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 can be stretched without problems such as breakage due to stretching because it is supported by the stretching resin base material.

<Transparent protective film>
The transparent protective film used in the present invention is not particularly limited. For example, a polymer solution in which a polymer is dissolved in a solvent is applied onto a support for film formation to form a coating film, and the solvent is volatilized from the formed coating film. While producing a film, the produced film is then peeled off from the film-forming support, which is produced by a so-called solution casting film forming method. Further, the transparent protective film may be produced on a film-forming support by extrusion molding.

One surface of the transparent protective film used in the present invention is a surface having a convex portion. As one aspect of the transparent protective film, the surface having the convex portion of the transparent protective film is a support peeling surface from which the film-forming support has been peeled off, and the convex portion is the surface of the film-forming support. It is formed due to the recess of. The shape of the convex portion is not particularly limited, but is mainly a mountain shape (for example, 80% or more of the total convex portion). The height of the convex portion varies depending on the type of the transparent protective film, but is usually about 6 μm at the maximum, for example, 0.5 to 3 μm, 1 to 2.5 μm, or 1.2 to 2 μm on average. The size (maximum width) of the convex portion varies depending on the type of the transparent protective film, but is usually about 50 μm at the maximum, for example, 5 to 30 μm, 10 to 20 μm, or 10 to 15 μm on average.

The transparent protective film preferably has excellent transparency, mechanical strength, thermal stability, moisture barrier property, isotropic property, 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, and styrene such as polystyrene and acrylonitrile-styrene copolymer (AS resin). Examples thereof include based polymers and polystyrene polymers. In addition, polyethylene, polypropylene, polyolefins having a cyclo or norbornene structure, polyolefin polymers such as ethylene / propylene copolymers, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamides, imide polymers, and sulfone polymers. , Polyether sulfone polymer, polyether ether ketone polymer, polyphenylene sulfide polymer, vinyl alcohol polymer, vinylidene chloride polymer, vinyl butyral polymer, allylate polymer, polyoxymethylene polymer, epoxy polymer, or the above. Polymer blends and the like are also examples of polymers that form the transparent protective film. The transparent protective film may contain one or more of any suitable additives. Examples of the additive include an ultraviolet absorber, an antioxidant, a lubricant, a plasticizer, a mold release agent, a color retardant, a flame retardant, a nucleating agent, an antistatic agent, a pigment, a colorant and the like. The content of the thermoplastic resin in the transparent protective film is preferably 50 to 100% by mass, more preferably 50 to 99% by mass, still more preferably 60 to 98% by mass, and particularly preferably 70 to 97% by mass. .. When the content of the thermoplastic resin in the transparent protective film is 50% by mass or less, the high transparency inherent in the thermoplastic resin may not be sufficiently exhibited.

Further, as the transparent protective film, a polymer film described in JP-A-2001-343529 (WO01 / 37007), for example, a thermoplastic resin having a substituted and / or unsubstituted imide group in the side chain (A) and a side thereof. Examples thereof include resin compositions containing a thermoplastic resin having a substituted and / or unsubstituted phenyl and a nitrile group in the chain. Specific examples thereof include a film of a resin composition containing an alternating copolymer composed of isobutylene and N-methylmaleimide and an acrylonitrile / styrene copolymer. As the film, a film made of a mixed extruded product of a resin composition or the like can be used. Since these films have a small phase difference and a small photoelastic coefficient, problems such as unevenness due to distortion of the polarizing film can be eliminated, and since the moisture permeability is small, they are excellent in humidification durability.

Further, in the present invention, the moisture permeability of the transparent protective film used is preferably 150 g / m ² / 24h or less. According to such a configuration, it is difficult for moisture in the air to enter the polarizing film, and it is possible to suppress a change in the moisture content of the polarizing film itself. As a result, it is possible to suppress curl and dimensional change of the polarizing film caused by the storage environment.

As the transparent protective film provided on one side or both sides of the polarizer, those having excellent transparency, mechanical strength, thermal stability, moisture blocking property, isotropic property, etc. are preferable, and the moisture permeability is particularly 150 g / m ² / 24h. The following is more preferable, 120 g / m ² / 24h or less is particularly preferable, and 5 to 70 g / m ² / 24h or less is even more preferable.

Examples of the material for forming the transparent protective film satisfying the low moisture permeability include polyester resins such as polyethylene terephthalate and polyethylene naphthalate; polycarbonate resins; allylate resins; amide resins such as nylon and aromatic polyamides; polyethylene and polypropylene. , Polyethylene-based polymers such as ethylene / propylene copolymers, cyclic olefin-based resins having a cyclo-based or norbornene structure, (meth) acrylic-based resins, or mixtures thereof can be used. Among the resins, a polycarbonate resin, a cyclic polyolefin resin, and a (meth) acrylic resin are preferable, and a cyclic polyolefin resin and a (meth) acrylic resin are particularly preferable.

Further, in the present invention, it is preferable to use a cellulosic resin film as the transparent protective film, and more preferably a triacetyl cellulose film.

The thickness of the transparent protective film can be appropriately determined, but is generally preferably 5 to 100 μm, more preferably 10 to 50 μm, still more preferably 10 to 50 μm, from the viewpoints of workability such as strength and handleability, and thin layer property. Is 10 to 30 μm, particularly preferably 10 to 25 μm.

As the transparent protective film, one having a front retardation of less than 40 nm and a thickness direction retardation of less than 80 nm is usually used. The front phase difference Re is represented by Re = (nx−ny) × d. The thickness direction phase difference Rth is represented by Rth = (nx−nz) × d. The Nz coefficient is represented by Nz = (nx-nz) / (nx-ny). [However, the refractive indexes in the slow axis direction, the phase advance axis direction, and the thickness direction of the film are nx, ny, and nz, respectively, and d (nm) is the thickness of the film. The slow-phase axial direction is the direction that maximizes the refractive index in the film plane. ]. It is preferable that the transparent protective film is not colored as much as possible. A protective film having a retardation value in the thickness direction of −90 nm to + 75 nm is preferably used. By using a film having a retardation value (Rth) of −90 nm to +75 nm in the thickness direction, coloring (optical coloring) of the polarizing film caused by the transparent protective film can be substantially eliminated. The thickness direction retardation value (Rth) is more preferably −80 nm to +60 nm, and particularly preferably −70 nm to +45 nm.

On the other hand, as the transparent protective film, a retardation plate having a front retardation of 40 nm or more and / or a thickness direction retardation of 80 nm or more can be used. The frontal phase difference is usually controlled in the range of 40 to 200 nm, and the thickness direction phase difference is usually controlled in the range of 80 to 300 nm. When a retardation plate is used as the transparent protective film, the retardation plate also functions as a transparent protective film, so that the thickness can be reduced.

Examples of the retardation plate include a birefringent film formed by uniaxially or biaxially stretching a polymer material, an alignment film of a liquid crystal polymer, and a film in which an alignment layer of a liquid crystal polymer is supported by a film. The thickness of the retardation plate is not particularly limited, but is generally about 20 to 150 μm. Examples of the polymer material include polyvinyl alcohol, polyvinyl butyral, polymethyl vinyl ether, polyhydroxyethyl acrylate, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, polycarbonate, polyarylate, polysulfone, polyethylene terephthalate, polyethylene naphthalate, polyether sulfone, and the like. Polyphenylene sulphide, polyphenylene oxide, polyallyl sulfone, polyamide, polyimide, polyolefin, polyvinyl chloride, cellulose resin, cyclic polyolefin resin (norbornene resin), or these binary and ternary various copolymers and grafts Examples include copolymers and blends. These polymer materials become oriented substances (stretched films) by stretching or the like.

Examples of the liquid crystal polymer include various types of main chain type and side chain type in which a conjugated linear atomic group (mesogen) that imparts liquid crystal orientation is introduced into the main chain or side chain of the polymer. .. Specific examples of the main chain type liquid crystal polymer include a nematically oriented polyester-based liquid crystal polymer, a discotic polymer, a cholesteric polymer, and the like having a structure in which a mesogen group is bonded at a spacer portion that imparts flexibility. Specific examples of the side chain type liquid crystal polymer include polysiloxane, polyacrylate, polymethacrylate or polymalonate as the main chain skeleton, and para-substitution of nematic orientation imparting via a spacer portion composed of conjugated atomic groups as the side chain. Examples thereof include those having a mesogen portion composed of a cyclic compound unit. For these liquid crystal polymers, for example, a solution of the liquid crystal polymer is applied on an alignment-treated surface such as a thin film formed on a glass plate, such as polyimide or polyvinyl alcohol, which is rubbed, or an obliquely vapor-deposited silicon oxide. It is performed by developing and heat-treating.

The retardation plate may have an appropriate phase difference according to the purpose of use, such as one for the purpose of compensating for coloring and viewing angle due to birefringence of various wave plates and liquid crystal layers, and may have two or more types. A phase difference plate may be laminated to control optical characteristics such as a phase difference.

The retardation plate has the relationship of nx = ny> nz, nx> ny> nz, nx> ny = nz, nz> nz> ny, nz = nz> ny, nz> ny> ny, nz> nz = ny. Satisfied ones are selected and used according to various uses. Note that ny = nz includes not only the case where ny and nz are completely the same, but also the case where ny and nz are substantially the same.

For example, as a retardation plate satisfying nx> ny> nz, a retardation plate satisfying a front retardation of 40 to 100 nm, a thickness direction retardation of 100 to 320 nm, and an Nz coefficient of 1.8 to 4.5 is used. Is preferable. For example, in a retardation plate (positive A plate) satisfying nx> ny = nz, it is preferable to use a retardation plate satisfying a front retardation of 100 to 200 nm. For example, in a retardation plate (negative A plate) satisfying nz = nx> ny, it is preferable to use a retardation plate satisfying a front retardation of 100 to 200 nm. For example, in a retardation plate satisfying nx> nz> ny, it is preferable to use a retardation plate having a front retardation of 150 to 300 nm and an Nz coefficient of more than 0 and satisfying ~ 0.7. Further, as described above, for example, those satisfying nx = ny> nz, nz> nx> ny, or nz> nx = ny can be used.

The transparent protective film can be appropriately selected depending on the liquid crystal display device to be applied. For example, in the case of VA (including Vertical Realing, MVA, PVA), it is desirable that at least one (cell side) transparent protective film of the polarizing film has a phase difference. As a specific phase difference, it is desirable that Re = 0 to 240 nm and Rth = 0 to 500 nm. In terms of the three-dimensional refractive index, the cases of nx> ny = nz, nx> ny> nz, nx> nz> ny, nx = ny> nz (positive A plate, biaxial, negative C plate) are desirable. In the VA type, it is preferable to use a combination of a positive A plate and a negative C plate, or a single biaxial film. When the polarizing films are used on the upper and lower sides of the liquid crystal cell, the upper and lower sides of the liquid crystal cell may have a phase difference, or either the upper or lower transparent protective film may have a phase difference.

For example, in the case of IPS (including In-Plane Switching and FFS), either the transparent protective film on one side of the polarizing film has a phase difference or the transparent protective film does not have a phase difference. For example, when there is no phase difference, it is desirable that there is no phase difference between the top and bottom (cell side) of the liquid crystal cell. In the case of having a phase difference, it is desirable that the upper and lower sides of the liquid crystal cell have a phase difference, and that either the upper or lower side has a phase difference (for example, nx> nz> ny on the upper side). A biaxial film that satisfies the relationship, when there is no phase difference on the lower side, or when there is a positive A plate on the upper side and a positive C plate on the lower side). When it has a phase difference, the range of Re = −500 to 500 nm and Rth = −500 to 500 nm is desirable. In terms of the three-dimensional refractive index, nx> ny = nz, nx> nz> ny, nz> nz = ny, nz> nz> ny (positive A plate, biaxial, positive C plate) are desirable.

で表される化合物（ただし、Ｘは反応性基を含む官能基であり、Ｒ^１およびＲ^２はそれぞれ独立に、水素原子、置換基を有してもよい、脂肪族炭化水素基、アリール基、またはヘテロ環基を表す）を含有することが好ましい。前記脂肪族炭化水素基としては、炭素数１〜２０の置換基を有してもよい直鎖または分岐のアルキル基、炭素数３〜２０の置換基を有してもよい環状アルキル基、炭素数２〜２０のアルケニル基が挙げられ、アリール基としては、炭素数６〜２０の置換基を有してもよいフェニル基、炭素数１０〜２０の置換基を有してもよいナフチル基などが挙げられ、ヘテロ環基としては例えば、少なくとも一つのヘテロ原子を含む、置換基を有してもよい５員環または６員環の基が挙げられる。これらは互いに連結して環を形成してもよい。一般式（１）中、Ｒ^１およびＲ^２として好ましくは、水素原子、炭素数１〜３の直鎖または分岐のアルキル基であり、最も好ましくは、水素原子である。なお、一般式（１）で表される化合物は、最終的に形成される易接着層中に未反応の状態で存在しても良く、各官能基が反応した状態で存在しても良い。 <Easy adhesive composition>
The easy-adhesion composition used in the present invention has the following general formula (1):

Compound represented by (where X is a functional group containing a reactive group, and R ¹ and R ² may independently have a hydrogen atom and a substituent, an aliphatic hydrocarbon group and an aryl group, respectively. , Or a heterocyclic group) is preferably contained. The aliphatic hydrocarbon group includes a linear or branched alkyl group which may have a substituent having 1 to 20 carbon atoms, a cyclic alkyl group which may have a substituent having 3 to 20 carbon atoms, and carbon. Examples thereof include an alkenyl group having a number of 2 to 20, and examples of the aryl group include a phenyl group which may have a substituent having 6 to 20 carbon atoms, a naphthyl group which may have a substituent having 10 to 20 carbon atoms and the like. Examples of the heterocyclic group include a 5-membered ring or 6-membered ring group which may have a substituent and contains at least one heteroatom. These may be connected to each other to form a ring. In the general formula (1), R ¹ and R ² are preferably a hydrogen atom, a linear or branched alkyl group having 1 to 3 carbon atoms, and most preferably a hydrogen atom. The compound represented by the general formula (1) may be present in the finally formed easy-adhesion layer in an unreacted state, or may be present in a state in which each functional group is reacted.

X contained in the compound represented by the general formula (1) is a functional group containing a reactive group, which is a functional group capable of reacting with a curable component constituting the adhesive layer, and is used as a reactive group contained in X. For example, hydroxyl group, amino group, aldehyde group, carboxyl group, vinyl group, (meth) acrylic group, styryl group, (meth) acrylamide group, vinyl ether group, epoxy group, oxetane group, α, β-unsaturated carbonyl. Groups, mercapto groups, halogen groups and the like can be mentioned. When the adhesive composition constituting the adhesive layer is active energy ray-curable, the reactive groups contained in X are vinyl group, (meth) acrylic group, styryl group, (meth) acrylamide group, vinyl ether group, epoxy. It is preferably at least one reactive group selected from the group consisting of a group, an oxetane group and a mercapto group, and particularly when the adhesive composition constituting the adhesive layer is radically polymerizable, the reaction contained in X. The sex group is preferably at least one reactive group selected from the group consisting of a (meth) acrylic group, a styryl group and a (meth) acrylamide group, and the compound represented by the general formula (1) is (1). When it has a meta) acrylamide group, it is more preferable because it has high reactivity and the copolymerization rate with the active energy ray adhesive composition increases. In addition, the (meth) acrylamide group has a high polarity and is excellent in adhesiveness, so that the effect of the present invention can be efficiently obtained, which is also preferable. When the adhesive composition constituting the adhesive layer is cationically polymerizable, the reactive group contained in X is selected from a hydroxyl group, an amino group, an aldehyde, a carboxyl group, a vinyl ether group, an epoxy group, an oxetane group and a mercapto group. It is preferable to have at least one functional group, particularly when it has an epoxy group, because it has excellent adhesion between the obtained adhesive layer and the adherend, and when it has a vinyl ether group, the curability of the adhesive composition Is preferable because it is excellent.

で表される化合物（ただし、Ｙは有機基であり、Ｘ、Ｒ^１およびＲ^２は前記と同じ）が挙げられる。さらに好適には、以下の化合物（１ａ）〜（１ｄ）が挙げられる。 As a preferable specific example of the compound represented by the general formula (1), the following general formula (1')

Examples thereof include compounds represented by (where Y is an organic group and X, R ¹ and R ² are the same as described above). More preferably, the following compounds (1a) to (1d) can be mentioned.

In the present invention, the compound represented by the general formula (1) may be a compound in which a reactive group and a boron atom are directly bonded, but as shown in the specific example, the general formula (1) It is preferable that the compound represented by (1) is a compound in which a reactive group and a boron atom are bonded via an organic group, that is, a compound represented by the general formula (1'). When the compound represented by the general formula (1) is bonded to a reactive group via, for example, an oxygen atom bonded to a boron atom, the water-resistant adhesiveness of the polarizing film tends to deteriorate. On the other hand, the compound represented by the general formula (1) does not have a boron-oxygen bond, but contains a reactive group while having a boron-carbon bond by bonding a boron atom and an organic group. When it is a compound (general formula (1')), it is preferable because the water resistance and adhesiveness of the polarizing film are improved. The organic group specifically means an organic group having 1 to 20 carbon atoms which may have a substituent, and more specifically, for example, having a substituent having 1 to 20 carbon atoms. It may have a linear or branched alkylene group, a cyclic alkylene group which may have a substituent having 3 to 20 carbon atoms, a phenylene group which may have a substituent having 6 to 20 carbon atoms, and 10 to 10 carbon atoms. Examples thereof include a naphthylene group which may have 20 substituents.

In addition to the compounds exemplified above, the compounds represented by the general formula (1) include hydroxyethyl acrylamide and boric acid ester, methylol acrylamide and boric acid ester, hydroxyethyl acrylate and boric acid ester, and hydroxybutyl. Esters of (meth) acrylate and boric acid, such as esters of acrylate and boric acid, can be exemplified.

If the content of the compound represented by the general formula (1) in the easy-adhesion composition is too small, the proportion of the compound represented by the general formula (1) present on the surface of the easy-adhesion layer decreases, and the easy-adhesion effect May be low. Therefore, the content of the compound represented by the general formula (1) in the easy-adhesion composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and 0. It is more preferably 1% by mass or more. The content of the compound represented by the general formula (1) in the easy-adhesion composition is usually 5% by mass or less, preferably 3% by mass or less, and more preferably 2% by mass or less. ..

Further, the easy-adhesion composition preferably contains an organometallic compound having an MO bond (M is silicon, titanium, aluminum, or zirconium, and O is an oxygen atom) in the structural formula. The organometallic compound may be present in the finally formed easy-adhesion layer in an unreacted state, or may be present in a state in which each functional group is reacted.

The organometallic compound has an MO bond (M is silicon, titanium, aluminum, or zirconium, and O is an oxygen atom) in the structural formula. The organometallic compound is preferably at least one selected from the group consisting of organosilicon compounds, metal alkoxides, and metal chelates.

As the organosilicon compound, one having a Si—O bond can be used without particular limitation, and as a specific example, an active energy ray-curable organosilicon compound or an organosilicon compound that is not active energy ray-curable can be used. Can be mentioned. In particular, it is preferable that the organic silicon compound has 3 or more carbon atoms. Specific examples of the active energy ray-curable compound include vinyl trichlorosilane, vinyl trimethoxysilane, vinyl triethoxysilane, 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, and 3-glycidoxypropyltrimethoxysilane. , 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacry Examples thereof include loxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane.

Preferred are 3-methacryloxypropyltrimethoxysilane and 3-acryloxypropyltrimethoxysilane.

As the compound which is not active energy ray-curable, a compound having an amino group is preferable. Specific examples of the compound having an amino group include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, and γ-aminopropylmethyldi. Ethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2-) Aminoethyl) Aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropyltriisopropoxysilane, γ- (2- (2-aminoethyl) aminoethyl) aminopropyltrimethoxysilane, γ- (6- (6- Aminohexyl) Aminopropyltrimethoxysilane, 3- (N-ethylamino) -2-methylpropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, N-phenyl-γ-aminopropyl Trimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N- Amino group-containing silanes such as phenylaminomethyltrimethoxysilane, (2-aminoethyl) aminomethyltrimethoxysilane, N, N'-bis [3- (trimethoxysilyl) propyl] ethylenediamine; N- (1,3) Examples of ketimine-type silanes such as −dimethylbutylidene) -3- (triethoxysilyl) -1-propaneamine can be mentioned.

As the compound having an amino group, only one kind may be used, or a plurality of kinds may be used in combination. Of these, in order to ensure good adhesion, γ-aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane , Γ- (2-Aminoethyl) Aminopropyltriethoxysilane, γ- (2-Aminoethyl) Aminopropylmethyldiethoxysilane, N- (1,3-dimethylbutylidene) -3- (Triethoxysilyl)- 1-Propylamine is preferred.

Specific examples of non-active energy ray-curable compounds other than the above include 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, and bis. Examples thereof include (triethoxysilylpropyl) tetrasulfide, 3-isocyanatepropyltriethoxysilane, and imidazolesilane.

The metal alkoxy is a compound in which at least one alkoxy group, which is an organic group, is bonded to a metal, and the metal chelate is a compound in which an organic group is bonded or coordinated to a metal via an oxygen atom. As the metal, titanium, aluminum and zirconium are preferable. Among these, aluminum and zirconium have faster reactivity than titanium, and the pot life of the easy-adhesion composition may be shortened, and the effect of improving the water-adhesion resistance may be reduced. Therefore, titanium is more preferable as the metal of the organometallic compound from the viewpoint of improving the water resistance of the adhesive layer.

When the easy-adhesion composition contains a metal alkoxide as an organic metal compound, it is preferable to use one having an organic group having 3 or more carbon atoms, and more preferably 6 or more carbon atoms. When the number of carbon atoms is 2 or less, the pot life of the easy-adhesion composition is shortened, and the effect of improving the water-resistant adhesiveness may be reduced. Examples of the organic group having 6 or more carbon atoms include an octoxy group, which can be preferably used. Suitable metal alkoxides include, for example, tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetraoctyl titanate, tertiary aluminum titanate, tetratershary butyl titanate, tetrastearyl titanate, zirconium tetraisopropoxide, zirconium tetranormal. Butoxyd, zirconium tetraoctoxide, zirconium tetratershaly butoxide, zirconium tetrapropoxide, aluminum sec butylate, aluminum ethylate, aluminum isoprepylate, aluminum butylate, aluminum diisopropirate monosecondary butylate, monosec butoxyaluminum diisopropi Rate, etc. Of these, tetraoctyl titanate is preferable.

When the easy-adhesion composition contains a metal chelate as an organometallic compound, it is preferable that the metal chelate contains an organic group having 3 or more carbon atoms. When the number of carbon atoms is 2 or less, the pot life of the easy-adhesion composition is shortened, and the effect of improving the water-resistant adhesiveness of the polarizing film may be reduced. Examples of the organic group having 3 or more carbon atoms include an acetylacetonate group, an ethylacetacetate group, an isostearate group, and an octylene glycolate group. Among these, an acetylacetonate group or an ethylacetacetate group is preferable as the organic group from the viewpoint of improving the water resistance of the adhesive layer. Suitable metal chelates include, for example, titanium acetylacetonate, titanium octylene glycolate, titanium tetraacetylacetonate, titanium ethylacetone acetate, polyhydroxytitanium stearate, dipropoxy-bis (acetylacetonato) titanium, dibutoxytitanium. -Bis (octylene glycolate), dipropoxytitanium-bis (ethylacetate acetate), titanium lactate, titanium diethanolaminate, titanium triethanolaminate, dipropoxytitanium-bis (lactate), dipropoxytitanium-bis (triethanol) Aminate), di-n-butoxytitanium-bis (triethanolaminet), tri-n-butoxytitanium monostearate, diisopropoxybis (ethylacetoneacetone) titanium, diisopropoxybis (acetylacetone) Titanium, diisopropoxybis (acetylacetone) titanium, titanium phosphate compound, titanium lactate ammonium salt, titanium-1,3-propanedioxybis (ethylacetoacetate), titanium dodecylbenzenesulfonate compound, titanium aminoethylamino etano Rate, zirconium tetraacetylacetonate, zirconium monoacetylacetonate, zirconium bisacetylacetonetate, zirconium acetylacetonate bisethylacetoneacetate, zirconium acetate, tri-n-butoxyethylacetone acetate zirconium, di-n-butoxybis (ethylacetate) Acetate) zirconium, n-butoxitris (ethylacetate acetate) zirconium, tetrakis (n-propylacetone acetate) zirconium, tetrakis (acetylacetone acetate) zirconium, tetrakis (ethylacetone acetate) zirconium, aluminum ethylacetate acetate, aluminum acetylacetoneate , Aluminum Acetylacetone Bisethylacetone Acetate, Diisopropoxyethylacetone Acetate Aluminum, Diisopropoxyacetylacetonate Aluminum, Isopropoxybis (Ethylacetone Acetate) Aluminum, Isopropoxybis (Acetylacetonate) Aluminum, Tris (Ethylacetone) Acetate) Aluminum, Tris (Acetylacetone) Aluminum, Monoacetylacetonate Bis (Acetylacetone Acetate) ) Aluminum is mentioned. Of these, titanium acetylacetonate and titanium ethylacetone acetate are preferable.

In addition to the above, organic metal compounds that can be used in the present invention include organic carboxylic acid metal salts such as zinc octylate, zinc laurate, zinc stearate, and tin octylate, acetylacetone zinc chelate, benzoylacetone zinc chelate, and dibenzoylmethane zinc. Examples thereof include chelates and zinc chelate compounds such as ethyl acetoacetate zinc chelate.

If the content of the organometallic compound in the easy-adhesion composition is too small, the proportion of the organometallic compound present on the surface of the easy-adhesion layer decreases, and the easy-adhesion effect may be lowered. Therefore, the content of the organometallic compound in the easy-adhesion composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and 0.1% by mass or more. Is even more preferable. The content of the organometallic compound in the easy-adhesion composition is usually 10% by mass or less, preferably 5% by mass or less.

The easy-adhesion composition may contain a polymerizable compound X having an SP value of 21.0 (MJ / m ³ ) ^1/2 or more and 26.0 (MJ / m ³ ) ^1/2 or less as a curable component. preferable.

The polymerizable compound X has a radically polymerizable group such as a (meth) acrylate group and has an SP value of 21.0 (MJ / m ³ ) ^1/2 or more and 26.0 (MJ / m ³ ) ^1/2. Any of the following compounds can be used without limitation. Examples of the polymerizable compound X include acryloyl morpholine (SP value 22.9), N-methoxymethyl acrylamide (SP value 22.9), N-ethoxymethyl acrylamide (SP value 22.3) and the like. Commercially available products can also be preferably used as the polymerizable compound X, for example, ACMO (manufactured by Kojin Co., Ltd., SP value 22.9), Wasmer 2MA (manufactured by Kasano Kosan Co., Ltd., SP value 22.9), Wasmer EMA. (Kasano Kosan Co., Ltd., SP value 22.3), Wasmer 3MA (Kasano Kosan Co., Ltd., SP value 22.4) and the like can be mentioned. These may be used alone or in combination of two or more. Of these, it is preferable to use acryloyl morpholine.

Here, the method of calculating the SP value (solubility parameter) in the present invention will be described below.

（ただしΔｅｉは原子または基に帰属する２５℃における蒸発エネルギー、Δｖｉは２５℃におけるモル体積である）にて計算して求めることができる。 (Calculation method of solubility parameter (SP value))
In the present invention, the solubility parameter (SP value) of the polymerizable compound X is determined by the Fedors calculation method [“Polymer Eng. & Sci.”, Vol. 14, No. 2 (1974). , Pages 148-154] That is,

(However, Δei is the evaporation energy at 25 ° C. attributable to the atom or group, and Δvi is the molar volume at 25 ° C.).

In Δei and Δvi in the above formula, constant numerical values given to i atoms and groups in the main molecule are shown. In addition, typical examples of the numerical values of Δe and Δv given to the atom or group are shown in Table 1 below.

The content of the polymerizable compound X in the easy-adhesive composition is not particularly limited, but as described above, it is transparent by blending the polymerizable compound X to be blended in the adhesive composition with the easy-adhesive composition. From the viewpoint of suppressing excessive penetration of the polymerizable compound X into the protective film, it is preferably 20% by mass or more, more preferably 30% by mass or more, while being blended in the adhesive composition. From the viewpoint of permeating the polymerizable compound X into the transparent protective film to impart an anchor effect, the content is preferably 85% by mass or less, more preferably 75% by mass or less. Regarding the content of the polymerizable compound X in the easy-adhesive composition, the total content of the polymerizable compound X in the easy-adhesive composition (excluding the solvent) and the adhesive composition is preferably 40 to 64% by mass. The content of the polymerizable compound X in the adhesive composition is adjusted in consideration of the content of the polymerizable compound X so as to be more preferably 50 to 62% by mass, still more preferably 53 to 61% by mass.

The easy-adhesion composition may contain a solvent and an additive.

As the solvent, those capable of stabilizing, dissolving or dispersing the compound represented by the general formula (1) and the organometallic compound are preferable. As such a solvent, an organic solvent, water, or a mixed solvent thereof can be used. Examples of the solvent include ethers such as ethyl acetate, butyl acetate and 2-hydroxyethyl acetate; ketones such as methyl ethyl ketone, acetone, cyclohexanone, methyl isobutyl ketone, diethyl ketone, methyl-n-propyl ketone and acetyl acetone; tetrahydrofuran ( Cyclic ethers such as THF) and dioxane; aliphatic or alicyclic hydrocarbons such as n-hexane and cyclohexane; aromatic hydrocarbons such as toluene and xylene; methanol, ethanol, n-propanol, isopropanol and cyclohexanol. Lipid or alicyclic alcohols such as; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether; glycol ether acetates such as diethylene glycol monomethyl ether acetate and diethylene glycol monoethyl ether acetate; etc. Is selected from. Of these, it is preferable to use water.

When the easy-adhesion composition contains an organic solvent, the content of the organic solvent is 100 mass by mass of the entire amount of the easy-adhesion composition from the viewpoint of improving the adhesiveness between the polarizer and the adhesive layer and improving the coatability. When it is%, it is preferably 5 to 80% by mass, more preferably 10 to 50% by mass. Further, when the easy-adhesion composition contains water, the content of water is increased from the viewpoint of increasing the reactivity of the boron-containing compound with the functional group contained in the polarizer and improving the adhesiveness between the polarizer and the adhesive layer. When the total amount of the easy-adhesion composition is 100% by mass, it is preferably 5 to 90% by mass, more preferably 30 to 80% by mass, and further preferably 40 to 60% by mass.

Examples of the additives include binder resins, surfactants, plasticizers, tackifiers, low molecular weight polymers, polymerizable monomers, surface lubricants, leveling agents, antioxidants, corrosion inhibitors, light stabilizers, and ultraviolet rays. Examples include absorbents, polymerization inhibitors, silane coupling agents, titanium coupling agents, inorganic or organic fillers, metal powders, particulates, foils and the like.

When the easy-adhesion composition contains a polymerization initiator, the polymerizable compound X or the boron-containing compound in the easy-adhesion composition reacts to sufficiently obtain the effect of improving the water-adhesion resistance of the polarizing film. May not be available. Therefore, the content of the polymerization initiator in the easy-adhesion composition is preferably 5% by mass or less, more preferably 3% by mass or less, and particularly preferably not containing the polymerization initiator.

<Adhesive composition>
The form of curing the adhesive composition can be roughly classified into thermosetting and active energy ray curing. Examples of the resin constituting the thermosetting adhesive composition include polyvinyl alcohol resin, epoxy resin, unsaturated polyester, urethane resin, acrylic resin, urea resin, melamine resin, and phenol resin, and if necessary, a curing agent. Is used in combination. As the resin constituting the thermosetting adhesive composition, a polyvinyl alcohol resin and an epoxy resin can be more preferably used. The active energy ray-curable adhesive composition can be roughly classified into electron beam curability, ultraviolet curability, and visible light curability as classified by active energy rays. Further, the form of curing can be classified into a radically polymerizable adhesive composition and a cationically polymerizable adhesive composition. In the present invention, active energy rays having a wavelength range of 10 nm to less than 380 nm are referred to as ultraviolet rays, and active energy rays having a wavelength range of 380 nm to 800 nm are referred to as visible light.

In the production of the polarizing film according to the present invention, it is preferable that the adhesive composition is active energy ray-curable. Further, it is particularly preferable that it is visible light curable using visible light of 380 nm to 450 nm.

Examples of the curable component contained in the radically polymerizable adhesive composition include radically polymerizable compounds used in the radically polymerizable adhesive composition. Examples of the radically polymerizable compound include compounds having a radically polymerizable functional group of a carbon-carbon double bond such as a (meth) acryloyl group and a vinyl group. As these curable components, either a monofunctional radical polymerizable compound or a bifunctional or higher polyfunctional radical polymerizable compound can be used. In addition, these radically polymerizable compounds may be used alone or in combination of two or more. As these radically polymerizable compounds, for example, compounds having a (meth) acryloyl group are suitable. In addition, in this invention, (meth) acryloyl means acryloyl group and / or methacryloyl group, and "(meth)" has the same meaning below.

で表される化合物（ただし、Ｒ^３は水素原子またはメチル基であり、Ｒ^４およびＲ^５はそれぞれ独立に、水素原子、アルキル基、ヒドロキシアルキル基、アルコキシアルキル基または環状エーテル基であって、Ｒ^４およびＲ^５は環状複素環を形成してもよい）が挙げられる。アルキル基、ヒドロキシアルキル基、および／またはアルコキシアルキル基のアルキル部分の炭素数は特に限定されないが、例えば１〜４個のものが例示される。また、Ｒ^４およびＲ^５が形成してもよい環状複素環は、例えばＮ−アクリロイルモルホリンなどが挙げられる。 Examples of the monofunctional radically polymerizable compound include the following general formula (2):

Compounds represented by (where R ³ is a hydrogen atom or a methyl group, and R ⁴ and R ⁵ are independently hydrogen atoms, alkyl groups, hydroxyalkyl groups, alkoxyalkyl groups or cyclic ether groups, respectively. R ⁴ and R ⁵ may form a cyclic heterocycle). The number of carbon atoms in the alkyl portion of the alkyl group, hydroxyalkyl group, and / or alkoxyalkyl group is not particularly limited, and examples thereof include 1 to 4 carbon atoms. Further, examples of the cyclic heterocycle that R ⁴ and R ⁵ may form include N-acryloyl morpholine and the like.

Specific examples of the compound represented by the general formula (2) include N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, and N-isopropyl ( N-alkyl group-containing (meth) acrylamide derivatives such as meta) acrylamide, N-butyl (meth) acrylamide, N-hexyl (meth) acrylamide; N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N -N-hydroxyalkyl group-containing (meth) acrylamide derivatives such as methylol-N-propane (meth) acrylamide; N-alkoxy group-containing (meth) acrylamide derivatives such as N-methoxymethylacrylamide and N-ethoxymethylacrylamide. Be done. Examples of the cyclic ether group-containing (meth) acrylamide derivative include a heterocycle-containing (meth) acrylamide derivative in which the nitrogen atom of the (meth) acrylamide group forms a heterocycle, and examples thereof include N-acrylloylmorpholine and N. -Acrylamide piperidine, N-methacryloyl piperidine, N-acrylamide and the like can be mentioned.

The adhesive composition used in the present invention preferably contains the polymerizable compound X as a curable component.

The content of the polymerizable compound X in the adhesive composition is not particularly limited, but as described above, 80% by mass from the viewpoint of suppressing excessive penetration of the polymerizable compound X into the transparent protective film. % Or less, more preferably 60% by mass or less, while 25% by mass or more, more preferably 35, from the viewpoint of improving the adhesiveness between the adhesive layer and the transparent protective film. It is mass% or more. The content of the polymerizable compound X in the adhesive composition is preferably 40 to 64% by mass in the easy-adhesive composition (excluding the solvent) and the total content of the polymerizable compound X in the adhesive composition. The content of the polymerizable compound X in the easy-adhesion composition is adjusted in consideration of the content of the polymerizable compound X so as to be more preferably 50 to 62% by mass, still more preferably 53 to 61% by mass.

In addition, the adhesive composition used in the present invention may contain a monofunctional radically polymerizable compound other than the above as a curable component. Examples of the monofunctional radically polymerizable compound include various (meth) acrylic acid derivatives having a (meth) acryloyloxy group. Examples of the (meth) acrylic acid derivative include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and 2-methyl-2-nitropropyl (meth) acrylate. , N-butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, t-pentyl (meth) acrylate, 3-pentyl (Meta) acrylate, 2,2-dimethylbutyl (meth) acrylate, n-hexyl (meth) acrylate, cetyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 4-methyl- Examples thereof include (meth) acrylic acid (1-20 carbon atoms) alkyl esters such as 2-propylpentyl (meth) acrylate and n-octadecyl (meth) acrylate.

Examples of the (meth) acrylic acid derivative include cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate and cyclopentyl (meth) acrylate; aralkyl (meth) acrylates such as benzyl (meth) acrylate; 2-isobornyl. (Meta) acrylate, 2-norbornylmethyl (meth) acrylate, 5-norbornen-2-yl-methyl (meth) acrylate, 3-methyl-2-norbornylmethyl (meth) acrylate, dicyclopentenyl (meth) ) Polycyclic (meth) acrylates such as acrylicate, dicyclopentenyloxyethyl (meth) acrylicate, dicyclopentanyl (meth) acrylicate, etc .; 2-methoxyethyl (meth) acrylate, 2-ethoxy Ethyl (meth) acrylate, 2-methoxymethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, alkylphenoxypolyethylene glycol (meth) acrylate, etc. An alkoxy group- or phenoxy group-containing (meth) acrylate; and the like. Among these, dicyclopentenyloxyethyl acrylate and phenoxyethyl acrylate are preferable because they are excellent in adhesiveness to various protective films.

Examples of the (meth) acrylic acid derivative include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate. Hydroxyalkyl (meth) acrylates such as 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, and 12-hydroxylauryl (meth) acrylate. ) Acrylate, hydroxyl group-containing (meth) acrylate such as [4- (hydroxymethyl) cyclohexyl] methyl acrylate, cyclohexanedimethanol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate; glycidyl (meth) Acrylate, 4-hydroxybutyl (meth) acrylate Epoxy group-containing (meth) acrylate such as glycidyl ether; 2,2,2-trifluoroethyl (meth) acrylate, 2,2,2-trifluoroethyl ethyl (meth) acrylate , Tetrafluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate and other halogen-containing (Meta) acrylate; Alkylaminoalkyl (meth) acrylate such as dimethylaminoethyl (meth) acrylate; 3-oxytenylmethyl (meth) acrylate, 3-methyl-oxetanylmethyl (meth) acrylate, 3-ethyl-oxetanylmethyl (meth) ) Oxetane group-containing (meth) acrylates such as acrylates, 3-butyl-oxetanylmethyl (meth) acrylates, 3-hexyluoxetanylmethyl (meth) acrylates; Examples thereof include (meth) acrylate having a heterocycle, neopentyl glycol (meth) acrylic acid adduct of hydroxypivalate, and p-phenylphenol (meth) acrylate. Among these, 2-hydroxy-3-phenoxypropyl acrylate is preferable because it has excellent adhesiveness to various protective films.

Examples of the monofunctional radically polymerizable compound include carboxyl group-containing monomers such as (meth) acrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid.

Examples of the monofunctional radically polymerizable compound include lactam-based vinyl monomers such as N-vinylpyrrolidone, N-vinyl-ε-caprolactam, and methylvinylpyrrolidone; vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazin, and vinylpyrazine. Examples thereof include vinyl-based monomers having a nitrogen-containing heterocycle such as vinylpyrrole, vinylimidazole, vinyloxazole, and vinylmorpholin.

In the adhesive composition used in the present invention, among the monofunctional radically polymerizable compounds, a hydroxyl group-containing (meth) acrylate having a high polarity, a carboxyl group-containing (meth) acrylate, a phosphate group-containing (meth) acrylate and the like When the above is contained, the adhesion to various substrates is improved. The content of the hydroxyl group-containing (meth) acrylate is preferably 1% by mass to 30% by mass with respect to the adhesive composition. If the content of the hydroxyl group-containing (meth) acrylate is too large, the water absorption rate of the cured product may increase and the water resistance may deteriorate. The content of the carboxyl group-containing (meth) acrylate is preferably 1% by mass to 20% by mass with respect to the adhesive composition. If the content of the carboxyl group-containing (meth) acrylate is too large, the optical durability of the polarizing film is lowered, which is not preferable. Examples of the phosphoric acid group-containing (meth) acrylate include 2- (meth) acryloyloxyethyl acid phosphate, and the content thereof is 0.1% by mass to 10% by mass with respect to the adhesive composition. Is preferable. If the content of the phosphoric acid group-containing (meth) acrylate is too large, the optical durability of the polarizing film is lowered, which is not preferable.

Further, as the monofunctional radically polymerizable compound, a radically polymerizable compound having an active methylene group can be used. A radically polymerizable compound having an active methylene group is a compound having an active double bond group such as a (meth) acrylic group at the terminal or in the molecule and having an active methylene group. Examples of the active methylene group include an acetoacetyl group, an alkoxymalonyl group, a cyanoacetyl group and the like. It is preferable that the active methylene group is an acetoacetyl group. Examples of the radically polymerizable compound having an active methylene group include acetoacetoxy such as 2-acetacetoxyethyl (meth) acrylate, 2-acetacetoxypropyl (meth) acrylate, and 2-acetacetoxy-1-methylethyl (meth) acrylate. Alkyl (meth) acrylate; 2-ethoxymalonyloxyethyl (meth) acrylate, 2-cyanoacetoxyethyl (meth) acrylate, N- (2-cyanoacetoxyethyl) acrylamide, N- (2-propionylacetoxybutyl) acrylamide, N -(4-Acetacetoxymethylbenzyl) acrylamide, N- (2-acetoacetylaminoethyl) acrylamide and the like can be mentioned. The radically polymerizable compound having an active methylene group is preferably acetoacetoxyalkyl (meth) acrylate.

Examples of the bifunctional or higher polyfunctional radical polymerizable compound include N, N'-methylenebis (meth) acrylamide, which is a polyfunctional (meth) acrylamide derivative, tripropylene glycol di (meth) acrylate, and tetraethylene glycol di. (Meta) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol diacrylate, 2-ethyl-2-butylpropanediol di (meth) ) Acrylate, bisphenol A di (meth) acrylate, bisphenol A ethylene oxide adduct di (meth) acrylate, bisphenol A propylene oxide adduct di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl Glycoldi (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, cyclic trimethylolpropaneformal (meth) acrylate, dioxane glycol di (meth) acrylate, trimethylolpropanetri (meth) acrylate, pentaerythritol tri ( (Meta) acrylic acid and polyhydric alcohols such as meta) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, EO-modified diglycerin tetra (meth) acrylate. , 9,9-Bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene. Specific examples include Aronix M-220 (manufactured by Toagosei Co., Ltd.), Light Acrylate 1,9ND-A (manufactured by Kyoeisha Chemical Co., Ltd.), Light Acrylate DGE-4A (manufactured by Kyoeisha Chemical Co., Ltd.), Light Acrylate DCP-A (manufactured by Kyoeisha Chemical Co., Ltd.). , SR-531 (manufactured by Sartomer), CD-536 (manufactured by Sartomer) and the like are preferable. Further, if necessary, various epoxy (meth) acrylates, urethane (meth) acrylates, polyester (meth) acrylates, various (meth) acrylate-based monomers and the like can be mentioned. The polyfunctional (meth) acrylamide derivative is preferably contained in the adhesive composition because the polymerization rate is high and the productivity is excellent, and the crosslinkability when the adhesive composition is a cured product is excellent.

For the radically polymerizable compound, a monofunctional radically polymerizable compound and a polyfunctional radically polymerizable compound should be used in combination from the viewpoint of achieving both adhesion to a polarizer and various transparent protective films and optical durability in a harsh environment. Is preferable. Since the monofunctional radical polymerizable compound has a relatively low liquid viscosity, the liquid viscosity of the adhesive composition can be lowered by including it in the adhesive composition. In addition, monofunctional radically polymerizable compounds often have functional groups that express various functions, and by incorporating them in the adhesive composition, various types of adhesive compositions and / or cured products of the adhesive composition can be obtained. The function can be expressed. The polyfunctional radical polymerizable compound is preferably contained in the adhesive composition because the cured product of the adhesive composition can be three-dimensionally crosslinked. The polyfunctional radical-polymerizable compound is preferably used in an amount of 10 to 1000 parts by mass with respect to 100 parts by mass of the monofunctional radical-polymerizable compound.

The radically polymerizable adhesive composition does not need to contain a photopolymerization initiator when an electron beam or the like is used for the active energy ray, but is adhered when ultraviolet rays or visible light are used for the active energy ray. The agent composition preferably contains a photopolymerization initiator.

When a radically polymerizable compound is used, the photopolymerization initiator is appropriately selected by the active energy ray. When curing by ultraviolet rays or visible light, a photopolymerization initiator that cleaves ultraviolet rays or visible light is used. Examples of the photopolymerization initiator include benzophenone compounds such as benzyl, benzophenone, benzoylbenzoic acid, and 3,3'-dimethyl-4-methoxybenzophenone; 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2). Aromatic ketone compounds such as -propyl) ketone, α-hydroxy-α, α'-dimethylacetophenone, 2-methyl-2-hydroxypropiophenone, α-hydroxycyclohexylphenylketone; methoxyacetophenone, 2,2-dimethoxy- Acetphenone compounds such as 2-phenylacetophenone, 2,2-diethoxyacetophenone, 2-methyl-1- [4- (methylthio) -phenyl] -2-morpholinopropane-1; benzophenone methyl ether, Benzophenone-BR> tower G-tel compounds such as benzoine ethyl ether, benzoin isopropyl ether, benzoine butyl ether, and anisoine methyl ether; aromatic ketal compounds such as benzyl dimethyl ketal; 2-naphthalene sulfonyl chloride, etc. Aromatic sulfonyl chloride compounds; photoactive oxime compounds such as 1-phenone-1,1-propanedione-2- (o-ethoxycarbonyl) oxime; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2, Thioxanthone compounds such as 4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, dodecylthioxanthone; benzophenone; ketone halide; acylphosphinoxide; acyl Examples include phosphonate.

The blending amount of the photopolymerization initiator is preferably 20% by mass or less, more preferably 0.01 to 20% by mass, and 0.05 to 10% by mass in the adhesive composition. Is more preferable, and 0.1 to 5% by mass is particularly preferable. As for the content of the photopolymerization initiator in the adhesive composition, the total content of the photopolymerization initiator in the easy-adhesive composition (excluding the solvent) and the adhesive composition is preferably 2.6 to 7 mass. %, More preferably 2.65 to 6% by mass, still more preferably 2.7 to 5% by mass, in consideration of the content of the photopolymerization initiator in the easy-adhesion composition.

When the adhesive composition used in the present invention is used with visible light curability containing a radically polymerizable compound as a curable component, a photopolymerization initiator having high sensitivity to light of 380 nm or more is used. Is preferable. A photopolymerization initiator having high sensitivity to light of 380 nm or more will be described later.

（式中、Ｒ^６およびＲ^７は−Ｈ、−ＣＨ_２ＣＨ_３、−ｉＰｒまたはＣｌを示し、Ｒ^６およびＲ^７は同一または異なっても良い）を単独で使用するか、あるいは一般式（３）で表される化合物と後述する３８０ｎｍ以上の光に対して高感度な光重合開始剤とを併用することが好ましい。一般式（３）で表される化合物を使用した場合、３８０ｎｍ以上の光に対して高感度な光重合開始剤を単独で使用した場合に比べて接着性に優れる。一般式（３）で表される化合物の中でも、Ｒ^６およびＲ^７が−ＣＨ_２ＣＨ_３であるジエチルチオキサントンが特に好ましい。接着剤組成物中の一般式（３）で表される化合物の組成比率は、接着剤組成物の全量に対して、０．１〜５質量％であることが好ましく、０．５〜４質量％であることがより好ましく、０．９〜３質量％であることがさらに好ましい。 The photopolymerization initiator is a compound represented by the following general formula (3);

(In the formula, R ⁶ and R ⁷ indicate -H, -CH ₂ CH ₃ , -iPr or Cl, and R ⁶ and R ⁷ may be the same or different), or the general formula (in the formula) may be used alone. It is preferable to use the compound represented by 3) in combination with a photopolymerization initiator having high sensitivity to light of 380 nm or more, which will be described later. When the compound represented by the general formula (3) is used, the adhesiveness is excellent as compared with the case where a photopolymerization initiator having high sensitivity to light of 380 nm or more is used alone. Among the compounds represented by the general formula (3), diethylthioxanthone in which R ⁶ and R ⁷ are −CH ₂ CH ₃ is particularly preferable. The composition ratio of the compound represented by the general formula (3) in the adhesive composition is preferably 0.1 to 5% by mass, and 0.5 to 4% by mass, based on the total amount of the adhesive composition. It is more preferably%, and further preferably 0.9 to 3% by mass.

In addition, it is preferable to add a polymerization initiator as needed. Examples of the polymerization initiator include triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and isoamyl 4-dimethylaminobenzoate. , And ethyl 4-dimethylaminobenzoate is particularly preferable. When a polymerization initiator is used, the amount added thereof is usually 0 to 5% by mass, preferably 0 to 4% by mass, and most preferably 0 to 3% by mass, based on the total amount of the adhesive composition.

In addition, a known photopolymerization initiator can be used in combination if necessary. Since the transparent protective film having a UV absorbing ability does not transmit light of 380 nm or less, it is preferable to use a photopolymerization initiator having high sensitivity to light of 380 nm or more as the photopolymerization initiator. Specifically, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 , 2- (Dimethylamino) -2-[(4-Methylphenyl) Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine Oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (η5-2,4-cyclopentadiene-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-) 1-yl) -phenyl) titanium and the like can be mentioned.

（式中、Ｒ^８、Ｒ^９およびＲ^１０は−Ｈ、−ＣＨ_３、−ＣＨ_２ＣＨ_３、−ｉＰｒまたはＣｌを示し、Ｒ^８、Ｒ^９およびＲ^１０は同一または異なっても良い）を使用することが好ましい。一般式（４）で表される化合物としては、市販品でもある２−メチル−１−（４−メチルチオフェニル）−２−モルフォリノプロパン−１−オン（商品名：ＩＲＧＡＣＵＲＥ９０７ メーカー：ＢＡＳＦ）が好適に使用可能である。その他、２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）−ブタノン−１（商品名：ＩＲＧＡＣＵＲＥ３６９ メーカー：ＢＡＳＦ）、２−（ジメチルアミノ）−２−［（４−メチルフェニル）メチル］−１−［４−（４−モルホリニル）フェニル］−１−ブタノン（商品名：ＩＲＧＡＣＵＲＥ３７９ メーカー：ＢＡＳＦ）が感度が高いため好ましい。 In particular, as the photopolymerization initiator, in addition to the photopolymerization initiator of the general formula (3), a compound represented by the following general formula (4);

(In the formula, R ⁸ , R ⁹ and R ¹⁰ indicate -H, -CH ₃ , -CH ₂ CH ₃ , -iPr or Cl, and R ⁸ , R ⁹ and R ¹⁰ may be the same or different). It is preferable to use it. As the compound represented by the general formula (4), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (trade name: IRGACURE907 manufacturer: BASF), which is also a commercially available product, is preferable. Can be used for. In addition, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (trade name: IRGACURE369 manufacturer: BASF), 2- (dimethylamino) -2-[(4-methylphenyl) Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name: IRGACURE379 manufacturer: BASF) is preferable because of its high sensitivity.

When a radically polymerizable compound having an active methylene group is used as the radically polymerizable compound in the above adhesive composition, it is preferably used in combination with a radical polymerization initiator having a hydrogen abstraction action. According to such a configuration, the adhesiveness of the adhesive layer of the polarizing film is remarkably improved even immediately after being taken out from a high humidity environment or water (non-drying state). The reason for this is not clear, but the following causes are possible. That is, the radically polymerizable compound having an active methylene group is incorporated into the main chain and / or side chain of the base polymer in the adhesive layer while being polymerized together with other radically polymerizable compounds constituting the adhesive layer, and adheres. Form a layer of agent. In such a polymerization process, when a radical polymerization initiator having a hydrogen abstraction action is present, hydrogen is abstracted from the radical polymerizable compound having an active methylene group to form a methylene group while forming a base polymer constituting the adhesive layer. Radicals are generated. Then, the methylene group in which radicals are generated reacts with the hydroxyl group of a polarizer such as PVA, and a covalent bond is formed between the adhesive layer and the polarizer. As a result, it is presumed that the adhesiveness of the adhesive layer of the polarizing film is remarkably improved even in a non-drying state.

In the present invention, examples of the radical polymerization initiator having a hydrogen abstraction action include a thioxanthone-based radical polymerization initiator and a benzophenone-based radical polymerization initiator. The radical polymerization initiator is preferably a thioxanthone-based radical polymerization initiator. Examples of the thioxanthone-based radical polymerization initiator include compounds represented by the above general formula (3). Specific examples of the compound represented by the general formula (3) include thioxanthone, dimethylthioxanthone, diethylthioxanthone, isopropylthioxanthone, chlorothioxanthone and the like. Among the compounds represented by the general formula (3), diethylthioxanthone in which R ⁶ and R ⁷ are −CH ₂ CH ₃ is particularly preferable.

When the adhesive composition contains a radically polymerizable compound having an active methylene group and a radical polymerization initiator having a hydrogen abstraction action, the active methylene is defined as 100% by mass of the curable component. It is preferable to contain 1 to 50% by mass of the radically polymerizable compound having a group and 0.1 to 10% by mass of the radical polymerization initiator with respect to the total amount of the adhesive composition.

As described above, in the present invention, in the presence of a radical polymerization initiator having a hydrogen abstraction action, a radical is generated in the methylene group of the radically polymerizable compound having an active methylene group, and the methylene group and a polarizer such as PVA are generated. Reacts with the hydroxyl group to form a covalent bond. Therefore, in order to generate a radical in the methylene group of the radically polymerizable compound having an active methylene group and sufficiently form such a covalent bond, when the total amount of the curable component is 100% by mass, the radical having an active methylene group The polymerizable compound is preferably contained in an amount of 1 to 50% by mass, more preferably 3 to 30% by mass. In order to sufficiently improve the water resistance and improve the adhesiveness in the non-drying state, the amount of the radically polymerizable compound having an active methylene group is preferably 1% by mass or more. On the other hand, if it exceeds 50% by mass, curing failure of the adhesive layer may occur. Further, the radical polymerization initiator having a hydrogen abstraction action is preferably contained in an amount of 0.1 to 10% by mass, more preferably 0.3 to 9% by mass, based on the total amount of the adhesive composition. .. In order for the hydrogen abstraction reaction to proceed sufficiently, it is preferable to use 0.1% by mass or more of the radical polymerization initiator. On the other hand, if it exceeds 10% by mass, it may not be completely dissolved in the composition.

The adhesive composition used in the present invention preferably further contains the following components, if necessary.

In the present invention, the compound described in the general formula (1), preferably the compound described in the general formula (1'), and more preferably the compound described in the general formulas (1a) to (1d) is used as an adhesive. It can be incorporated into the composition. Further, in the present invention, the organometallic compound can be blended into the adhesive composition. When these compounds are blended in the adhesive composition, the adhesiveness to the polarizer or the transparent protective film may be improved, which is preferable. From the viewpoint of improving adhesiveness and water resistance when the polarizer and the transparent protective film are adhered via the adhesive layer, the content of the compound represented by the general formula (1) in the adhesive composition is 0. It is preferably .001 to 50% by mass, more preferably 0.1 to 30% by mass, and even more preferably 1 to 10% by mass. The content of the organometallic compound in the adhesive composition is preferably 0.1 to 10% by mass, more preferably 0.5 to 7% by mass, and 1 to 5% by mass. It is more preferable to have.

The bubble suppressant is a compound that can reduce the surface tension of the adhesive composition when blended in the adhesive composition, and has an effect of reducing bubbles between the bubble inhibitor and the transparent protective film to be bonded. Examples of the bubble inhibitor include a silicone-based bubble inhibitor having a polysiloxane skeleton such as polydimethylsiloxane, and a (meth) acrylic bubble inhibitor having a (meth) acrylic skeleton obtained by polymerizing a (meth) acrylic acid ester or the like. When added to an adhesive composition, such as a polyether bubble inhibitor obtained by polymerizing vinyl ether or cyclic ether, or a fluorobubble inhibitor composed of a fluorine-based compound having a perfluoroalkyl group, the surface tension is reduced. Anything that has the effect of

The bubble suppressant preferably has a reactive group in the compound. In this case, the generation of Lami bubbles can be reduced when the polarizer and the transparent protective film are attached. Examples of the reactive group of the bubble inhibitor include a polymerizable functional group, and specifically, a radically polymerizable functional group having an ethylenic double bond such as a (meth) acryloyl group, a vinyl group and an allyl group, and glycidyl. Examples thereof include an epoxy group such as a group, an oxetane group, a vinyl ether group, a cyclic ether group, a cyclic thioether group, a cationically polymerizable functional group such as a lactone group and the like. From the viewpoint of reactivity in the adhesive composition, a bubble inhibitor having a double bond as a reactive group is preferable, and a bubble inhibitor having a (meth) acrylic loyl group is more preferable.

Considering the effect of suppressing Lami bubbles and the effect of improving adhesiveness, a silicone-based bubble inhibitor is preferable among the bubble inhibitors. Further, among the bubble suppressants, those containing a urethane bond or an isocyanurate ring structure in the main chain skeleton or the side chain are preferable in consideration of the adhesiveness of the adhesive layer. As the silicone-based bubble inhibitor, a commercially available product can also be preferably used, and examples thereof include "BYK-UV3505" (manufactured by Big Chemie Japan), which is an acrylic group-modified polydimethylsiloxane.

In order to achieve both the adhesive strength of the obtained adhesive layer and the effect of reducing lami bubbles, the content of the bubble inhibitor is 0.01 to 0. When the total amount of the adhesive composition is 100% by mass. It is preferably 6% by mass.

The adhesive composition used in the present invention may contain an acrylic oligomer obtained by polymerizing a (meth) acrylic monomer in addition to the curable component of the radically polymerizable compound. By containing the acrylic oligomer in the adhesive composition, the curing shrinkage when irradiating and curing the composition with active energy rays is reduced, and the adhesive is adhered to a polarizer, a transparent protective film, and the like. The interfacial stress with the body can be reduced. As a result, it is possible to suppress a decrease in the adhesiveness between the adhesive layer and the adherend. In order to sufficiently suppress the curing shrinkage of the adhesive layer, the content of the acrylic oligomer is preferably 20% by mass or less, preferably 15% by mass or less, based on the total amount of the adhesive composition. Is more preferable. If the content of the acrylic oligomer in the adhesive composition is too large, the reaction rate when the composition is irradiated with active energy rays is drastically reduced, which may result in poor curing. On the other hand, the acrylic oligomer is preferably contained in an amount of 3% by mass or more, more preferably 5% by mass or more, based on the total amount of the adhesive composition.

Since the adhesive composition preferably has a low viscosity in consideration of workability and uniformity during coating, it is preferable that the acrylic oligomer obtained by polymerizing the (meth) acrylic monomer also has a low viscosity. .. As the acrylic oligomer having a low viscosity and capable of preventing curing shrinkage of the adhesive layer, those having a weight average molecular weight (Mw) of 15,000 or less are preferable, those having a weight average molecular weight (Mw) of 15,000 or less are more preferable, and those having a weight average molecular weight (Mw) of 5,000 or less are particularly preferable. preferable. On the other hand, in order to sufficiently suppress the curing shrinkage of the adhesive layer, the weight average molecular weight (Mw) of the acrylic oligomer is preferably 500 or more, more preferably 1000 or more, and 1500 or more. Is particularly preferable. Specific examples of the (meth) acrylic monomer constituting the acrylic oligomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and 2-methyl-. 2-Nitropropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, S-butyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, t-pentyl (Meta) acrylate, 3-pentyl (meth) acrylate, 2,2-dimethylbutyl (meth) acrylate, n-hexyl (meth) acrylate, cetyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl ( (Meta) acrylic acid (1-20 carbon atoms) alkyl esters such as meta) acrylates, 4-methyl-2-propylpentyl (meth) acrylates, N-octadecyl (meth) acrylates, and more, for example, cycloalkyl (meth). ) Acrylate (eg, cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, etc.), aralkyl (meth) acrylate (eg, benzyl (meth) acrylate, etc.), polycyclic (meth) acrylate (eg, 2-isobornyl (meth) acrylate, etc.) ) Acrylate, 2-norbornylmethyl (meth) acrylate, 5-norbornen-2-yl-methyl (meth) acrylate, 3-methyl-2-norbornylmethyl (meth) acrylate, etc.), hydroxyl group-containing (meth) ) Acrylate esters (eg, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2,3-dihydroxypropylmethyl-butyl (meth) methacrylate, etc.), alkoxy group- or phenoxy group-containing (meth) acrylic Acid esters (2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-methoxymethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethylcarbitol (meth) acrylate, phenoxy Ethyl (meth) acrylate, etc.), epoxy group-containing (meth) acrylic acid esters (eg, glycidyl (meth) acrylate, etc.), halogen-containing (meth) acrylic acid esters (eg, 2,2,2-trifluoroethyl) (Meta) acrylate, 2,2,2- Trifluoroethyl ethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, etc.), alkylaminoalkyl (meth) Acrylate (eg, dimethylaminoethyl (meth) acrylate, etc.) and the like can be mentioned. These (meth) acrylates can be used alone or in combination of two or more. Specific examples of the acrylic oligomer include "ARUFON" manufactured by Toagosei Co., Ltd., "Actflow" manufactured by Soken Chemical Co., Ltd., and "JONCRYL" manufactured by BASF Japan Ltd.

（ただし、Ｌ^＋は、任意のオニウムカチオンを表す。また、Ｘ⁻は、ＰＦ_６ ⁻、ＳｂＦ_６ ⁻、ＡｓＦ_６ ⁻、ＳｂＣｌ_６ ⁻、ＢｉＣｌ_５ ⁻、ＳｎＣｌ_６ ⁻、ＣｌＯ_４ ⁻、ジチオカルバメートアニオン、ＳＣＮ⁻よりからなる群より選択されるカウンターアニオンを表す。） The adhesive composition can contain a photoacid generator. When the adhesive composition contains a photoacid generator, the water resistance and durability of the adhesive layer can be dramatically improved as compared with the case where the adhesive composition does not contain a photoacid generator. The photoacid generator can be represented by the following general formula (5).
General formula (5)

(However, L ⁺ represents an arbitrary onium cation. X ⁻ is PF ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , SbCl ₆ ⁻ , BiCl ₅ ⁻ , SnCl ₆ ⁻ , ClO ₄ ⁻ , dithiocarbamate. Represents a counter anion selected from the group consisting of anions and SCN ⁻ ).

Next, the counter anion X ⁻ in the general formula (5) will be described.

The counter anion X ⁻ in the general formula (5) is not particularly limited in principle, but a non-nucleophilic anion is preferable. When the counter anion X ⁻ is a non-nucleophilic anion, the nucleophilic reaction does not easily occur in the cation coexisting in the molecule or various materials used in combination, and as a result, the photoacid generator itself represented by the general formula (5) itself. And it is possible to improve the stability of the composition using it over time. The non-nucleophilic anion referred to here refers to an anion having a low ability to cause a nucleophilic reaction. Examples of such anions include PF ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , SbCl ₆ ⁻ , BiCl _5- ⁻ , SnCl ₆ ⁻ , ClO ₄ ⁻ , dithiocarbamate anion, SCN ^{− and the} like.

Specifically, "Cyracure UVI-6992", "Cyracure UVI-6974" (above, manufactured by Dow Chemical Japan Co., Ltd.), "Adeka Putmer SP150", "Adeka Putmer SP152", "Adeka Putmer" SP170 "," ADEKA PUTMER SP172 "(above, ADEKA Corporation)," IRGACURE250 "(manufactured by Ciba Specialty Chemicals)," CI-5102 "," CI-2855 "(above, manufactured by Nippon Soda), "Sun Aid SI-60L", "Sun Aid SI-80L", "Sun Aid SI-100L", "Sun Aid SI-110L", "Sun Aid SI-180L" (all manufactured by Sanshin Chemical Co., Ltd.), "CPI-100P", "CPI-100A" (manufactured by Sun Appro Corporation), "WPI-069", "WPI-113", "WPI-116", "WPI-041", "WPI-044", "WPI-054", "WPI-055", "WPAG-281", "WPAG-567", and "WPAG-596" (all manufactured by Wako Pure Chemical Industries, Ltd.) are mentioned as preferable specific examples of the photoacid generator of the present invention.

The content of the photoacid generator is 10% by mass or less, preferably 0.01 to 10% by mass, and preferably 0.05 to 5% by mass, based on the total amount of the adhesive composition. More preferably, it is particularly preferably 0.1 to 3% by mass.

The photobase generator can function as a catalyst for the polymerization reaction of a radically polymerizable compound or an epoxy resin by changing the molecular structure by irradiation with light such as ultraviolet rays or visible light or by cleaving the molecule. A compound that produces one or more basic substances. Examples of the basic substance are secondary amines and tertiary amines. Examples of the photobase generator include the above α-aminoacetophenone compound, the above oxime ester compound, an acyloxyimino group, an N-formylated aromatic amino group, an N-acylated aromatic amino group, a nitrobenzyl carbamate group, and an alcohol. Examples thereof include compounds having a substituent such as an oxybenzyl carbamate group. Of these, the oxime ester compound is preferable.

Examples of the compound having an acyloxyimino group include O, O'-diacetophenone succinate, O, O'-dinaphthophenone succinate, and benzophenone oxime acrylate-styrene copolymer.

Examples of the compound having an N-formylated aromatic amino group and an N-acylated aromatic amino group include di-N- (p-formylamino) diphenylmethane and di-N (p-aceethylamino) diphenylmelan. Di-N- (p-benzoamide) diphenylmethane, 4-formylaminotoluylene, 4-acetylaminotoluylene, 2,4-diformylaminotoluylene, 1-formylaminonaphthalene, 1-acetylaminonaphthalene, 1,5 -Diformylaminonaphthalene, 1-formylaminoanthracene, 1,4-diformylaminoanthracene, 1-acetylaminoanthracene, 1,4-diformylaminoanthraquinone, 1,5-diformylaminoanthraquinone, 3,3'- Examples thereof include dimethyl-4,4'-diformylaminobiphenyl and 4,4'-diformylaminobenzophenone.

Examples of the compound having a nitrobenzyl carbamate group and an alcooxybenzyl carbamate group include bis {{(2-nitrobenzyl) oxy} carbonyl} diaminodiphenylmethane, 2,4-di {(2-nitrobenzyl) oxy} toluylene, and the like. Examples thereof include bis {(2-nitrobenzyloxy) carbonyl} hexane-1,6-diamine and m-xylidine {{(2-nitro-4-chlorobenzyl) oxy} amide}.

The photobase generator is preferably at least one of an oxime ester compound and an α-aminoacetophenone compound, and more preferably an oxime ester compound. As the α-aminoacetophenone compound, those having two or more nitrogen atoms are particularly preferable.

As other photobase generators, WPBG-018 (trade name: 9-anthrylmethyl N, N'-dieshylcabamate), WPBG-027 (trade name: (E) -1- [3- (2-hydroxyphenyl) -2-) Propionic] piperidine), WPBG-082 (trade name: guanidinium2- (3-benzoylphenyl) propionate), WPBG-140 (trade name: 1- (anthraquinone-2-yl) ethyyl base, etc.) You can also do it.

In the above-mentioned adhesive composition, a compound containing a photoacid generator and any of an alkoxy group and an epoxy group can be used in combination in the adhesive composition.

When a compound having one or more epoxy groups in the molecule or a polymer having two or more epoxy groups in the molecule (epoxy resin) is used, two functional groups having reactivity with the epoxy group are used in the molecule. Compounds having two or more may be used in combination. Here, examples of the functional group having reactivity with the epoxy group include a carboxyl group, a phenolic hydroxyl group, a mercapto group, a primary or secondary aromatic amino group, and the like. It is particularly preferable to have two or more of these functional groups in one molecule in consideration of three-dimensional curability.

Examples of the polymer having one or more epoxy groups in the molecule include epoxy resins, bisphenol A type epoxy resins derived from bisphenol A and epichlorohydrin, and bisphenol F type epoxy derived from bisphenol F and epichlorohydrin. Resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin, alicyclic epoxy resin, diphenyl ether type epoxy resin, hydroquinone type epoxy resin, Naphthalene type epoxy resin, biphenyl type epoxy resin, fluorene type epoxy resin, polyfunctional type epoxy resin such as trifunctional type epoxy resin and tetrafunctional type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, hidden in type epoxy resin , Isocyanurate type epoxy resin, aliphatic chain epoxy resin and the like, and these epoxy resins may be halogenated or hydrogenated. Examples of commercially available epoxy resin products include JER Coat 828, 1001, 801N, 806, 807, 152, 604, 630, 871, YX8000, YX8034, YX4000 manufactured by Japan Epoxy Resin Co., Ltd., and Epicron manufactured by DIC Co., Ltd. 830, EXA835LV, HP4032D, HP820, EP4100 series, EP4000 series, EPU series manufactured by ADEKA Co., Ltd., seroxide series manufactured by Daicel Chemical Co., Ltd. Series, YD series manufactured by Nippon Steel Chemical Co., Ltd., YDF series, YDCN series, YDB series, phenoxy resin (polyhydroxypolyether synthesized from bisphenols and epichlorohydrin, which has epoxy groups at both ends; YP series, etc.), Examples include, but are not limited to, the Denacol series manufactured by Nagase ChemteX and the Epoxy series manufactured by Kyoeisha Chemical Co., Ltd. Two or more of these epoxy resins may be used in combination.

The compound having an alkoxyl group in the molecule is not particularly limited as long as it has one or more alkoxyl groups in the molecule, and known compounds can be used. Typical examples of such compounds include melamine compounds, amino resins, and silane coupling agents.

The blending amount of the compound containing either the alkoxy group or the epoxy group is usually 30% by mass or less with respect to the total amount of the adhesive composition, and if the content of the compound in the composition is too large, the adhesiveness becomes poor. It may decrease and the impact resistance to the drop test may deteriorate. The content of the compound in the composition is more preferably 20% by mass or less. On the other hand, from the viewpoint of water resistance, the composition preferably contains 2% by mass or more of the compound, and more preferably 5% by mass or more.

When the adhesive composition used in the present invention is active energy ray-curable, it is preferable to use an active energy ray-curable compound as the silane coupling agent, even if it is not active energy ray-curable. Similar water resistance can be imparted.

Specific examples of the silane coupling agent include vinyl trichlorosilane, vinyl trimethoxysilane, vinyl triethoxysilane, 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, and 3-glycid as active energy ray-curable compounds. Xipropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxy Examples thereof include silane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane.

Preferred are 3-methacryloxypropyltrimethoxysilane and 3-acryloxypropyltrimethoxysilane.

As a specific example of a silane coupling agent having no active energy ray curability, a silane coupling agent having an amino group is preferable. Specific examples of the silane coupling agent having an amino group include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, and γ-amino. Propylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2-Aminoethyl) Aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropyltriisopropoxysilane, γ- (2- (2-aminoethyl) aminoethyl) aminopropyltrimethoxysilane, γ- (6-Aminohexyl) Aminopropyltrimethoxysilane, 3- (N-ethylamino) -2-methylpropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, N-phenyl-γ -Aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane , N-Phenylaminomethyltrimethoxysilane, (2-aminoethyl) aminomethyltrimethoxysilane, N, N'-bis [3- (trimethoxysilyl) propyl] ethylenediamine and other amino group-containing silanes; N-( Examples of ketimine-type silanes such as 1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propaneamine can be mentioned.

As the silane coupling agent having an amino group, only one type may be used, or a plurality of types may be used in combination. Of these, in order to ensure good adhesion, γ-aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane , Γ- (2-Aminoethyl) Aminopropyltriethoxysilane, γ- (2-Aminoethyl) Aminopropylmethyldiethoxysilane, N- (1,3-dimethylbutylidene) -3- (Triethoxysilyl)- 1-Propylamine is preferred.

The blending amount of the silane coupling agent is preferably in the range of 0.01 to 20% by mass, preferably 0.05 to 15% by mass, and 0.1 to 10% by mass with respect to the total amount of the adhesive composition. It is more preferably%. This is because if the blending amount exceeds 20% by mass, the storage stability of the adhesive composition deteriorates, and if it is less than 0.1% by mass, the effect of water resistance is not sufficiently exhibited.

Specific examples of non-active energy ray-curable silane coupling agents other than the above include 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropyltrimethoxy. Examples thereof include silane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatepropyltriethoxysilane, and imidazole silane.

When the adhesive composition used in the present invention contains a compound having a vinyl ether group, it is preferable because the water resistance of the polarizer and the adhesive layer is improved. The reason why such an effect is obtained is not clear, but it is presumed that one of the reasons is that the vinyl ether group of the compound interacts with the polarizer to increase the adhesive force between the polarizer and the adhesive layer. To. In order to further enhance the water resistance of the polarizer and the adhesive layer, the compound is preferably a radically polymerizable compound having a vinyl ether group. The content of the compound is preferably 0.1 to 19% by mass with respect to the total amount of the adhesive composition.

The adhesive composition used in the present invention may contain a compound that causes keto-enol tautomerism. For example, in an adhesive composition containing a cross-linking agent or an adhesive composition that can be used by blending a cross-linking agent, an embodiment containing the above-mentioned compound that causes keto-enol tautomerism can be preferably adopted. As a result, the effect of suppressing an excessive increase in viscosity and gelation of the adhesive composition after blending the organometallic compound and the formation of a microgel product, and extending the pot life of the composition can be realized.

Various β-dicarbonyl compounds can be used as the compound that causes the above-mentioned keto-enol tvariability. Specific examples include acetylacetone, 2,4-hexanedione, 3,5-heptanedione, 2-methylhexane-3,5-dione, 6-methylheptane-2,4-dione, 2,6-dimethylheptane-. Β-Diketones such as 3,5-dione; acetoacetate esters such as methyl acetoacetate, ethyl acetoacetate, isopropyl acetoacetate, tert-butyl acetoacetate; ethyl propionyl acetate, ethyl propionyl acetate, isopropyl propionyl acetate, propionyl acetate Propionyl acetates such as tert-butyl; isobutyryl acetates such as ethyl isobutyryl acetate, ethyl isobutyryl acetate, isopropyl isobutyryl acetate, tert-butyl isobutyryl acetate; malonic acid esters such as methyl malate and ethyl malonate; etc. Can be mentioned. Among them, acetylacetone and acetoacetic ester are preferable compounds. The compounds that cause such keto-enol tautomerism may be used alone or in combination of two or more.

The amount of the compound that causes keto-enol tvariability is, for example, 0.05 parts by mass to 10 parts by mass, preferably 0.2 parts by mass to 3 parts by mass (for example, 0.3) with respect to 1 part by mass of the organic metal compound. By mass to 2 parts by mass). If the amount of the compound used is less than 0.05 parts by mass with respect to 1 part by mass of the organometallic compound, it may be difficult to exert a sufficient effect of use. On the other hand, if the amount of the compound used exceeds 10 parts by mass with respect to 1 part by mass of the organometallic compound, it may excessively interact with the organometallic compound and it may be difficult to develop the desired water resistance.

The adhesive composition of the present invention can contain polyrotaxane. The polyrotaxane is a cyclic molecule, a linear molecule penetrating the opening of the cyclic molecule, and a seal placed at both ends of the linear molecule so that the cyclic molecule is not detached from the linear molecule. It has a group and. The cyclic molecule preferably has an active energy ray-curable functional group.

The cyclic molecule is not particularly limited as long as it is a molecule in which a linear molecule is skewered in its opening and can move on the linear molecule and has an active energy ray-polymerizable group. In addition, in this specification, "cyclic" of "cyclic molecule" means substantially "cyclic". That is, the cyclic molecule does not have to be completely ring-closed as long as it can move on the linear molecule.

Specific examples of the cyclic molecule include cyclic polymers such as cyclic polyethers, cyclic polyesters, cyclic polyether amines, and cyclic polyamines, and cyclodextrins such as α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin. Be done. Among them, cyclodextrins such as α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin are preferable because they are relatively easily available and a large number of types of blocking groups can be selected. Two or more kinds of cyclic molecules may be mixed in the polyrotaxane or the adhesive.

In the polyrotaxane used in the present invention, the cyclic molecule has an active energy ray-polymerizable group. As a result, the polyrotaxane reacts with the active energy ray-curable component to obtain an adhesive whose cross-linking point is movable even after curing. The active energy ray-polymerizable group of the cyclic molecule may be a group that can be polymerized with the active energy ray-curable compound, and for example, a radical polymerizable group such as a (meth) acryloyl group or a (meth) acryloyloxy group may be used. Can be mentioned.

When cyclodextrin is used as the cyclic molecule, the active energy ray-polymerizable group is preferably introduced into the hydroxyl group of the cyclodextrin via any suitable linker. The number of active energy ray-polymerizable groups contained in one molecule of polyrotaxane is preferably 2 to 1280, more preferably 50 to 1000, and even more preferably 90 to 900.

It is preferable that a hydrophobic modifying group is introduced into the cyclic molecule. The introduction of the hydrophobic modifying group can improve the compatibility with the active energy ray-curable component. Further, since hydrophobicity is imparted, it is possible to prevent water from entering the interface between the adhesive layer and the polarizer when used in a polarizing film, and further improve water resistance. Examples of the hydrophobic modifying group include polyester chains, polyamide chains, alkyl chains, oxyalkylene chains, ether chains and the like. Specific examples include the groups described in [0027] to [0042] of WO2009 / 145073.

A polarizing film using a resin composition containing polyrotaxane as an adhesive has excellent water resistance. The reason why the water resistance of the polarizing film is improved is not clear, but it is presumed as follows. That is, the cross-linking point can move due to the mobility of the cyclic molecule of polyrotaxane (so-called gliding effect), which imparts flexibility to the cured adhesive and increases the adhesion of the polarizer to the surface irregularities. As a result, it is considered that the intrusion of water into the interface between the polarizer and the adhesive layer was prevented. Further, it is considered that the addition of hydrophobicity to the adhesive by having the hydrophobic modifying group of polyrotaxane also contributed to the prevention of water intrusion into the interface between the polarizer and the adhesive layer. The content of polyrotaxane is preferably 2% by mass to 50% by mass with respect to the resin composition.

In the present invention, a cationically polymerizable adhesive composition may be used for forming the adhesive layer. The cationically polymerizable compound used in the cationically polymerizable adhesive composition includes a monofunctional cationically polymerizable compound having one cationically polymerizable functional group in the molecule and two or more cationically polymerizable functional groups in the molecule. It is classified as a polyfunctional cationically polymerizable compound having. Since the monofunctional cationically polymerizable compound has a relatively low liquid viscosity, the liquid viscosity of the adhesive composition can be lowered by including it in the adhesive composition. In addition, monofunctional cationically polymerizable compounds often have functional groups that exhibit various functions, and by incorporating them in the adhesive composition, various types of adhesive compositions and / or cured products of the adhesive composition can be obtained. The function can be expressed. The polyfunctional cationically polymerizable compound is preferably contained in the adhesive composition because the cured product of the adhesive composition can be three-dimensionally crosslinked. The ratio of the monofunctional cationically polymerizable compound to the polyfunctional cationically polymerizable compound is such that the polyfunctional cationically polymerizable compound is mixed in the range of 10 parts by mass to 1000 parts by mass with respect to 100 parts by mass of the monofunctional cationically polymerizable compound. Is preferable. Examples of the cationically polymerizable functional group include an epoxy group, an oxetanyl group, and a vinyl ether group. Examples of the compound having an epoxy group include an aliphatic epoxy compound, an alicyclic epoxy compound, and an aromatic epoxy compound. The cationically polymerizable adhesive composition of the present invention is excellent in curability and adhesiveness. It is particularly preferable to contain an alicyclic epoxy compound. Examples of the alicyclic epoxy compound include caprolactone-modified products and trimethylcaprolactone-modified products of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate. , Valerolactone modified products, and specifically, seroxide 2021, seroxide 2021A, seroxide 2021P, seroxide 2081, seroxide 2083, seroxide 2085 (all manufactured by Daicel Chemical Industries, Ltd.), silacure UVR-6105, silacure UVR- 6107, Cyracure 30, R-6110 (all manufactured by Dow Chemical Japan Co., Ltd.) and the like can be mentioned. A compound having an oxetanyl group is preferably contained because it has the effect of improving the curability of the cationically polymerizable adhesive composition of the present invention and lowering the liquid viscosity of the composition. Compounds having an oxetane group include 3-ethyl-3-hydroxymethyloxetane, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, 3-ethyl-3- (phenoxymethyl) oxetane, and the like. Di [(3-ethyl-3-oxetanyl) methyl] ether, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, phenol novolac oxetane, etc. are mentioned, and Aron oxetane OXT-101 and Aron oxetane OXT-121 are mentioned. , Aron Oxetane OXT-221, Aron Oxetane OXT-221, Aron Oxetane OXT-212 (all manufactured by Toa Synthetic Co., Ltd.) and the like are commercially available. A compound having a vinyl ether group is preferably contained because it has the effect of improving the curability of the cationically polymerizable adhesive composition of the present invention and lowering the liquid viscosity of the composition. Examples of compounds having a vinyl ether group include 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol vinyl ether, triethylene glycol divinyl ether, cyclohexanedimethanol divinyl ether, cyclohexanedimethanol monovinyl ether, and tricyclodecane vinyl ether. , Cyclohexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, pentaerythritol type tetravinyl ether and the like.

The cationically polymerizable adhesive composition contains at least one compound selected as a curable component from a compound having an epoxy group, a compound having an oxetanyl group, and a compound having a vinyl ether group described above, all of which are cationically polymerized. Since it is cured by, a photocationic polymerization initiator is blended. This photocationic polymerization initiator generates a cationic species or Lewis acid by irradiation with active energy rays such as visible light, ultraviolet rays, X-rays, and electron beams, and initiates a polymerization reaction of an epoxy group or an oxetanyl group. As the photocationic polymerization initiator, a photoacid generator and a photobase generator can be used, and the photoacid generator described later is preferably used. When the adhesive composition used in the present invention is used with visible light curability, it is particularly preferable to use a photocationic polymerization initiator having high sensitivity to light of 380 nm or more, but the photocationic polymerization initiator is In general, since it is a compound that exhibits maximum absorption in a wavelength region near 300 nm or shorter, it is possible to add a light sensitizer that exhibits maximum absorption in light in a longer wavelength region, specifically, a wavelength longer than 380 nm. , Sensitive to light of wavelengths in the vicinity of this, can promote the generation of cation species or acids from the photocationic polymerization initiator. Examples of the photosensitizer include anthracene compounds, pyrene compounds, carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, halogen compounds, photoreducing dyes and the like. Two or more types may be mixed and used. In particular, anthracene compounds are preferable because they have an excellent photosensitizing effect, and specific examples thereof include anthracene UVS-1331 and anthracene UVS-1221 (manufactured by Kawasaki Kasei Chemicals, Inc.). The content of the photosensitizer is preferably 0.1% by mass to 5% by mass, and more preferably 0.5% by mass to 3% by mass.

In addition, various additives can be added to the adhesive composition as other optional components as long as the object and effect of the present invention are not impaired. Examples of such additives include epoxy resins, polyamides, polyamideimides, polyurethanes, polybutadienes, polychloroprenes, polyethers, polyesters, styrene-butadiene block copolymers, petroleum resins, xylene resins, ketone resins, cellulose resins, and fluorine-based oligomers. Polymers or oligomers such as silicone-based oligomers and polysulfide-based oligomers; polymerization inhibitors such as phenothiazine and 2,6-di-t-butyl-4-methylphenol; polymerization initiators; leveling agents; wettability improvers; surface activity Agents; plasticizers; UV absorbers; inorganic fillers; pigments; dyes and the like.

When the adhesive composition is applied to the surface of the transparent protective film having the convex portion, the viscosity of the adhesive composition at the time of coating is preferably set in order to prevent air bubbles from being mixed around the convex portion. It is 0.5 to 100 mPa · s, more preferably 1 to 50 mPa · s. The viscosity of the adhesive composition at the time of coating can be adjusted by the type and amount of the curable component used, the acrylic oligomer, and the additive. Further, the temperature of the adhesive composition at the time of coating may be adjusted to adjust the viscosity of the adhesive composition within the above range. The temperature of the adhesive composition at the time of coating is not particularly limited, but is preferably 15 to 40 ° C, more preferably 20 to 35 ° C.

<Manufacturing method of polarizing film>
Hereinafter, each step in the method for producing a polarizing film according to the present invention will be described.

The method for producing a polarizing film according to the present invention includes a coating step of applying an adhesive composition to a surface having a convex portion of the transparent protective film, a bonding step of bonding a polarizing element and the transparent protective film, and the bonding. It includes an adhesion step of adhering the polarizer and the transparent protective film via an adhesive layer having a thickness of 1.6 μm or more obtained by curing the agent composition.

The method for producing a polarizing film according to the present invention further preferably includes a coating step of applying an easy-adhesion composition to the bonded surface of the polarizer.

The polarizer and the transparent protective film may be surface-modified before the coating process. In particular, it is preferable to perform a surface modification treatment on the surface of the polarizer. Examples of the surface modification treatment include corona treatment, plasma treatment, excimer treatment, frame treatment, and the like, and corona treatment is particularly preferable. By performing the corona treatment, reactive functional groups such as carbonyl groups and amino groups are generated on the surface of the polarizer, and the adhesion with the adhesive layer is improved. Further, the ashing effect removes foreign substances on the surface and reduces the unevenness of the surface, so that a polarizing film having excellent appearance characteristics can be produced.

<Coating process of easy-adhesive composition>
Examples of the method of applying the easy-adhesion composition to the bonding surface of the polarizer include a method of applying the easy-adhesion composition to the bonding surface of the polarizer. The coating method is not particularly limited, and examples thereof include a roll coat, a gravure coat, a reverse coat, a roll brush, a spray coat, an air knife coat, and a curtain coat method.

When the easy-adhesion composition contains a solvent, the easy-adhesion composition may be applied to the bonded surface of the polarizer and then a drying step may be performed if necessary.

If the thickness of the easy-adhesion composition layer (after drying) obtained by applying the easy-adhesion composition is too thick, the cohesive force of the easy-adhesion layer obtained by curing the easy-adhesion composition layer decreases, and easy adhesion occurs. The effect may be reduced. Therefore, the thickness of the easy-adhesion composition layer (after drying) is preferably 1000 nm or less, more preferably 800 nm or less, and further preferably 600 nm or less. On the other hand, in order for the easy-adhesion layer to fully exert its effect, the thickness of the easy-adhesion composition layer (after drying) is usually 50 nm or more, preferably 100 nm or more, and more preferably 200 nm or more.

<Coating process of adhesive composition>
The method of applying the adhesive composition to the peeling surface side of the support of the transparent protective film is appropriately selected depending on the viscosity of the adhesive composition and the desired thickness. For example, a reverse coater or a gravure coater (direct, reverse or offset) ), Bar reverse coater, roll coater, die coater, bar coater, rod coater and the like.

The thickness of the adhesive layer obtained by curing the adhesive composition of the adhesive composition is 1.6 μm or more, 2 μm or more, 3 μm or more, or 5 μm or more, depending on the height of the convex portion of the transparent protective film. Apply so that When the easy-adhesive layer is formed on the bonding surface of the polarizer, the easy-adhesive layer becomes a part of the adhesive layer, so that the thickness of the adhesive layer including the easy-adhesive layer is 1.6 μm or more. The adhesive composition is applied to.

<Lasting process>
The polarizer and the transparent protective film are bonded to each other via the adhesive composition (and the easy-adhesion composition layer) coated as described above. The polarizer and the transparent protective film can be bonded by a roll laminator or the like.

<Adhesion process>
After the polarizer and the transparent protective film are bonded together, an active energy ray (electron beam, ultraviolet rays, visible light, etc.) is irradiated to cure the adhesive composition (and the easy-adhesion composition layer) to form an adhesive layer. Form. The irradiation direction of the active energy beam (electron beam, ultraviolet ray, visible light, etc.) can be any suitable direction. Preferably, the irradiation is performed from the transparent protective film side. When irradiated from the polarizer side, the polarizer may be deteriorated by active energy rays (electron beam, ultraviolet rays, visible light, etc.).

As the irradiation conditions for irradiating the electron beam, any appropriate conditions can be adopted as long as the above-mentioned adhesive composition can be cured. For example, in electron beam irradiation, the acceleration voltage is preferably 5 kV to 300 kV, and more preferably 10 kV to 250 kV. If the acceleration voltage is less than 5 kV, the electron beam may not reach the adhesive and curing may be insufficient. If the acceleration voltage exceeds 300 kV, the penetrating power through the sample is too strong and damages the transparent protective film and the polarizer. May be given. The irradiation dose is 5 to 100 kGy, more preferably 10 to 75 kGy. When the irradiation dose is less than 5 kGy, the adhesive is insufficiently cured, and when it exceeds 100 kGy, the transparent protective film and the polarizer are damaged, the mechanical strength is lowered and yellowing occurs, and the predetermined optical characteristics are obtained. I can't.

The electron beam irradiation is usually performed in an inert gas, but if necessary, it may be performed in the atmosphere or under the condition that a small amount of oxygen is introduced. Depending on the material of the transparent protective film, by appropriately introducing oxygen, oxygen inhibition can be caused on the surface of the transparent protective film that is first hit by the electron beam, and damage to the transparent protective film can be prevented, only for the adhesive. The electron beam can be efficiently irradiated.

In the method for producing a polarizing film according to the present invention, as the active energy ray, one containing visible light having a wavelength range of 380 nm to 450 nm, particularly an active energy ray having the largest irradiation amount of visible light having a wavelength range of 380 nm to 450 nm is used. Is preferable. When using ultraviolet rays and visible light, and when using a transparent protective film with ultraviolet absorbing ability (ultraviolet opaque transparent protective film), it is shorter than 380 nm because it absorbs light with a wavelength shorter than about 380 nm. Light of wavelength does not reach the adhesive composition and does not contribute to its polymerization reaction. Further, the light having a wavelength shorter than 380 nm absorbed by the transparent protective film is converted into heat, and the transparent protective film itself generates heat, which causes defects such as curl and wrinkles of the polarizing film. Therefore, when ultraviolet rays and visible rays are adopted in the present invention, it is preferable to use a device that does not emit light having a wavelength shorter than 380 nm as an active energy ray generator, and more specifically, integration in a wavelength range of 380 to 440 nm. The ratio of the illuminance to the integrated illuminance in the wavelength range of 250 to 370 nm is preferably 100: 0 to 100: 50, and more preferably 100: 0 to 100:40. In the method for producing a polarizing film according to the present invention, as the active energy ray, a gallium-filled metal halide lamp and an LED light source that emits a wavelength range of 380 to 440 nm are preferable. Alternatively, with ultraviolet rays such as low-pressure mercury lamp, medium-pressure mercury lamp, high-pressure mercury lamp, ultra-high pressure mercury lamp, incandescent lamp, xenon lamp, halogen lamp, carbon arc lamp, metal halide lamp, fluorescent lamp, tungsten lamp, gallium lamp, excima laser or sunlight. A light source containing visible light can be used, and a bandpass filter can be used to block ultraviolet rays having a wavelength shorter than 380 nm. In order to prevent curling of the polarizing film while improving the adhesive performance of the adhesive layer between the polarizer and the transparent protective film, a gallium-filled metal halide lamp can be used and light having a wavelength shorter than 380 nm can be blocked. It is preferable to use an active energy ray obtained through a bandpass filter or an active energy ray having a wavelength of 405 nm obtained by using an LED light source.

It is preferable to heat the adhesive composition before irradiating it with ultraviolet rays or visible light (warming before irradiation), in which case it is preferable to heat it to 40 ° C. or higher, and it is more preferable to heat it to 50 ° C. or higher. preferable. It is also preferable to heat the active energy ray-curable adhesive composition after irradiation with ultraviolet rays or visible light (warming after irradiation), in which case the temperature is preferably 40 ° C. or higher, and 50 ° C. or higher. It is more preferable to warm it.

The adhesive composition used in the present invention can be suitably used particularly when forming an adhesive layer for adhering a polarizer and a transparent protective film having a light transmittance of less than 5% at a wavelength of 365 nm. Here, the adhesive composition used in the present invention contains the above-mentioned photopolymerization initiator of the general formula (3), thereby irradiating ultraviolet rays through a transparent protective film having UV absorbing ability to form an adhesive. The layer can be cured and formed. Therefore, the adhesive layer can be cured even in a polarizing film in which a transparent protective film having a UV absorbing ability is laminated on both sides of the polarizing element. However, as a matter of course, the adhesive layer can be cured even in a polarizing film in which a transparent protective film having no UV absorption ability is laminated. The transparent protective film having a UV absorbing ability means a transparent protective film having a transmittance of less than 10% for light at 380 nm.

Examples of the method of imparting the UV absorbing ability to the transparent protective film include a method of incorporating an ultraviolet absorber in the transparent protective film and a method of laminating a surface treatment layer containing an ultraviolet absorber on the surface of the transparent protective film.

Specific examples of the ultraviolet absorber include conventionally known oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex salt compounds, triazine compounds and the like. ..

When the polarizing film according to the present invention is produced in a continuous line, the line speed depends on the curing time of the adhesive composition, but is preferably 1 to 500 m / min, more preferably 5 to 300 m / min, and further preferably 10 to 10. It is 100 m / min. If the line speed is too low, productivity will decrease and the transparent protective film will be damaged. If the line speed is too high, the adhesive composition may not be sufficiently cured and the desired adhesiveness may not be obtained.

The thickness of the adhesive layer (including the easy-adhesive layer) must be 1.6 μm or more in order to produce a polarizing film without spot-like white spot defects and partial swelling on the surface of the transparent protective film. Yes, preferably 2 μm or more, more preferably 3 μm or more, still more preferably 5 μm or more. The upper limit of the thickness of the adhesive layer (including the easy-adhesive layer) is not particularly limited, but is preferably 10 μm or less, more preferably 7 μm or less, from the viewpoint of curability of the adhesive layer.

<Optical film>
The polarizing film of the present invention can be used as an optical film laminated with another optical layer in practical use. The optical layer is not particularly limited, but for example, a liquid crystal such as a retardation film (including a wave plate such as 1/2 or 1/4), a visual compensation film, a brightness improving film, a reflecting plate or an antitransmissive plate, etc. Examples thereof include an optical layer that may be used for forming a display device or the like.

As the retardation film, a film having a frontal retardation of 40 nm or more and / or a thickness direction retardation of 80 nm or more can be used. The frontal phase difference is usually controlled in the range of 40 to 200 nm, and the thickness direction phase difference is usually controlled in the range of 80 to 300 nm.

Examples of the retardation film include a birefringent film obtained by uniaxially or biaxially stretching a polymer material, an alignment film of a liquid crystal polymer, and a film in which an alignment layer of a liquid crystal polymer is supported by a film. The thickness of the retardation film is not particularly limited, but is generally about 20 to 150 μm.

As the retardation film, the following formulas (1) to (3):
0.70 <Re [450] / Re [550] <0.97 ... (1)
1.5 × 10-3 <Δn <6 × 10-3 ... (2)
1.13 <NZ <1.50 ... (3)
(In the equation, Re [450] and Re [550] are in-plane retardation values of the retardation film measured with light having wavelengths of 450 nm and 550 nm at 23 ° C., respectively, and Δn is the slow phase of the retardation film. In-plane birefringence, which is nx-ny when the refractive indexes in the axial direction and the phase-advancing axis direction are nx and ny, respectively, and NZ is the refractive index when nz is the refractive index in the thickness direction of the retardation film. An inverse wavelength dispersion type retardation film satisfying (the ratio of nx-nz which is birefringence in the thickness direction to nx-ny which is in-plane birefringence) may be used.

An adhesive layer for adhering to other members such as a liquid crystal cell may be provided on the above-mentioned polarizing film or an optical film in which at least one polarizing film is laminated. The pressure-sensitive adhesive forming the pressure-sensitive adhesive layer is not particularly limited, and for example, a polymer based on an acrylic polymer, a silicone-based polymer, polyester, polyurethane, polyamide, polyether, fluorine-based or rubber-based polymer is appropriately selected. Can be used. In particular, an acrylic pressure-sensitive adhesive that has excellent optical transparency, exhibits appropriate wettability, cohesiveness, and adhesiveness, and has excellent weather resistance and heat resistance can be preferably used.

The adhesive layer can also be provided on one or both sides of a polarizing film or an optical film as a superimposing layer of different compositions or types. Further, when provided on both sides, adhesive layers having different compositions, types and thicknesses can be formed on the front and back surfaces of the polarizing film or the optical film. The thickness of the adhesive layer can be appropriately determined according to the purpose of use, adhesive strength, etc., and is generally 1 to 500 μm, preferably 1 to 200 μm, and particularly preferably 1 to 100 μm.

The exposed surface of the adhesive layer is temporarily covered with a separator for the purpose of preventing contamination until it is put into practical use. As a result, it is possible to prevent contact with the adhesive layer in the usual handling state. As the separator, except for the above-mentioned thickness condition, for example, an appropriate thin leaf body such as a plastic film, a rubber sheet, a paper, a cloth, a non-woven fabric, a net, a foam sheet or a metal leaf, or a laminate thereof may be used as a silicone-based or long separator. Appropriate conventional ones such as those coated with an appropriate release agent such as chain alkyl type, fluorine type and molybdenum sulfide can be used.

<Image display device>
The polarizing film or optical film of the present invention can be preferably used for forming various devices such as a liquid crystal display device. The liquid crystal display device can be formed according to the conventional method. That is, the liquid crystal display device is generally formed by appropriately assembling a liquid crystal cell, a polarizing film or an optical film, and if necessary, components such as a lighting system, and incorporating a drive circuit. There is no particular limitation except that the polarizing film or the optical film according to the invention is used, and the conventional method can be applied. As the liquid crystal cell, any type such as TN type, STN type, and π type can be used.

An appropriate liquid crystal display device such as a liquid crystal display device in which a polarizing film or an optical film is arranged on one side or both sides of the liquid crystal cell, or a lighting system using a backlight or a reflector can be formed. In that case, the polarizing film or optical film according to the present invention can be arranged on one side or both sides of the liquid crystal cell. When polarizing films or optical films are provided on both sides, they may be the same or different. Further, when forming the liquid crystal display device, for example, an appropriate component such as a diffuser plate, an anti-glare layer, an antireflection film, a protective plate, a prism array, a lens array sheet, a light diffuser plate, and a backlight is placed in one layer or at an appropriate position. Two or more layers can be arranged.

Examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

<Polarizer>
First, a stretched laminate in which a 9 μm-thick PVA layer was formed on an amorphous PET substrate was subjected to aerial auxiliary stretching at a stretching temperature of 130 ° C. to produce a stretched laminate, and then the stretched laminate was dyed to form a colored laminate. The colored laminate is further stretched in boric acid at a stretching temperature of 65 ° C. to include a 5 μm-thick PVA layer integrally stretched with an amorphous PET substrate so that the total stretching ratio is 5.94 times. An optical film laminate was produced. The PVA molecules in the PVA layer formed on the amorphous PET substrate by such two-step stretching are highly oriented, and the iodine adsorbed by dyeing is highly oriented in one direction as a polyiodine ion complex. An optical film laminate containing a PVA layer having a thickness of 5 μm, which constitutes a thin polarizing element, was obtained. The water content of the thin polarizer (PVA layer) was 10% by mass.

<Transparent protective film>
As the transparent protective film, a triacetyl cellulose film having a thickness of 25 μm (manufactured by Konica Minolta: KC2UA) was used. The film is manufactured by a solution casting film forming method, and the surface of the film on the side where the film-forming support is peeled off (support peeling surface) is present on the surface of the film-forming support. It had a convex portion due to a concave portion such as a scratch and a pinhole.

<Active energy ray>
Visible light (gallium-filled metal halide lamp) Irradiator: Fusion UV Systems, Inc. Light HAMMER10 bulb: V bulb Peak illuminance: 1600 mW / cm ² , integrated irradiation dose 1000 / mJ / cm2 (wavelength 380-440 nm) )It was used. The illuminance of visible light was measured using a Solar-Check system manufactured by Solarll.

<Preparation of easy-adhesion composition>
Obtained by mixing 50 parts by mass of acryloylmorpholin (manufactured by KJ Chemicals, trade name "ACMO", SP value: 22.9) and 0.9 parts by mass of 3-acrylamide phenylboronic acid (manufactured by Genuine Chemicals). The mixture was stirred at 25 ° C. for 30 minutes, and further mixed with 48.3 parts by mass of water and 0.8 parts by mass of a leveling agent (manufactured by Nisshin Chemical Industry Co., Ltd., trade name "Orfin EXP.4123"). , The easy-adhesion composition was prepared by stirring at 25 ° C. for 10 minutes.

Example 1
<Preparation of adhesive composition>
Acryloylmorpholin (manufactured by KJ Chemicals, trade name "ACMO", SP value: 22.9) 45 parts by mass, 1,9-nonandiol diacrylate (trade name "light acrylate 1.9ND-A", manufactured by Kyoeisha Chemical Co., Ltd. ) 41 parts by mass, 10 parts by mass of an acrylic oligomer (trade name "ARUFON UG4010", manufactured by Toa Synthetic Co., Ltd.) obtained by polymerizing a (meth) acrylic monomer, diethylthioxanthone as a photoinitiator (described in the general formula (3)). Compound, trade name "KAYACURE DETX-S", manufactured by Nippon Kayaku Co., Ltd.) 1.5 parts by mass, and 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-, which is a photopolymerization initiator. An adhesive composition is prepared by mixing 2.5 parts by mass of 1-on (compound according to general formula (4), trade name "Omnirad 907", manufactured by IGM RESINS) and stirring at 50 ° C. for 1 hour. did. The viscosity of the prepared adhesive composition at 25 ° C. was measured using an E-type viscometer (TVE22LT manufactured by Toki Sangyo Co., Ltd.) and found to be 15.3 mPa · s.

<Manufacturing of polarizing film>
On a continuous line, using a gravure roll coating method including a gravure roll, the prepared easy-adhesion composition is coated on the PVA surface of an optical film laminate containing a PVA layer having a thickness of 5 μm to obtain a thickness. A coating film having a thickness of 1100 nm was formed, and then the coating film was dried using a dryer to form an easy-adhesion composition layer having a thickness of 550 nm.
On the other hand, an adhesive composition (25 ° C.) prepared on a support peeling surface (surface having a convex portion) of the transparent protective film by using a gravure roll coating method including a gravure roll on another continuous line. ) Was applied to form an adhesive composition layer having a thickness of 1500 nm.
Next, using a roll machine, the bonded surface on which the easy-adhesive composition layer of the optical film laminate was formed and the bonded surface on which the adhesive composition layer of the transparent protective film was formed were bonded. After that, the visible light is irradiated from the bonded transparent protective film side by an active energy ray irradiator to bond the polarizing element and the transparent protective film via an adhesive layer (including an easy-adhesive layer), and further. The amorphous PET substrate was peeled off and removed by hot air drying at 70 ° C. for 3 minutes to obtain a polarizing film having a transparent protective film on one side of the polarizer. The thickness of the adhesive layer (including the easy-adhesive layer) was 2050 nm.

Example 2
<Preparation of adhesive composition>
An adhesive composition was prepared in the same manner as in Example 1.

<Manufacturing of polarizing film>
On a continuous line, using a gravure roll coating method including a gravure roll, the prepared easy-adhesion composition is coated on the PVA surface of an optical film laminate containing a PVA layer having a thickness of 5 μm to obtain a thickness. A coating film having a thickness of 950 nm was formed, and then the coating film was dried using a dryer to form an easy-adhesion composition layer having a thickness of 475 nm.
On the other hand, an adhesive composition (25 ° C.) prepared on a support peeling surface (surface having a convex portion) of the transparent protective film by using a gravure roll coating method including a gravure roll on another continuous line. ) Was applied to form an adhesive composition layer having a thickness of 1500 nm.
Then, a polarizing film was obtained in the same manner as in Example 1. The thickness of the adhesive layer (including the easy-adhesive layer) was 1975 nm.

Example 3
<Preparation of adhesive composition>
An adhesive composition was prepared in the same manner as in Example 1 using the raw materials and blending amounts shown in Table 2. When the viscosity of the prepared adhesive composition at 25 ° C. was measured using an E-type viscometer (TVE22LT manufactured by Toki Sangyo Co., Ltd.), it was 42 mPa · s. The light acrylate DCP-A in Table 2 is dimethylol-tricyclodecanediacrylate (trade name "light acrylate DCP-A", manufactured by Kyoeisha Chemical Co., Ltd.).

<Manufacturing of polarizing film>
On a continuous line, using a gravure roll coating method including a gravure roll, the prepared easy-adhesion composition is coated on the PVA surface of an optical film laminate containing a PVA layer having a thickness of 5 μm to obtain a thickness. A coating film having a thickness of 950 nm was formed, and then the coating film was dried using a dryer to form an easy-adhesion composition layer having a thickness of 475 nm.
On the other hand, an adhesive composition (25 ° C.) prepared on a support peeling surface (surface having a convex portion) of the transparent protective film by using a gravure roll coating method including a gravure roll on another continuous line. ) Was applied to form an adhesive composition layer having a thickness of 1500 nm.
Then, a polarizing film was obtained in the same manner as in Example 1. The thickness of the adhesive layer (including the easy-adhesive layer) was 1975 nm.

Comparative Example 1
<Preparation of adhesive composition>
An adhesive composition was prepared in the same manner as in Example 1.

<Manufacturing of polarizing film>
On a continuous line, using a gravure roll coating method including a gravure roll, the prepared easy-adhesion composition is coated on the PVA surface of an optical film laminate containing a PVA layer having a thickness of 5 μm to obtain a thickness. A coating film having a thickness of 950 nm was formed, and then the coating film was dried using a dryer to form an easy-adhesion composition layer having a thickness of 475 nm.
On the other hand, an adhesive composition (25 ° C.) prepared on a support peeling surface (surface having a convex portion) of the transparent protective film by using a gravure roll coating method including a gravure roll on another continuous line. ) Was applied to form an adhesive composition layer having a thickness of 1100 nm.
Then, a polarizing film was obtained in the same manner as in Example 1. The thickness of the adhesive layer (including the easy-adhesive layer) was 1575 nm.

Reference example 1
<Preparation of adhesive composition>
An adhesive composition was prepared in the same manner as in Example 1 using the raw materials and blending amounts shown in Table 2. When the viscosity of the prepared adhesive composition at 25 ° C. was measured using an E-type viscometer (TVE22LT manufactured by Toki Sangyo Co., Ltd.), it was 109 mPa · s. The light acrylate DCP-A in Table 2 is dimethylol-tricyclodecanediacrylate (trade name "light acrylate DCP-A", manufactured by Kyoeisha Chemical Co., Ltd.).

<Manufacturing of polarizing film>
On a continuous line, using a gravure roll coating method including a gravure roll, the prepared easy-adhesion composition is coated on the PVA surface of an optical film laminate containing a PVA layer having a thickness of 5 μm to obtain a thickness. A coating film having a thickness of 950 nm was formed, and then the coating film was dried using a dryer to form an easy-adhesion composition layer having a thickness of 475 nm.
On the other hand, an adhesive composition (25 ° C.) prepared on a support peeling surface (surface having a convex portion) of the transparent protective film by using a gravure roll coating method including a gravure roll on another continuous line. ) Was applied to form an adhesive composition layer having a thickness of 1500 nm.
Then, a polarizing film was obtained in the same manner as in Example 1. The thickness of the adhesive layer (including the easy-adhesive layer) was 1975 nm.

(Evaluation of dot-shaped white spot defects)
Using a xenon lamp light source (manufactured by Hamamatsu Photonics Co., Ltd., model: L8425-01), the obtained polarizing film was transmitted and projected onto a white screen 1 m away from the light source. Then, the projected image on the screen was observed, and the number of white spot defects appearing as white dots in the projected image range corresponding to the range of 1 m × 1 m of the polarizing film was counted. The evaluation was performed in a dark room. The results are shown in Table 2.

(Evaluation of swelling on the surface of transparent protective film)
Under a fluorescent lamp, light was applied to the transparent protective film side of the obtained polarizing film, and the surface shape was observed from the reflected light reflected on the surface of the polarizing film. Then, in the area of 1 m × 1 m on the surface of the polarizing film, the number of places where there was a convex bulge was counted in the places where the white spots were reflected in the evaluation of the white spot defect. The evaluation was performed in a dark room. The results are shown in Table 2.

(Evaluation of bubbles)
The appearance of the obtained polarizing film was observed with an optical microscope, and the number of bubbles having a maximum diameter of 5 μm to 200 μm in the range of 5 cm × 5 cm was counted. The case where the number of bubbles was 0 was evaluated as 0, and the case where the number of bubbles was 1 or more was evaluated as ×. The results are shown in Table 2.

The polarizing film of the present invention is used alone or as an optical film in which it is laminated in an image display device such as a liquid crystal display (LCD), an organic EL display device, a CRT, or a PDP.

Claims (16)

A polarizing film in which a transparent protective film is provided on at least one surface of the polarizing element via an adhesive layer.
One surface of the transparent protective film is a surface having a convex portion.
The adhesive layer is provided on the surface of the transparent protective film having a convex portion.
A polarizing film having a thickness of 1.6 μm or more of the adhesive layer. The surface of the transparent protective film having a convex portion is a support peeling surface from which the film-forming support has been peeled off.
The polarizing film according to claim 1, wherein the convex portion is formed due to a concave portion on the surface of the film-forming support. The polarizing film according to claim 1 or 2, wherein the transparent protective film is a cellulosic resin film. The polarizing film according to any one of claims 1 to 3, wherein the thickness of the transparent protective film is 30 μm or less. The polarizing film according to any one of claims 1 to 4, which has an easy-adhesive layer that is a part of the adhesive layer on the bonding surface of the polarizer. The easy-adhesion composition, which is the material for forming the easy-adhesion layer, has the following general formula (1):

Compound represented by (where X is a functional group containing a reactive group, and R ¹ and R ² may independently have a hydrogen atom and a substituent, an aliphatic hydrocarbon group and an aryl group, respectively. , Or a heterocyclic group) and / or an organometallic compound having an MO bond (M is silicon, titanium, aluminum, or zirconium and O is an oxygen atom) in the structural formula. 5. The polarizing film according to 5. The compound represented by the general formula (1) is the following general formula (1').

The polarizing film according to claim 6, wherein Y is an organic group, and X, R ¹ and R ² are the same as described above. The reactive groups of the compound represented by the general formula (1) are α, β-unsaturated carbonyl group, vinyl group, vinyl ether group, epoxy group, oxetane group, amino group, aldehyde group, mercapto group, and halogen. The polarizing film according to claim 6 or 7, which is at least one reactive group selected from the group consisting of groups. Claims 6 to 8 include the polymerizable compound X having an SP value of 21.0 (MJ / m ³ ) ^1/2 or more and 26.0 (MJ / m ³ ) ^1/2 or less in the easy-adhesion composition. The polarizing film according to any one of. A method for manufacturing a polarizing film in which a transparent protective film is provided on at least one surface of a polarizing element via an adhesive layer.
One surface of the transparent protective film is a surface having a convex portion.
A coating step of applying the adhesive composition to the surface of the transparent protective film having a convex portion,
The polarizer and the transparent protective film are attached via a bonding step of bonding the polarizing element and the transparent protective film, and the adhesive layer having a thickness of 1.6 μm or more obtained by curing the adhesive composition. A method for producing a polarizing film, which comprises a bonding step of bonding. The surface of the transparent protective film having a convex portion is a support peeling surface from which the film-forming support has been peeled off.
The method for producing a polarizing film according to claim 10, wherein the convex portion is formed due to a concave portion on the surface of the film-forming support. The method for producing a polarizing film according to claim 10 or 11, wherein the viscosity of the adhesive composition at the time of coating is 0.5 to 100 mPa · s. On the bonding surface of the polarizer, the following general formula (1):

Compound represented by (where X is a functional group containing a reactive group, and R ¹ and R ² may independently have a hydrogen atom and a substituent, an aliphatic hydrocarbon group and an aryl group, respectively. , Or a heterocyclic group) and / or easy adhesion containing an organometallic compound having an MO bond (M is silicon, titanium, aluminum, or zirconium and O is an oxygen atom) in the structural formula. The method for producing a polarizing film according to any one of claims 10 to 12, which comprises a coating step of coating the composition. The easy-adhesion composition according to claim 13, which contains a polymerizable compound X having an SP value of 21.0 (MJ / m ³ ) ^1/2 or more and 26.0 (MJ / m ³ ) ^1/2 or less. How to make a polarizing film. An optical film having the polarizing film according to any one of claims 1 to 9. An image display device having the polarizing film according to any one of claims 1 to 9 or the optical film according to claim 15.