TW202112545A - Polarizing film and manufacturing method thereof, optical film, and image display device in which the polarizing film includes a transparent protective film provided, by means of an adhesive agent layer, on at least a surface of a polarizing element - Google Patents

Abstract

An objective of the present invention is to provide a polarizing film that does not include a spot-like whitish defect and no partial swelling on a surface of a transparent protective film. A solution is that a polarizing film according to the present invention includes a transparent protective film provided, by means of an adhesive agent layer, on at least a surface of a polarizing element. The abovesaid transparent protective film has a surface that is a surface including a raised portion. The abovesaid adhesive agent layer is provided on the surface of the abovesaid transparent protective film including the raised portion, and the abovesaid adhesive agent layer has a thickness that is at least 1.6 [mu]m.

Description

Polarizing film, manufacturing method thereof, optical film, and image display device

The present invention relates to a method for manufacturing a polarizing film in which a transparent protective film is provided on at least one side of a polarizer via an adhesive layer. The polarizing film can be used alone or in the form of a laminated optical film to form image display devices such as liquid crystal display devices (LCD), organic EL display devices, CRTs, and PDPs.

Among clocks, mobile phones, PDAs, notebook computers, computer monitors, DVD players, TVs, etc., liquid crystal display devices are rapidly opening up the market. The liquid crystal display device uses the switch of the liquid crystal to visualize the polarization state, and uses a polarizer based on its display principle. Especially in TV applications, high brightness, high contrast, and wide viewing angle are increasingly required, and polarizing films are also increasingly required to have high transmittance, high degree of polarization, and high color reproducibility.

As a polarizer, from the viewpoint of having high transmittance and high degree of polarization, for example, the most widely used iodine system is a structure in which iodine is adsorbed on polyvinyl alcohol (hereinafter, also abbreviated as "PVA") and stretched. Polarized parts. Generally, a polarizing film is used to laminate a transparent protective film on both sides of a polarizer using a so-called water-based adhesive, which is made by dissolving a polyvinyl alcohol-based material in water (Patent Documents 1 and 2 below) . As the transparent protective film, cellulose triacetate with high moisture permeability or the like is used. In the case of using the aforementioned aqueous adhesive (so-called wet lamination), a drying step is required after bonding the polarizer and the transparent protective film.

On the other hand, instead of the aforementioned aqueous adhesive, an active energy ray-curable adhesive has been proposed. In the case of manufacturing a polarizing film using an active energy ray curable adhesive, since a drying step is not required, the productivity of the polarizing film can be improved. For example, the inventors of the present invention have proposed a radical polymerization type active energy ray curable adhesive that uses an N-substituted amide-based monomer as a curable component (Patent Document 3 below). Prior art literature Patent literature

Patent Document 1: Japanese Patent Laid-Open No. 2001-296427 Patent Document 2: Japanese Patent Laid-Open No. 2007-256569 Patent Document 3: Japanese Patent Laid-Open No. 2012-052000

The problem to be solved by the invention However, in the conventional polarizing film obtained by bonding a polarizer and a transparent protective film with an adhesive layer, spot-like whitening defects or local swelling may occur on the surface of the transparent protective film.

The present invention solves the above-mentioned problems, and its object is to provide a polarizing film that has no spot-like whitening defects and no local swelling on the surface of the transparent protective film.

Means to solve the problem The above-mentioned problem can be solved by the following configuration.

That is, the present invention relates to a polarizing film in which a transparent protective film is provided on at least one side of a polarizer via an adhesive layer, and the characteristics of the polarizing film are: One surface of the aforementioned transparent protective film is a surface with convex portions, The adhesive layer is disposed on the convex surface of the transparent protective film, and The thickness of the aforementioned adhesive layer is 1.6 μm or more.

As an aspect of the aforementioned transparent protective film, the surface with convex portions of the transparent protective film is the peeling surface of the support after the support for film formation is peeled off, and the convex portions are the recesses on the surface of the support for film formation. Formed by.

The aforementioned transparent protective film is preferably a cellulose resin film.

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

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

(惟，X為包含反應性基的官能基，R¹ 及R² 分別獨立表示氫原子、可具有取代基的脂肪族烴基、芳基或雜環基)；及/或結構式中具有M-O鍵(M為矽、鈦、鋁或鋯，O為氧原子)的有機金屬化合物。此外，在本發明中，亦將前述通式(1)所示化合物稱為「含硼化合物」。The easy-adhesive composition, which is the forming material of the aforementioned easy-adhesive layer, preferably contains: a compound represented by the following general formula (1): [Chemical formula 1]

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

(惟，Y為有機基，X、R¹ 及R² 與前述相同)。The compound represented by the aforementioned general formula (1) is preferably a compound represented by the following general formula (1'): [Chemical formula 2]

(However, Y is an organic group, and X, R ¹ and R ^{2 are the} same as above).

The reactive group of the compound represented by the aforementioned general formula (1) is preferably selected from α, β-unsaturated carbonyl, vinyl, vinyl ether, epoxy, oxetanyl, amino, aldehyde At least one reactive group in the group consisting of a sulfhydryl group, a mercapto group, and a halogen group.

The aforementioned easy-to-bond 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.}

In addition, the present invention relates to a method of manufacturing a polarizing film, the polarizing film is provided with a transparent protective film on at least one side of the polarizer via an adhesive layer, The manufacturing method is characterized by: One surface of the aforementioned transparent protective film is a surface with convex portions; And the manufacturing method includes the following steps: The coating step is to coat the adhesive composition on the convex surface of the aforementioned transparent protective film; The laminating step is laminating the aforementioned polarizer and the aforementioned transparent protective film; and The next step is to bond the polarizer and the transparent protective film through the adhesive layer having a thickness of 1.6 μm or more, wherein the adhesive layer is obtained by curing the adhesive composition.

As an aspect of the aforementioned transparent protective film, the surface with convex portions of the transparent protective film is the peeling surface of the support after the support for film formation is peeled off, and the convex portions are the recesses on the surface of the support for film formation. Formed by.

The viscosity of the aforementioned adhesive composition during application is preferably 0.5-100 mPa･s.

(惟，X為包含反應性基的官能基，R¹ 及R² 分別獨立表示氫原子、可具有取代基的脂肪族烴基、芳基或雜環基)；及/或在結構式中具有M-O鍵(M為矽、鈦、鋁或鋯，O為氧原子)的有機金屬化合物。The manufacturing method of the aforementioned polarizing film preferably includes a coating step of applying an easy-to-adhesive composition on the bonding surface of the aforementioned polarizer, wherein the easy-to-adhesive composition contains: a compound represented by the following general formula (1): [Chemical formula 3]

(However, X is a functional group including a reactive group, and R ¹ and R ² each independently represent a hydrogen atom, an aliphatic hydrocarbon group that may have a substituent, an aryl group, or a heterocyclic group); and/or have MO in the structural formula Bond (M is silicon, titanium, aluminum or zirconium, O is an oxygen atom) organometallic compound.

The aforementioned easy-to-bond 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.}

In addition, the present invention relates to an optical film having the aforementioned polarizing film.

In addition, the present invention relates to an image display device having the aforementioned polarizing film or the aforementioned optical film.

Invention effect The present inventors studied the causes of spot whitening defects or local swelling on the surface of the transparent protective film in the conventional polarizing film. Then think that the aforementioned problem is caused by the following reasons.

In the past, when a polarizer and a transparent protective film were laminated with an adhesive layer to produce a polarizing film, the surface of the transparent protective film on which the adhesive layer was provided was not particularly limited, and the adhesive layer was provided on any surface of the transparent protective film. .

We believe that during the manufacturing process of the aforementioned transparent protective film, due to some reasons, tiny convex portions are formed on the surface of the aforementioned transparent protective film, and if an adhesive layer is formed on the convex surface of the aforementioned transparent protective film, It becomes difficult to form an adhesive layer on the convex portion, and therefore, a whitening defect occurs in the convex portion. In addition, we believe that when the bonding surface of the polarizer and the surface with the convex portion of the transparent protective film are bonded via the adhesive composition, the bonding surface of the polarizer will contact the convex portion and apply pressure to the convex portion. As a result, the transparent protective film around the convex portion is pressed to the outside by the pressure-applied convex portion to deform, and the surface of the transparent protective film locally swells.

The inventors found that even when the adhesive layer is provided on the convex surface of the transparent protective film, by setting the thickness of the adhesive layer to 1.6 μm or more, it is possible to obtain no point whitening defects and transparent There is no partially swollen polarizing film on the surface of the protective film. We believe that by setting the thickness of the adhesive layer to 1.6 μm or more, the convex portions on the surface of the transparent protective film are completely covered by the adhesive layer, thereby suppressing the occurrence of whitening defects. In addition, we believe that by setting the thickness of the adhesive layer to 1.6 μm or more, the pressure applied to the convex part during bonding will be relieved by the adhesive composition, and the transparent protective film around the convex part will not be easily affected by the convex part. It is pressed to the outside, so it is not easy to locally swell on the surface of the transparent protective film.

We believe that one of the reasons for the formation of protrusions on the surface of the aforementioned transparent protective film is the following.

Transparent protective films such as cellulose triacetate films are usually produced by the so-called solution casting film forming method, which dissolves a polymer in a solvent and coats the resulting polymer solution on the film forming method. A coating film is formed on the support, a thin film is produced while volatilizing the solvent from the formed coating film, and then the produced thin film is peeled from the aforementioned support for film formation.

We believe that during the manufacturing process of the aforementioned transparent protective film, the small scratches and pores and other recesses on the surface of the aforementioned film-forming support will cause the side of the aforementioned transparent protective film after the aforementioned film-forming support is peeled off. The surface (support peeling surface) forms convex portions.

As a solution to the problem of spot-like whitening defects or local swelling on the surface of the transparent protective film, a method of providing an adhesive layer on the non-support peeling surface (air side) of the transparent protective film is considered. However, it is known that on the air side of the transparent protective film, specific curable components in the adhesive composition tend to penetrate into the film, and when the curable component penetrates excessively into the film, a fragile layer is formed in the adhesive layer. Causes a decrease in adhesion. Therefore, the method of providing the adhesive layer on the air side of the transparent protective film limits the design of the adhesive composition. When the adhesive layer is provided on the release side of the support of the transparent protective film, as described above, by setting the thickness of the adhesive layer to 1.6 μm or more, it is possible to obtain no spot-like whitening defects and no localization on the surface of the transparent protective film. Expanded polarizing film.

In addition, the inventors of the present invention found that the problem of spot-like whitening defects or local swelling on the surface of the transparent protective film is likely to occur when a cellulose resin film is used. Therefore, the present invention can exert an effect particularly when a cellulose resin film is used.

In addition, the inventors found that the problem of local swelling on the surface of the transparent protective film is likely 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.

In addition, when the bonding surface of the polarizer and the surface of the transparent protective film having convex portions are bonded via the adhesive composition, there is a problem that air bubbles are easily mixed between the bonding surface of the polarizer and the convex portions. The inventor found that by pre-arranging an easy-to-adhesive composition layer on the bonding surface of the polarizer (the easy-to-adhesive composition layer becomes an easy-to-adhesive layer that is part of the adhesive layer after hardening), the bubbles become less likely to be mixed into the polarized light. Between the fitting surface of the piece and the convex part.

The easy-adhesion composition, which is the material for forming the aforementioned easy-adhesion layer, preferably contains the aforementioned boron-containing compound. The aforementioned boron-containing compound can react with functional groups such as hydroxyl groups of the polarizer. Thereby, the adhesiveness of the polarizer and the adhesive layer can be improved, and as a result, the effect of improving the water-resistant adhesiveness of the polarizing film can be exhibited. Here, when the moisture 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 cannot fully react with the functional group of the polarizer, and the effect may not be sufficiently obtained. . However, even when the moisture content of the polarizer is low, the reactivity of the boron-containing compound with the functional group of the polarizer can be improved by mixing water in the easy-to-bond composition, thereby improving the polarizer and the polarizer. Adhesion of the adhesive layer. As a result, even when the moisture content of the polarizing material is low, it is possible to achieve both the improvement of the water-resistant adhesiveness of the polarizing film and the improvement of the coatability of the easy-to-bond composition.

In addition, the easy-to-bond composition preferably contains the organometallic compound. The aforementioned organometallic compound becomes an active metal species by inclusion of moisture, and as a result, the organometallic compound can form a strong bond with the polarizer. However, the aforementioned organometallic compound has multiple reaction points, so the organometallic compound that reacts with the polarizer also has unreacted points. Furthermore, the aforementioned organometallic compound can form a strong bond with the curable component in the adhesive composition coated on the bonding surface of the transparent protective film. As described above, since the aforementioned organometallic compound can form a strong bond with both the polarizer and the adhesive layer, the water-resistant adhesiveness between the polarizer and the adhesive layer will be greatly improved.

In addition, the aforementioned easy-to-bond 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 SP value of the polymerizable compound X is close to the SP value of transparent protective films such as unsaponified cellulose triacetate films and acrylic films. Therefore, the polymerizable compound X contributes to the improvement of the adhesion between the adhesive layer and the transparent protective film. The aforementioned polymerizable compound X is a raw material of the adhesive layer, and therefore is usually blended into the adhesive composition. As described above, the aforementioned polymerizable compound X contributes to the improvement of the adhesion between the adhesive layer and the transparent protective film, and therefore, it is preferable to blend it in a large amount in the adhesive composition. However, if the polymerizable compound X is blended in a large amount in the adhesive composition, the polymerizable compound X will easily penetrate into the transparent protective film. If the aforementioned polymerizable compound X penetrates excessively into the transparent protective film, a fragile layer will be formed in the adhesive layer, resulting in a decrease in adhesive strength. As a result, the adhesiveness of the adhesive layer and the transparent protective film is reduced. By blending the polymerizable compound X in the easy-to-bond composition in advance, not only can the polymerizable compound X be prevented from penetrating excessively into the transparent protective film, but also the polymerizable compound X in the easy-to-bond composition will interact with the adhesive. The curable component in the composition reacts, and the easy-adhesive layer and the adhesive layer can be integrated (make the easy-adhesive layer part of the adhesive layer). Thus, the adhesion between the polarizer and the adhesive layer can be improved without reducing the adhesion between the adhesive layer and the transparent protective film.

In addition, 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 easily mixed into the periphery of the convex portion. The inventors found that by adjusting the viscosity of the adhesive composition during application to 0.5-100 mPa·s, air bubbles are less likely to be mixed into the periphery of the convex portion.

The polarizing film of the present invention is provided with a transparent protective film on at least one side of the polarizer via an adhesive layer, one side of the transparent protective film is a surface with convex portions, and the adhesive layer is provided on the convex portion of the transparent protective film On the surface, and the thickness of the aforementioned adhesive layer is 1.6 μm or more.

Hereinafter, the polarizing film of the present invention will be described in detail. ＜Polarizers＞ In the present invention, from the viewpoint of improving the optical durability in a severe environment under high temperature and high humidity, a thin polarizer with a thickness of 3 μm or more and 15 μm or less is preferably used as the polarizer, preferably 12 μm or less, and more preferably It is 10 μm or less, particularly preferably 8 μm or less. Such a thin polarizer has little variation in thickness, is excellent in visibility, and has little dimensional change, so it is excellent in durability against thermal shock.

In addition, thin polarizers generally have a low moisture content. Specifically, in many cases, the moisture content is 15% by mass or less. Such a thin polarizer with a low moisture content has the aforementioned effects, but on the other hand, it has low reactivity with the boron-containing compound or organometallic compound contained in the easy-to-bond composition used in the present invention, and there are polarizers and When the adhesion improvement effect of the adhesive layer is insufficient. Therefore, in the polarizing film of the present invention, when a polarizer with a moisture content of 15% by mass or less is used, the easy-to-bond composition preferably contains water. Specifically, when the total amount of the easy-to-bond composition is 100% by mass, The water content is preferably 5 to 90% by mass, more preferably 30 to 80% by mass.

The polarizer uses a polyvinyl alcohol resin. Examples of polarizers include: absorbing dichroic substances such as iodine or dichroic dyes on polyvinyl alcohol-based films, partially formalized polyvinyl alcohol-based films, ethylene-vinyl acetate copolymer-based partially saponified films, etc. Hydrophilic polymer film obtained by uniaxial stretching; polyene-based oriented films such as dehydrated polyvinyl alcohol or dehydrated polyvinyl chloride. Among these, a polarizing material composed 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 stretched can be produced, for example, by immersing polyvinyl alcohol in an aqueous solution of iodine for dyeing, and stretched to 3-7 of the original length. Times. You may immerse it in the aqueous solution containing potassium iodide, etc., such as boric acid, zinc sulfate, zinc chloride, etc. as needed. Furthermore, if necessary, the polyvinyl alcohol-based film may be immersed in water and washed with water before dyeing. By washing the polyvinyl alcohol-based film with water, not only the stains and anti-blocking agents on the surface of the polyvinyl alcohol-based film can be cleaned, but also the effect of preventing unevenness such as uneven dyeing by swelling the polyvinyl alcohol-based film. Stretching may be performed after dyeing with iodine, or may be performed while dyeing, or dyeing with iodine may be performed after stretching. It can also be stretched in an aqueous solution such as boric acid or potassium iodide or in a water bath.

From the viewpoint of elongation stability or humidification reliability, the polarizing member preferably contains boric acid. In addition, from the viewpoint of suppressing the occurrence of penetration cracks, the content of boric acid contained in the polarizer is preferably 22% by mass or less, and more preferably 20% by mass or less relative to the total amount of the polarizer. From the viewpoint of extension stability or humidification reliability, the content of boric acid is preferably 10% by mass or more, and more preferably 12% by mass or more, relative to the total amount of the polarizer.

Representative thin polarizers include Japanese Patent No. 4751486, Japanese Patent No. 4751481, Japanese Patent No. 4815544, Japanese Patent No. 5048120, International Publication No. 2014/077599 Pamphlet, International Publication The thin polarizer described in pamphlet No. 2014/077636, etc., or the thin polarizer obtained by the manufacturing method described in these documents.

As the aforementioned thin polarizer, in the manufacturing method including the step of stretching in the state of a laminate and the step of dyeing, from the viewpoint that it can be stretched to a high magnification to improve the polarization performance, it is suitable to use, for example, the specification of Japanese Patent No. 4751486, The thin polarizer obtained by the manufacturing method including the step of stretching in an aqueous solution of boric acid as described in Japanese Patent No. 4751481 and Japanese Patent No. 4815544 is particularly suitable as described in Japanese Patent No. 4751481 and Japanese Patent The thin-shaped polarizer obtained by the manufacturing method in the specification No. 4815544 including the step of auxiliaryly performing aerial stretching before stretching in an aqueous solution of boric acid. These thin polarizing films can be obtained by a manufacturing method including a step of stretching a polyvinyl alcohol-based resin (hereinafter, also referred to as a PVA-based resin) layer and a resin substrate for stretching in a laminated state and a step of dyeing. According to this manufacturing method, even if the PVA-based resin layer is thin, it can be stretched by being supported by the resin base material for stretching without inconveniences such as breakage due to stretching.

＜Transparent protective film＞ The transparent protective film used in the present invention is not particularly limited. For example, it can be produced by a so-called solution casting film forming method, which dissolves a polymer in a solvent and combines the resulting polymer solution It is applied on a support for film formation to form a coating film, a thin film is produced while volatilizing the solvent from the formed coating film, and then the produced film is peeled from the support for film formation. In addition, the transparent protective film may be produced on a support for film formation by extrusion molding.

One surface of the transparent protective film used in the present invention is a surface having convex portions. As an aspect of the aforementioned transparent protective film, the surface of the transparent protective film having convex portions is the peeling surface of the support after peeling off the support for film formation, and the convex portions are the concave portions on the surface of the support for film formation. Formed by. The shape of the aforementioned convex portion is not particularly limited, but mainly (for example, 80% or more of all convex portions) is a mountain shape. The height of the aforementioned convex portion varies with 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. In addition, 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.

As a transparent protective film, it should be excellent in transparency, mechanical strength, thermal stability, moisture barrier properties, and isotropy. Examples include polyester-based polymers such as polyethylene terephthalate or polyethylene naphthalate, cellulose-based polymers such as cellulose diacetate or cellulose triacetate, polymethyl methacrylate, etc. Acrylic polymers, styrene polymers such as polystyrene or acrylonitrile-styrene copolymer (AS resin), polycarbonate polymers, etc. In addition, polyethylene, polypropylene, polyolefins having cyclic or norbornene structures, polyolefin polymers such as ethylene-propylene copolymers, vinyl chloride polymers, amide-based polymers such as nylon or aromatic polyamides Polymers, imine-based polymers, turbidity-based polymers, polyether turbidity-based polymers, polyetheretherketone-based polymers, polyphenylene sulfide-based polymers, vinyl alcohol-based polymers, and vinylidene chloride-based polymerizations Polymers, vinyl butyral-based polymers, polyarylate-based polymers, polyoxymethylene-based polymers, epoxy-based polymers, or mixtures of the above-mentioned polymers, etc. can also be used as examples of polymers that form the above-mentioned transparent protective film. And enumerate. One or more arbitrary suitable additives may be contained in the transparent protective film. Examples of additives include ultraviolet absorbers, antioxidants, lubricants, plasticizers, mold release agents, anti-coloring agents, flame retardants, nucleating agents, antistatic agents, pigments, colorants, and the like. The content of the above-mentioned thermoplastic resin in the transparent protective film is preferably 50-100% by mass, more preferably 50-99% by mass, more preferably 60-98% by mass, and particularly preferably 70-97% 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 expressed.

In addition, examples of the transparent protective film include polymer films described in Japanese Patent Application Laid-Open No. 2001-343529 (WO01/37007), such as (A) a thermoplastic resin containing a substituted and/or unsubstituted imidine group on the side chain A resin composition with a thermoplastic resin having a substituted and/or unsubstituted phenyl group and a nitrile group in the side chain. As a specific example, a film containing a resin composition of an alternating copolymer composed of isobutylene and N-methylmaleimide and an acrylonitrile-styrene copolymer can be cited. As the film, a film composed of a mixed extruded product of a resin composition or the like can be used. These films have a small retardation and a small photoelastic coefficient, and therefore can eliminate problems such as unevenness caused by the strain of the polarizing film. In addition, the moisture permeability is small, and therefore, the humidification durability is excellent.

In addition, the moisture permeability of the transparent protective film used in the present invention is preferably 150 g/m ² /24h or less. According to this structure, the moisture in the air does not easily enter the polarizing film, and the change in the moisture content of the polarizing film itself can be suppressed. As a result, it is possible to suppress curling or dimensional change of the polarizing film due to the storage environment.

As a transparent protective film provided on one or both sides of the polarizer, it is preferable to have excellent transparency, mechanical strength, thermal stability, moisture barrier properties, isotropy, etc., especially the moisture permeability of 150g/m ² /24h or less Preferably, it is ^{less than 120g/m 2} /24h, more preferably less than 5~70g/m ² /24h.

As a material for forming a transparent protective film that satisfies the aforementioned low moisture permeability, for example, polyester resin such as polyethylene terephthalate or polyethylene naphthalate; polycarbonate resin; polyarylate resin; nylon can be used. Or aromatic polyamide resins; polyolefin polymers such as polyethylene, polypropylene, and ethylene-propylene copolymers, cyclic olefin resins having cyclic or norbornene structures, (methyl) Acrylic resin, or a mixture of these. Among the aforementioned resins, polycarbonate resins, cyclic polyolefin resins, and (meth)acrylic resins are preferred, and cyclic polyolefin resins and (meth)acrylic resins are particularly preferred.

In addition, in the present invention, as the transparent protective film, a cellulose resin film is preferably used, and a cellulose triacetate film is more preferable.

The thickness of the transparent protective film can be determined appropriately. Generally speaking, from the viewpoints of strength, handleability and other workability, thin layer properties, etc., it is preferably 5-100μm, more preferably 10-50μm, and more preferably 10-30μm. It is preferably 10~25μm.

The aforementioned transparent protective film generally uses a transparent protective film with a frontal retardation of less than 40 nm and a thickness direction retardation of less than 80 nm. The frontal phase difference Re is represented by Re=(nx-ny)×d. The thickness direction retardation Rth is represented by Rth=(nx-nz)×d. In addition, the Nz coefficient is represented by Nz=(nx-nz)/(nx-ny). [However, let the refractive index of the slow axis direction, the fast axis direction, and the thickness direction of the film be nx, ny, and nz, respectively, and let d (nm) be the thickness of the film. The slow axis direction is defined as the direction in which the refractive index in the film plane reaches the maximum. ]. In addition, the transparent protective film should be as colorless as possible. It is advisable to use a protective film with a retardation value of -90nm~+75nm in the thickness direction. By using the protective film with the retardation value (Rth) in the thickness direction of -90nm~+75nm, the coloring (optical coloring) of the polarizing film caused by the transparent protective film can be almost eliminated. The thickness direction retardation value (Rth) is more preferably -80nm~+60nm, particularly preferably -70nm~+45nm.

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

Examples of the retardation plate include a birefringent film obtained by uniaxially or biaxially stretching a polymer material, an oriented film of a liquid crystal polymer, and a film supporting an oriented layer of a liquid crystal polymer. The thickness of the phase difference plate is also not particularly limited, and it is usually about 20 to 150 μm. Examples of polymer materials include polyvinyl alcohol, polyvinyl butyral, polymethyl vinyl ether, polyhydroxyethyl acrylate, hydroxyethyl cellulose, hydroxypropyl cellulose, and methyl cellulose. , Polycarbonate, polyarylate, polyethylene, polyethylene terephthalate, polyethylene naphthalate, polyether sulfide, polyphenylene sulfide, polyphenylene ether, polyallyl sulfonic acid, poly Amide, polyimide, polyolefin, polyvinyl chloride, cellulose resin, cyclic polyolefin resin (norbornene resin), or binary or ternary copolymers of these, and graft copolymers Products, mixtures, etc. These polymer materials become oriented objects (stretched films) by stretching or the like.

Examples of liquid crystal polymers include various types of main chain type and side chain type in which conjugated linear atomic groups (mesogen) that can impart orientation to the liquid crystal are introduced into the main chain or side chain of the polymer. . As a specific example of the main chain type liquid crystal polymer, a structure in which a mesogen is bonded via a spacer that can impart flexibility, such as a nematic polyester-based liquid crystal polymer, a discotic polymer, or Cholesterol-type polymers, etc. Specific examples of the side chain type liquid crystal polymer include polysiloxane, polyacrylate, polymethacrylate, or polymalonate as the main chain skeleton, and spacers composed of conjugated atomic groups are interposed. A liquid crystal polymer having a mesogen part composed of a nematic orientation-imparting para-substituted cyclic compound unit as a side chain. These liquid crystal polymers are those obtained by polishing the surface of a thin film of polyimide or polyvinyl alcohol formed on a glass plate, or those obtained by obliquely vapor-depositing silicon oxide. It is performed by developing a liquid crystalline polymer solution and performing a heat treatment.

The retardation plate can be, for example, various wavelength plates or those whose purpose is to compensate for the coloring or viewing angle of the birefringence of the liquid crystal layer, etc., which have appropriate retardation according to the purpose of use, or it can be laminated with two or more types of retardation plates to control the retardation. Those with optical characteristics.

The phase difference plate can be selected and used according to various purposes. It satisfies nx=ny＞nz, nx＞ny＞nz, nx＞ny=nz, nx＞nz＞ny, nz=nx＞ny, nz＞nx＞ny, nz＞nx= ny related person. In addition, ny=nz includes not only the case where ny and nz are exactly the same, but also the case where ny and nz are substantially the same.

For example, in a phase difference plate that satisfies nx>ny>nz, it is advisable to use a front phase difference of 40-100nm, a thickness direction retardation of 100-320nm, and an Nz coefficient of 1.8-4.5. For example, for a phase difference plate (positive A plate) that satisfies nx>ny=nz, it is advisable to use a front phase difference that satisfies 100~200nm. For example, for a phase difference plate (negative A plate) that satisfies nz=nx>ny, it is advisable to use a front phase difference that satisfies 100~200nm. For example, for a phase difference plate that satisfies nx>nz>ny, it is advisable to use a front phase difference of 150 to 300 nm and an Nz coefficient of greater than 0 and less than 0.7. In addition, 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 according to the liquid crystal display device to be applied. For example, in the case of VA (Vertical Alignment, including MVA and PVA), it is preferable that at least one side (cell side) of the transparent protective film of the polarizing film has a phase difference. The specific phase difference is preferably in the range of Re=0~240nm and Rth=0~500nm. When describing in three-dimensional refractive index, it is suitable to be nx>ny=nz, nx>ny>nz, nx>nz>ny, nx=ny>nz (positive A plate, biaxial, negative C plate). In the VA type, it is suitable to use a combination of a positive A plate and a negative C plate, or a biaxial film. When a polarizing film is used above and below the liquid crystal cell, both the top and bottom of the liquid crystal cell may have a phase difference, or any one of the transparent protective films between the top and bottom may have a phase difference.

For example, it can be used in the case of IPS (In-Plane Switching, including FFS), the case where the transparent protective film on one side of the polarizing film has a phase difference, and the case where it does not have a phase difference. For example, when there is no phase difference, it is suitable that there is no phase difference between the upper and lower sides (cell side) of the liquid crystal cell. When there is a phase difference, it is preferable to have a phase difference between the upper and lower sides of the liquid crystal cell, and a case where any one of the upper and lower sides has a phase difference (for example, the upper side has a biaxial film satisfying the relationship of nx>nz>ny and the lower side has no phase difference. In the case of a phase difference, or a case where the upper side has a positive A plate and the lower side has a positive C plate). When there is a phase difference, it should be in the range of Re=-500~500nm and Rth=-500~500nm. When described in three-dimensional refractive index, nx>ny=nz, nx>nz>ny, nz>nx=ny, nz>nx>ny (positive A plate, biaxial, positive C plate).

(惟，X為含有反應性基的官能基，R¹ 及R² 分別獨立表示氫原子、可具有取代基之脂肪族烴基、芳基、或雜環基)。作為前述脂肪族烴基，可列舉碳數1~20之可具有取代基的直鏈或支鏈烷基、碳數3~20之可具有取代基的環狀烷基、碳數2~20的烯基；作為芳基，可列舉碳數6~20之可具有取代基的苯基、碳數10~20之可具有取代基的萘基等；作為雜環基，可列舉例如至少包含一個雜原子且可具有取代基的5元環或6元環的基團。該等可以相互連結而形成環。在通式(1)中，作為R¹ 及R² ，宜為氫原子、碳數1~3之直鏈或支鏈烷基，最宜為氫原子。此外，通式(1)所示化合物在最終形成的易接著層中可以未反應的狀態存在，也可以各官能基發生了反應的狀態存在。<Easy bonding composition> The easily bonding composition used in the present invention preferably contains a compound represented by the following general formula (1): [Chemical formula 4]

(However, X is a functional group containing a reactive group, and R ¹ and R ² each independently represent a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, an aryl group, or a heterocyclic group). Examples of the aforementioned aliphatic hydrocarbon groups include linear or branched alkyl groups having 1 to 20 carbon atoms, optionally substituted cyclic alkyl groups having 3 to 20 carbon atoms, and alkenes having 2 to 20 carbon atoms. Examples of the aryl group include a substituted phenyl group with 6 to 20 carbons, and a substituted naphthyl group with 10 to 20 carbons. Examples of the heterocyclic group include, for example, at least one heteroatom And may have a 5-membered ring or 6-membered ring group with a substituent. These can 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. In addition, the compound represented by the general formula (1) may exist in an unreacted state in the easily adhesive layer finally formed, or may exist in a state in which each functional group has reacted.

The X contained in the compound represented by the general formula (1) is a functional group containing a reactive group, and is a functional group capable of reacting with the curable component constituting the adhesive layer. Examples of the reactive group contained in X include: Hydroxyl group, amino group, aldehyde group, carboxyl group, vinyl group, (meth)acrylic acid group, styryl group, (meth)acrylic acid amino group, vinyl ether group, epoxy group, oxetanyl group, α , β-unsaturated carbonyl, mercapto, halogen, etc. In the case where the adhesive composition constituting the adhesive layer is curable with active energy rays, the reactive group contained in X is preferably selected from vinyl, (meth)acryloyl, styryl, (form) Group) at least one reactive group in the group consisting of acrylamido group, vinyl ether group, epoxy group, oxetanyl group and mercapto group, especially in the adhesive composition constituting the adhesive layer is free In the case of group polymerizability, the reactive group contained in X is preferably at least one reaction selected from the group consisting of (meth)acrylic acid groups, styryl groups, and (meth)acrylic acid amino groups. When the compound represented by the general formula (1) has a (meth)acrylamido group, the reactive group has high reactivity, and the copolymerization rate with the active energy ray adhesive composition is improved, which is more preferable. In addition, the (meth)acrylamide group has high polarity and excellent adhesiveness, so it is also preferable from the viewpoint of efficiently obtaining the effects of the present invention. When the adhesive composition constituting the adhesive layer is cationic polymerizable, the reactive group contained in X preferably has a reactive group selected from the group consisting of a hydroxyl group, an amino group, an aldehyde group, a carboxyl group, a vinyl ether group, an epoxy group, At least one functional group in the group consisting of oxetanyl group and mercapto group, especially when it has an epoxy group, has excellent adhesion between the obtained adhesive layer and the adherend, and is therefore preferred. When it has a vinyl ether group, the adhesive composition is excellent in curability, which is preferable.

(惟，Y為有機基，X、R¹ 及R² 與前述相同)。更可適宜列舉以下化合物(1a)~(1d)。As a preferred specific example of the compound represented by the general formula (1), a compound represented by the following general formula (1') can be cited, [Chemical formula 5]

(However, Y is an organic group, and X, R ¹ and R ^{2 are the} same as above). More suitable examples are the following compounds (1a) to (1d).

[Chemical formula 6]

In the present invention, the compound represented by the general formula (1) may be a compound in which a reactive group is directly bonded to a boron atom, but as shown in the foregoing specific examples, the compound represented by the general formula (1) is preferably a reaction A compound formed by bonding between a sex group and a boron atom through an organic group, that is to say, it is preferably a compound represented by the general formula (1'). When the compound represented by the general formula (1) is, for example, a compound in which an oxygen atom bonded to a boron atom is bonded to a reactive group, the water adhesion resistance of the polarizing film tends to deteriorate. On the other hand, when the compound represented by the general formula (1) does not have a boron-oxygen bond, but is bonded to an organic group through a boron atom, has a boron-carbon bond and contains a reactive group (for the general formula (1) ')), the water resistance of the polarizing film will be improved, which is better. The aforementioned organic group specifically refers to an organic group having 1 to 20 carbons that may have a substituent. More specifically, examples include: linear or branched alkylene having 1 to 20 carbons and optionally having substituents, carbon Cyclic alkylene groups with 3-20 substituents, phenylenes with 6-20 carbon atoms, and naphthylenes with 10-20 carbon atoms.

As the compound represented by the general formula (1), in addition to the compounds exemplified above, the ester formed by hydroxyethyl acrylamide and boric acid, the ester formed by hydroxymethacrylamide and boric acid, hydroxyethyl acrylate and Esters formed by boric acid, esters formed by hydroxybutyl acrylate and boric acid, etc. are esters formed by (meth)acrylates and boric acid.

In the easy-adhesive composition, when the content of the compound represented by the general formula (1) is too small, the ratio of the compound represented by the general formula (1) present on the surface of the easy-adhesive layer decreases, and the easy-adhesive effect may be reduced. Therefore, in the easy-to-bond composition, the content of the compound represented by the general formula (1) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and more preferably 0.1% by mass or more. In addition, in the easy-to-bond composition, the content of the compound represented by the general formula (1) is usually 5% by mass or less, preferably 3% by mass or less, and more preferably 2% by mass or less.

In addition, the easy-to-bond composition preferably contains an organometallic compound having an M-O bond (M is silicon, titanium, aluminum or zirconium, and O is an oxygen atom) in the structural formula. In addition, the aforementioned organometallic compound may exist in an unreacted state in the easily adhesive layer that is finally formed, or may exist in a state in which each functional group has reacted.

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

As the aforementioned organosilicon compound, those having Si-O bonds can be used without particular limitation. Specific examples include active energy ray-curable organosilicon compounds or inactive energy ray-curable organosilicon compounds. It is particularly preferable that the carbon number of the organic group contained in the organosilicon compound is 3 or more. Specific examples of active energy ray-curable compounds include vinyl trichlorosilane, vinyl trimethoxy silane, vinyl triethoxy silane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy Silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, right Styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyl Methyl diethoxy silane, 3-methacryloxy propyl triethoxy silane, 3-acryloxy propyl trimethoxy silane, etc.

Preferably, they are 3-methacryloxypropyl trimethoxysilane and 3-acryloxypropyl trimethoxysilane.

As the inactive energy ray-curable compound, a compound having an amine group is preferred. Specific examples of the compound having an amino group include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, and γ-aminopropyltriethoxysilane. Aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, γ-(2- Aminoethyl)aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)aminopropyl triethoxysilane, γ-(2-aminoethyl)aminopropyl Methyl diethoxysilane, γ-(2-aminoethyl)aminopropyl triisopropoxysilane, γ-(2-(2-aminoethyl)aminoethyl)amino Propyl trimethoxysilane, γ-(6-aminohexyl)aminopropyltrimethoxysilane, 3-(N-ethylamino)-2-methylpropyltrimethoxysilane, γ-urea Propyl propyl trimethoxy silane, γ-ureidopropyl triethoxy silane, N-phenyl-γ-aminopropyl trimethoxy silane, N-benzyl-γ-amino propyl trimethoxy silane Silane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane , N-Phenylaminomethyltrimethoxysilane, (2-aminoethyl)aminomethyltrimethoxysilane, N,N'-bis[3-(trimethoxysilyl)propyl] Amino-containing silanes such as ethylenediamine; ketimine silanes such as N-(1,3-dimethylbutylene)-3-(triethoxysilyl)-1-propylamine.

As for the compound which has an amine group, only 1 type may be used, and multiple types may be combined and used for it. Among them, in order to ensure good adhesion, γ-aminopropyltrimethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, γ-(2-aminoethyl) Ethyl)aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)aminopropyl triethoxysilane, γ-(2-aminoethyl)aminopropylmethyl Diethoxysilane, N-(1,3-dimethylbutylene)-3-(triethoxysilyl)-1-propylamine.

As specific examples of inactive energy ray-curable compounds other than the above, 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, and 3-mercaptopropylmethyldimethoxysilane can be cited. Silane, 3-mercaptopropyl trimethoxysilane, bis(triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane, imidazole silane, etc.

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

When the easy-to-bond composition contains a metal alkoxide as the organometallic compound, it is preferable to use a carbon number of the organic group of the metal alkoxide having 3 or more, and more preferably 6 or more. When the carbon number is 2 or less, the pot life of the easy-to-bond composition may be shortened, and the effect of improving the water-resistant adhesiveness may be low. As the organic group having 6 or more carbon atoms, for example, an octyloxy group can be mentioned, and it can be suitably used. Suitable metal alkoxides include, for example, tetraisopropyl titanate, tetra-n-butyl titanate, butyl titanate dimer, tetraoctyl titanate, tertiary pentyl titanate, and tetra-n-butyl titanate. Tertiary butyl ester, tetrastearyl titanate, zirconium tetraisopropoxide, zirconium tetra-n-butoxide, zirconium tetraoctoxide, zirconium tertiary butoxide, zirconium tetrapropoxide, secondary aluminum butoxide, aluminum ethoxide, Aluminum isopropoxide, aluminum butoxide, diisopropoxide single and two-stage aluminum butoxide, single and two-stage butoxy aluminum diisopropoxide, etc. Among them, tetraoctyl titanate is suitable.

When the easy-to-bond composition contains a metal chelate compound as an organometallic compound, it is preferable to contain a carbon number 3 or more of the organic group of the metal chelate compound. When the carbon number is 2 or less, the pot life of the easy-to-bond composition may be shortened, and the effect of improving the water adhesion resistance of the polarizing film may be low. As the organic group having a carbon number of 3 or more, for example, an acetacetone group, an ethylacetate group, an isostearate group, an octanediol ester group, and the like can be mentioned. Among these, from the viewpoint of improving the water adhesion resistance of the adhesive layer, the organic group is preferably an acetacetone group or an ethylacetate group. Suitable metal chelate compounds include, for example, titanium acetone acetonate, titanium caprylate, titanium tetraacetone acetonate, titanium acetoacetate, titanium polyhydroxy stearate, and dipropoxy bis(ethyl acetonate). (Acetone) titanium, dibutoxy bis (octanediol acid) titanium, dipropoxy bis (ethyl acetate) titanium, titanium lactate, diethanolamine titanium, triethanolamine titanium, dipropoxy bis (lactic acid) ) Titanium, dipropoxy bis(triethanolamine) titanium, di-n-butoxy bis(triethanolamine) titanium, tri-n-butoxy titanium monostearate, diisopropoxy bis(ethyl acetyl acetate) Titanium, diisopropoxy bis (acetate) titanium, diisopropoxy bis (acetone) titanium, titanium phosphate compound, titanium ammonium lactate, 1,3-propane dioxy bis (acetate) Ethyl acetate) titanium, titanium dodecylbenzenesulfonate compound, aminoethylamino titanium ethoxide, zirconium tetraacetylacetonate, zirconium monoacetylacetonate, zirconium diacetylacetonate, zirconium acetylacetonate, acetone bis(acetate acetic acid) Ethyl) zirconium, zirconium acetate, tri-n-butoxy (ethyl acetate) zirconium, di-n-butoxy bis (ethyl acetate) zirconium, n-butoxy ginseng (ethyl acetate) zirconium , Si (n-propyl acetyl acetate) zirconium, Si (acetyl acetyl acetate) zirconium, Si (ethyl acetyl acetate) zirconium, (ethyl acetyl acetate) aluminum, aluminum acetyl acetone, ethyl acetate Acetone bis(acetate ethyl acetate) aluminum, diisopropoxy (acetate ethyl acetate) aluminum, diisopropoxy (acetone acetone) aluminum, isopropoxy bis(acetate ethyl acetate) Aluminum, isopropoxy bis (acetone acetone) aluminum, ginseng (acetate ethyl acetate) aluminum, ginseng (acetone acetone) aluminum, monoacetone bis (acetate ethyl acetone) aluminum. Among them, titanium acetylacetonate and titanium acetylacetate are preferable.

As the organometallic compound that can be used in the present invention, in addition to the above, metal salts of organic carboxylic acids such as zinc octoate, zinc laurate, zinc stearate, and tin octoate, zinc acetone chelate, and benzyl can be cited. Zinc chelate compounds such as zinc acetone chelate, zinc dibenzylidene methane chelate, zinc ethyl acetate chelate, and the like.

In the easy-to-bond composition, when the content of the organometallic compound is too small, the ratio of the organometallic compound present on the surface of the easy-to-bond layer decreases, and the easy-to-bond effect may decrease. Therefore, in the easy bonding composition, the content of the organometallic compound is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and more preferably 0.1% by mass or more. In addition, in the easy-to-bond composition, the content of the organometallic compound is usually 10% by mass or less, preferably 5% by mass or less.

The easy bonding 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 as a curable component.

As long as the polymerizable compound X has a radical 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 or less The compound can be used without limitation. As the polymerizable compound X, for example, acrylomorpholine (SP value 22.9), N-methoxy methacrylate (SP value 22.9), N-ethoxy methacrylate (SP value) 22.3) etc. In addition, as the polymerizable compound X, commercially available products can also be suitably used. Examples thereof include ACMO (manufactured by Koto Co., Ltd., SP value 22.9), Wasmer 2MA (manufactured by Kasano Kosan Co., Ltd., SP value 22.9), and Wasmer EMA (Kasano Kosan Co., Ltd., SP value 22.9). Produced by the company, SP value 22.3), Wasmer 3MA (manufactured by Kasano Kosan Co., Ltd., SP value 22.4), etc. These may be used singly or in combination of two or more kinds. Among these, acrylomorpholine is preferably used.

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

(惟，Δei為歸屬於原子或基團之在25℃下的蒸發能，Δvi為25℃下的莫耳體積)。(Calculation method of solubility parameter (SP value)) In the present invention, the solubility parameter (SP value) of polymerizable compound X is calculated by Fedors [refer to "Polymer Eng. &Sci."", Vol. 14, No. 2 (1974), pp. 148~154] calculated and found, namely [Math 1]

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

The Δei and Δvi in the above-mentioned mathematical formula represent constant numerical values assigned to i atoms and groups in the main molecule. In addition, representative examples of the numerical values of Δe and Δv given to atoms or groups are shown in Table 1 below.

[Table 1]

The content of the polymerizable compound X in the easy-adhesive composition is not particularly limited. As described above, the polymerizable compound X is suppressed by blending the polymerizable compound X blended in the adhesive composition into the easy-adhesive composition. From the viewpoint of excessive penetration into the transparent protective film, it is preferably 20% by mass or more, more preferably 30% by mass or more. On the other hand, the polymerizable compound X blended in the adhesive composition is penetrated into the transparent protective film From the viewpoint of imparting an anchoring effect, it is preferably 85% by mass or less, more preferably 75% by mass or less. In addition, with regard to the content of the polymerizable compound X in the easy-to-bond composition, the total content of the polymerizable compound X in the easy-to-bond 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 preferably adjusted to 50 to 62% by mass, and more preferably 53 to 61% by mass.

The easy-to-bond composition may contain solvents and additives.

The solvent is preferably one that can stably dissolve or disperse the compound represented by the general formula (1) and the organometallic compound. As the solvent, an organic solvent, water, or a mixed solvent of these can be used. As the aforementioned solvent, for example, it can be selected from the following: ethyl acetate, butyl acetate, 2-hydroxyethyl acetate and other esters; methyl ethyl ketone, acetone, cyclohexanone, methyl isobutyl ketone, two Ketones such as ethyl ketone, methyl-n-propyl ketone, and acetone; cyclic ethers such as tetrahydrofuran (THF) and dioxane; aliphatic or cycloaliphatic hydrocarbons such as n-hexane and cyclohexane; toluene , Xylene and other aromatic hydrocarbons; methanol, ethanol, n-propanol, isopropanol, cyclohexanol and other aliphatic or alicyclic alcohols; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Glycol ethers such as diethylene glycol monoethyl ether; glycol ether acetates such as diethylene glycol monomethyl ether acetate and diethylene glycol monoethyl ether acetate; etc. Among these, water should be used.

When the easy-to-bond composition contains an organic solvent, from the viewpoint of achieving both improved adhesion between the polarizer and the adhesive layer and improved coatability, when the total amount of the easy-to-bond composition is 100% by mass, the organic The content of the solvent is preferably 5 to 80% by mass, more preferably 10 to 50% by mass. In addition, when the easy-to-bond composition contains water, from the viewpoint of increasing the reactivity of the boron-containing compound with the functional group of the polarizer and improving the adhesion between the polarizing member and the adhesive layer, the easy-to-bond composition When the total amount is set to 100% by mass, the water content is preferably 5 to 90% by mass, more preferably 30 to 80% by mass, and more preferably 40 to 60% by mass.

Examples of the aforementioned additives include: binder resins, surfactants, plasticizers, tackifiers, low molecular weight polymers, polymerizable monomers, surface lubricants, leveling agents, antioxidants, preservatives, and light stabilizers. Agents, ultraviolet absorbers, polymerization inhibitors, silane coupling agents, titanium coupling agents, inorganic or organic fillers, metal powders, particles, foils, etc.

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

＜Adhesive composition＞ The form of curing the adhesive composition can be roughly classified into thermal curing and active energy ray curing. Examples of resins constituting the thermosetting adhesive composition include polyvinyl alcohol resins, epoxy resins, unsaturated polyesters, urethane resins, acrylic resins, urea resins, melamine resins, phenol resins, etc., and as required Use hardener together. As the resin constituting the thermosetting adhesive composition, polyvinyl alcohol resin and epoxy resin are more preferably used. As an active energy ray curable adhesive composition, classification based on active energy rays can be roughly classified into electron beam curability, ultraviolet curability, and visible light curability. In addition, the cured form can be divided into a radical polymerizable adhesive composition and a cation polymerizable adhesive composition. In the present invention, active energy rays having a wavelength range of 10 nm to less than 380 nm are described as ultraviolet rays, and active energy rays having a wavelength range of 380 nm to 800 nm are described as visible light.

In the production of the polarizing film of the present invention, the adhesive composition is preferably curable with active energy rays. Furthermore, it is particularly suitable for visible light curability 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 having carbon-carbon double bonds 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. Moreover, these radically polymerizable compounds can be used individually by 1 type or in combination of 2 or more types. As these radically polymerizable compounds, for example, a compound having a (meth)acryloyl group is preferable. In addition, in the present invention, the (meth)acryloyl group means an allyl group and/or methacryloyl group, and "(meth)" has the same meaning in the following.

(惟，R³ 為氫原子或甲基，R⁴ 及R⁵ 分別獨立為氫原子、烷基、羥基烷基、烷氧基烷基或環狀醚基，R⁴ 及R⁵ 亦可形成環狀雜環)。烷基、羥基烷基、及/或烷氧基烷基的烷基部分的碳數沒有特別限定，可示例出例如1~4個者。另外，R⁴ 及R⁵ 可形成的環狀雜環可舉例如N-丙烯醯基嗎啉等。Examples of the monofunctional radical polymerizable compound include compounds represented by the following general formula (2): [Chemical formula 7]

(However, R ³ is a hydrogen atom or a methyl group, R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group or a cyclic ether group. R ⁴ and R ⁵ may also form a ring Like 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, for example, 1 to 4 can be exemplified. In addition, ^{the cyclic heterocyclic ring that R 4} and R ⁵ can form includes, for example, N-propenylmorpholine and the like.

As specific examples of the compound represented by the general formula (2), for example, N-methyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl N-alkyl (meth)acrylamide, N-isopropyl(meth)acrylamide, N-butyl(meth)acrylamide, N-hexyl(meth)acrylamide, etc. (Meth)acrylamide derivatives; N-hydroxymethyl (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, N-hydroxymethyl-N-propane (meth)propylene N-hydroxyalkyl (meth)acrylamide derivatives such as amide; N-methoxymethacrylamide, N-ethoxymethacrylamide, etc. containing N-alkoxy (methyl) ) Acrylamide derivatives, etc. In addition, examples of cyclic ether group-containing (meth)acrylamide derivatives include heterocyclic (meth)acrylamide derivatives in which the nitrogen atom of the (meth)acrylamide group forms a heterocyclic ring, such as N-acryloylmorpholine, N-acryloylpiperidine, N-methacryloylpiperidine, N-acryloylpyrrolidine, etc. can be mentioned.

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

The content of the aforementioned polymerizable compound X in the adhesive composition is not particularly limited. As described above, from the viewpoint of suppressing excessive permeation of the polymerizable compound X into the transparent protective film, it is preferably 80% by mass or less, more preferably 60% by mass. % Or less. On the other hand, from the viewpoint of improving the adhesion between the adhesive layer and the transparent protective film, it is preferably 25% by mass or more, and more preferably 35% by mass or more. In addition, the content of the polymerizable compound X in the adhesive composition is preferably such that the total content of the easily bondable composition (excluding the solvent) and the polymerizable compound X in the adhesive composition becomes 40 to 64% by mass. The content of the polymerizable compound X in the easy-to-bond composition is preferably adjusted to be 50 to 62% by mass, and more preferably 53 to 61% by mass.

In addition, the adhesive composition used in the present invention may contain a monofunctional radical polymerizable compound other than the above as a curable component. As a monofunctional radical polymerizable compound, various (meth)acrylic acid derivatives which have a (meth)acryloyloxy group are mentioned, for example. Examples of the aforementioned (meth)acrylic acid derivatives include: methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate Base) 2-methyl-2-nitropropyl acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, secondary butyl (meth)acrylate, tertiary (meth)acrylate Butyl ester, n-pentyl (meth)acrylate, tertiary pentyl (meth)acrylate, 3-pentyl (meth)acrylate, 2,2-dimethylbutyl (meth)acrylate, (methyl) ) N-hexyl acrylate, cetyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 4-methyl-2-propylpentene (meth)acrylate (Meth)acrylic acid (carbon number 1-20) alkyl esters such as esters and n-octadecyl (meth)acrylate.

In addition, examples of the aforementioned (meth)acrylic acid derivatives include: cyclohexyl (meth)acrylate, cyclopentyl (meth)acrylate, and other cycloalkyl (meth)acrylates; benzyl (meth)acrylate, etc. Aralkyl (meth)acrylate; 2-isobornyl (meth)acrylate, 2-norbornyl methyl (meth)acrylate, 5-norbornen-2-yl-methyl (meth)acrylate , 3-Methyl-2-norbornyl methyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenoxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate Polycyclic (meth)acrylates such as cyclopentyl ester; 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate Ethyl methoxyethyl, 3-methoxybutyl (meth)acrylate, ethyl carbitol (meth)acrylate, phenoxyethyl (meth)acrylate, alkylphenoxy polyethylene Alkoxy or phenoxy-containing (meth)acrylates such as alcohol (meth)acrylates and the like. Among them, dicyclopentenoxyethyl acrylate and phenoxyethyl acrylate are preferable because they have excellent adhesion to various protective films.

In addition, as the aforementioned (meth)acrylic acid derivative, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, ( 2-hydroxybutyl meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-(meth)acrylate Hydroxydecyl ester, 12-hydroxylauryl (meth)acrylate and other hydroxyalkyl (meth)acrylates, or [4-(hydroxymethyl)cyclohexyl]methyl acrylate, cyclohexanedimethanol mono(methyl) ) Acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate and other hydroxyl-containing (meth)acrylates; glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate Epoxy group-containing (meth)acrylates such as glycidyl ether; 2,2,2-trifluoroethyl (meth)acrylate, 2,2,2-trifluoroethylethyl (meth)acrylate, ( Tetrafluoropropyl (meth)acrylate, hexafluoropropyl (meth)acrylate, octafluoropentyl (meth)acrylate, heptafluorodecyl (meth)acrylate, 3-chloro-2 (meth)acrylate -Halogen-containing (meth)acrylates such as hydroxypropyl ester; (meth)acrylic acid alkylaminoalkyl esters such as dimethylaminoethyl (meth)acrylate; (meth)acrylic acid 3-oxo heterocycle Butyl methyl ester, 3-methyl-oxetanyl methyl (meth)acrylate, 3-ethyl-oxetanyl methyl (meth)acrylate, (meth)acrylic acid 3 -Butyl-oxetanyl methyl ester, 3-hexyl-oxetanyl methyl (meth)acrylate and other oxetanyl (meth)acrylates; (meth)acrylic acid Heterocyclic (meth)acrylates such as tetrahydrofurfuryl ester and butyrolactone (meth)acrylate, or hydroxytrimethylacetate neopentyl glycol (meth)acrylic acid adduct, p-phenylphenol ( Meth) acrylate and the like. Among them, 2-hydroxy-3-phenoxypropyl acrylate is preferred because of its excellent adhesion to various protective films.

In addition, examples of monofunctional radical polymerizable compounds include (meth)acrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid, etc. Carboxyl-containing monomers.

In addition, examples of monofunctional radically polymerizable compounds include internal vinyl amines such as N-vinylpyrrolidone, N-vinyl-ε-caprolactone, and methylvinylpyrrolidone. Monomers; vinyl pyridine, vinyl piperidone, vinyl pyrimidine, vinyl piperidine, vinyl pyridine, vinyl pyrrole, vinyl imidazole, vinyl azole, vinyl morpholine, etc. Have nitrogen-containing heterocycles The vinyl monomers and so on.

The adhesive composition used in the present invention contains hydroxyl-containing (meth)acrylates, carboxyl-containing (meth)acrylates, and phosphoric acid-containing (meth) groups that have high polarity among monofunctional radical polymerizable compounds. In the case of acrylate etc., the adhesion to various substrates will be improved. The content of the hydroxyl group-containing (meth)acrylate relative to the adhesive composition is preferably 1% by mass to 30% by mass. When 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 be deteriorated. The content of the carboxyl group-containing (meth)acrylate relative to the adhesive composition is preferably 1% by mass to 20% by mass. When the content of the carboxyl group-containing (meth)acrylate is too large, the optical durability of the polarizing film decreases, which is not suitable. The phosphoric acid group-containing (meth)acrylate includes 2-(meth)acryloyloxyethyl acid phosphate, and its content is preferably 0.1% by mass to 10% by mass relative to the adhesive composition . When the content of the phosphoric acid group-containing (meth)acrylate is too large, the optical durability of the polarizing film decreases, which is not suitable.

In addition, as the monofunctional radical polymerizable compound, a radical polymerizable compound having an active methylene group can be used. The radically polymerizable compound having an active methylene group is a compound having an active double bond group such as a (meth)acrylic group in the terminal or in the molecule, and an active methylene group. As the active methylene group, for example, acetylacetoxy, alkoxypropanedioxin, cyanoacetoxy, and the like can be mentioned. The aforementioned active methylene group is preferably acetylacetonyl. Examples of radical polymerizable compounds having active methylene groups include: 2-acetylacetoxyethyl (meth)acrylate, 2-acetylacetoxypropyl (meth)acrylate, ( Acetyl acetoxy alkyl (meth)acrylate such as 2-ethoxy acetoxy-1-methyl ethyl acrylate; 2-ethoxy propane diacetoxy (meth) acrylate Ethyl, 2-cyanoacetoxyethyl (meth)acrylate, N-(2-cyanoacetoxyethyl)acrylamide, N-(2-propionylacetoxybutyl) Yl)acrylamide, N-(4-acetylacetoxymethylbenzyl)acrylamide, N-(2-acetylacetaminoethyl)acrylamide, and the like. The radically polymerizable compound having an active methylene group is preferably acetoxyalkyl (meth)acrylate.

In addition, examples of polyfunctional radical polymerizable compounds having two or more functions include N,N'-methylenebis(meth)acrylamide, trifunctional (meth)acrylamide derivatives, and trifunctional (meth)acrylamide derivatives. Propylene glycol di(meth)acrylate, tetraethylene glycol di(meth)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 addition Di(meth)acrylate, bisphenol A propylene oxide adduct di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol di(meth) Acrylate, tricyclodecane dimethanol di(meth)acrylate, cyclic trimethylolpropane methylal (meth)acrylate, dioxanediol di(meth)acrylate, trimethylol Propane tri (meth) acrylate, neopentyl erythritol tri (meth) acrylate, neopentyl erythritol tetra (meth) acrylate, dineopentyl pentaerythritol penta (meth) acrylate, dineopentyl Tetraol hexa(meth)acrylate, EO modified diglycerol tetra(meth)acrylate and other (meth)acrylic acid and polyol esterification products, 9,9-bis[4-(2-(methyl) Allyloxyethoxy)phenyl]茀. As specific examples, 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 Co., Ltd.), CD-536 (manufactured by Sartomer Co., Ltd.), etc. In addition, if necessary, various epoxy (meth)acrylates, urethane (meth)acrylates, polyester (meth)acrylates, various (meth)acrylate monomers, etc. can be cited . In addition, the polyfunctional (meth)acrylamide derivative is not only fast in polymerization rate and excellent in productivity, but also has excellent crosslinkability when the adhesive composition is made into a cured product, so it is preferably included in the adhesive composition.

From the viewpoint of compatibility with polarizers or various transparent protective films and optical durability in severe environments, the radical polymerizable compound is preferably used in combination with a monofunctional radical polymerizable compound and a polyfunctional radical polymerizable compound. In addition, the monofunctional radically polymerizable compound has a low liquid viscosity, so by containing it in the adhesive composition, the liquid viscosity of the adhesive composition can be reduced. In addition, monofunctional radical polymerizable compounds often have functional groups that can exhibit various functions. By including them in the adhesive composition, they can be used in the adhesive composition and/or the cured product of the adhesive composition. Exhibit various functions. Since the polyfunctional radical polymerizable compound can three-dimensionally crosslink the cured product of the adhesive composition, it is preferably contained in the adhesive composition. It is preferable to use 10 to 1000 parts by mass of the polyfunctional radical polymerizable compound with respect to 100 parts by mass of the monofunctional radical polymerizable compound.

When an electron beam or the like is used for the active energy rays, the radically polymerizable adhesive composition does not need to contain a photopolymerization initiator, but when the active energy rays use ultraviolet or visible light, it is preferable to contain a photopolymerization initiator.

、2-氯9-氧硫𠮿

、2-甲基9-氧硫𠮿

、2,4-二甲基9-氧硫𠮿

、異丙基9-氧硫𠮿

、2,4-二氯9-氧硫𠮿

、2,4-二乙基9-氧硫𠮿

、2,4-二異丙基9-氧硫𠮿

、十二烷基9-氧硫𠮿

等9-氧硫𠮿

系化合物；樟腦醌；鹵化酮；醯基氧化膦；醯基膦酸酯等。The photopolymerization initiator in the case of using a radically polymerizable compound can be appropriately selected according to active energy rays. In the case of curing by ultraviolet or visible light, a photopolymerization initiator that is cleaved by ultraviolet or visible light is used. As the aforementioned photopolymerization initiator, for example, benzil, diphenyl ketone, benzyl benzoic acid, 3,3′-dimethyl-4-methoxydiphenyl Ketones and other diphenyl ketone compounds; 4-(2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, α-hydroxy-α,α'-dimethylacetophenone, 2 -Methyl-2-hydroxypropiophenone, α-hydroxycyclohexyl phenyl ketone and other aromatic ketone compounds; methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2, Acetophenone compounds such as 2-diethoxyacetophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1; benzoin methyl ether, Benzoin ether compounds such as benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, and anisin methyl ether; aromatic ketals such as benzyl dimethyl ketal Compounds; Aromatic sulfonyl chloride compounds such as 2-naphthalenesulfonyl chloride; Photoactive oxime compounds such as 1-phenone-1,1-propanedione-2-(o-ethoxycarbonyl)oxime; 9-oxygen Sulfur

, 2-chloro-9-oxysulfur 𠮿

, 2-Methyl 9-oxysulfur 𠮿

, 2,4-Dimethyl 9-oxysulfur 𠮿

, Isopropyl 9-oxysulfur 𠮿

, 2,4-Dichloro 9-oxysulfur 𠮿

, 2,4-Diethyl 9-oxysulfur 𠮿

, 2,4-Diisopropyl 9-oxysulfur 𠮿

, Dodecyl 9-oxysulfur 𠮿

Waiting for 9-oxysulfur 𠮿

Series compounds; camphorquinone; halogenated ketones; acyl phosphine oxide; acyl phosphonate and the like.

The blending amount of the aforementioned photopolymerization initiator in the adhesive composition is preferably 20% by mass or less, more preferably 0.01-20% by mass, more preferably 0.05-10% by mass, and particularly preferably 0.1-5% by mass. In addition, the content of the photopolymerization initiator in the adhesive composition is preferably such that the total content of the easily-adhesive composition (excluding the solvent) and the photopolymerization initiator in the adhesive composition is 2.6 to 7% by mass. The content of the photopolymerization initiator in the easy-to-bond composition is preferably adjusted to be 2.65-6 mass%, and more preferably 2.7-5 mass%.

In addition, when the adhesive composition used in the present invention is used for visible light curability containing a radically polymerizable compound as a curable component, it is particularly suitable to use a photopolymerization initiator that is highly sensitive to light of 380 nm or more. The photopolymerization initiator that is highly sensitive to light of 380 nm or more will be described later.

(式中，R⁶ 及R⁷ 表示-H、-CH₂ CH₃ 、-iPr或Cl，R⁶ 及R⁷ 可以相同或不同)。與單獨使用對380nm以上的光為高靈敏度的光聚合引發劑的情況相比，使用了通式(3)所示化合物的情況下接著性優異。通式(3)所示化合物中，特別宜為R⁶ 及R⁷ 為-CH₂ CH₃ 的二乙基9-氧硫𠮿

。相對於接著劑組成物的總量，接著劑組成物中的通式(3)所示化合物的組成比率宜為0.1~5質量%，較宜為0.5~4質量%，更宜為0.9~3質量%。As the aforementioned photopolymerization initiator, it is preferable to use the compound represented by the following general formula (3) alone or in combination with the compound represented by the general formula (3) and a photopolymerization initiator that is highly sensitive to light of 380 nm or more described later: [Chemical formula 8 ]

(In the formula, R ⁶ and R ⁷ represent -H, -CH ₂ CH ₃ , -iPr or Cl, and R ⁶ and R ⁷ may be the same or different). Compared with the case of using a photopolymerization initiator that is highly sensitive to light of 380 nm or more, the use of the compound represented by the general formula (3) is superior in adhesiveness. Among the compounds represented by the general formula (3), it is particularly ^{preferred that R 6} and R ⁷ are -CH ₂ CH ₃ diethyl 9-oxysulfur 𠮿

. Relative to the total amount of the adhesive composition, the composition ratio of the compound represented by the general formula (3) in the adhesive composition is preferably 0.1-5 mass%, more preferably 0.5-4 mass%, and more preferably 0.9-3 quality%.

In addition, it is advisable to add a polymerization initiation assistant as necessary. Examples of the polymerization initiation aids include triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, 4 -Ethyl dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, etc., ethyl 4-dimethylaminobenzoate is particularly suitable. When a polymerization initiation aid is used, its addition amount is usually 0 to 5% by mass relative to the total amount of the curable resin composition, preferably 0 to 4% by mass, and most preferably 0 to 3% by mass.

In addition, if necessary, a known photopolymerization initiator can be used in combination. Since the transparent protective film having UV absorption energy does not transmit light of 380 nm or less, it is preferable to use a photopolymerization initiator that is highly sensitive to light of 380 nm or more as the photopolymerization initiator. Specifically, examples include: 2-methyl-1-(4-methylthiophenyl)-2-morpholin-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinephenyl)-butan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholine) (Yl)phenyl)-1-butanone, 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzyl)phenylphosphine oxide , Bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium and the like.

(式中，R⁸ 、R⁹ 及R¹⁰ 表示-H、-CH₃ 、-CH₂ CH₃ 、-iPr或Cl，R⁸ 、R⁹ 及R¹⁰ 可以相同或不同)。作為通式(4)所示化合物，可以適宜使用作為市售品的2-甲基-1-(4-甲硫基苯基)-2-嗎啉丙-1-酮(商品名：IRGACURE907 製造商：BASF)。此外，2-苄基-2-二甲基胺基-1-(4-嗎啉苯基)-丁-1-酮(商品名：IRGACURE369 製造商：BASF)、2-(二甲基胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-嗎啉基)苯基]-1-丁酮(商品名：IRGACURE379 製造商：BASF)由於靈敏度高，因此佳。In particular, as the photopolymerization initiator, in addition to the photopolymerization initiator of the general formula (3), it is preferable to further use a compound represented by the following general formula (4): [Chemical formula 9]

(In the formula, R ⁸ , R ⁹ and R ¹⁰ represent -H, -CH ₃ , -CH ₂ CH ₃ , -iPr or Cl, and R ⁸ , R ⁹ and R ¹⁰ may be the same or different). As the compound represented by the general formula (4), commercially available 2-methyl-1-(4-methylthiophenyl)-2-morpholin-1-one (trade name: manufactured by IRGACURE907) can be suitably used. Quotient: BASF). In addition, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one (trade name: IRGACURE369 manufacturer: BASF), 2-(dimethylamino )-2-[(4-Methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: IRGACURE379 Manufacturer: BASF) due to high sensitivity , So good.

In the above-mentioned adhesive composition, when a radical polymerizable compound having a living methylene group is used as the radical polymerizable compound, it is preferably used in combination with a radical polymerization initiator having a hydrogen abstraction action. According to this configuration, the adhesiveness of the adhesive layer of the polarizing film can be remarkably improved even immediately after being taken out from a high-humidity environment or water (in a non-dried state). The reason is not clear, but it is believed to be the following reason. That is, the radical polymerizable compound having a living methylene group is polymerized together with other radical polymerizable compounds constituting the adhesive layer, and is incorporated into the main chain and/or side chain of the base polymer in the adhesive layer , And the formation of an adhesive layer. In the polymerization process, if a radical polymerization initiator with hydrogen abstraction is present, it will form the base polymer constituting the adhesive layer, and will abstract hydrogen from the radical polymerizable compound with active methylene groups, and then Free radicals are generated in the methyl group. In addition, the methylene group that generates radicals reacts with the hydroxyl group of the polarizer such as PVA to form a covalent bond between the adhesive layer and the polarizer. As a result, it is estimated that the adhesiveness of the adhesive layer of the polarizing film can be significantly improved even in a non-dried state.

系自由基聚合引發劑、二苯基酮系自由基聚合引發劑等。前述自由基聚合引發劑宜為9-氧硫𠮿

系自由基聚合引發劑。作為9-氧硫𠮿

系自由基聚合引發劑，可列舉例如前述通式(3)所示化合物。作為通式(3)所示化合物的具體例，可列舉例如：9-氧硫𠮿

、二甲基9-氧硫𠮿

、二乙基9-氧硫𠮿

、異丙基9-氧硫𠮿

、氯9-氧硫𠮿

等。通式(3)所示化合物中，特別宜為R⁶ 及R⁷ 為-CH₂ CH₃ 的二乙基9-氧硫𠮿

。In the present invention, as a radical polymerization initiator having a hydrogen abstraction effect, for example: 9-oxysulfur 𠮿

-Based radical polymerization initiators, benzophenone-based radical polymerization initiators, etc. The aforementioned free radical polymerization initiator is preferably 9-oxysulfur 𠮿

It is a radical polymerization initiator. As 9-oxysulfur 𠮿

The radical polymerization initiator includes, for example, the compound represented by the aforementioned general formula (3). As a specific example of the compound represented by the general formula (3), for example: 9-oxysulfur 𠮿

, Dimethyl 9-oxysulfur 𠮿

, Diethyl 9-oxysulfur 𠮿

, Isopropyl 9-oxysulfur 𠮿

, Chlorine 9-oxysulfur 𠮿

Wait. Among the compounds represented by the general formula (3), it is particularly ^{preferred that R 6} and R ⁷ are -CH ₂ CH ₃ diethyl 9-oxysulfur 𠮿

.

When the above-mentioned adhesive composition contains a radical polymerizable compound having a reactive methylene group and a radical polymerization initiator having a hydrogen abstraction effect, when the total amount of the curable component is 100% by mass, relative to The total amount of the adhesive composition preferably contains 1 to 50% by mass of the radical polymerizable compound having an active methylene group and 0.1 to 10% by mass of the radical polymerization initiator.

As described above, in the present invention, in the presence of a radical polymerization initiator having a hydrogen abstraction effect, the methylene group of the radical polymerizable compound having a reactive methylene group is caused to generate free radicals, and the methylene group interacts with PVA. The hydroxyl groups of the polarizer will react to form a covalent bond. Therefore, in order to generate free radicals from the methylene group of the radically polymerizable compound having an active methylene group and sufficiently form the covalent bond, when the total amount of the curable component is 100% by weight, it is preferable to contain an active methylene group. The radical polymerizable compound contains 1-50% by mass, preferably 3-30% by mass. In order to sufficiently improve the water resistance and improve the adhesiveness in a non-dry state, the radical polymerizable compound having an active methylene group is preferably 1% by mass or more. On the other hand, if it exceeds 50% by mass, poor curing of the adhesive layer may occur. In addition, with respect to the total amount of the adhesive composition, a radical polymerization initiator having a hydrogen abstraction effect is preferably contained in 0.1-10% by mass, and more preferably 0.3-9% by mass. In order to allow the hydrogen abstraction reaction to proceed sufficiently, it is preferable to use a radical polymerization initiator of 0.1% by mass or more. On the other hand, if it exceeds 10% by mass, it may not completely dissolve in the composition.

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

In the present invention, the compound described in the aforementioned general formula (1) may be blended into the adhesive composition, the compound described in the foregoing general formula (1') is preferably blended, and the foregoing general formula (1a) is more preferably blended ~(1d) The compound described in. In addition, in the present invention, the aforementioned organometallic compound may be blended in the adhesive composition. When these compounds are blended in the adhesive composition, the adhesiveness with the polarizer or the transparent protective film may be improved, which is preferable. From the viewpoint of improving the adhesiveness and water resistance when the polarizer and the transparent protective film are bonded via the adhesive layer, the content of the compound described in the aforementioned general formula (1) in the adhesive composition is preferably 0.001~ 50% by mass, preferably 0.1-30% by mass, more preferably 1-10% by mass. In addition, in the adhesive composition, the content of the aforementioned organometallic compound is preferably 0.1 to 10% by mass, more preferably 0.5 to 7% by mass, and more preferably 1 to 5% by mass.

The bubble inhibitor is a compound that can reduce the surface tension by being blended into the adhesive composition, and thus has the effect of reducing bubbles between the transparent protective film attached to the drug. As the bubble inhibitor, for example, polysiloxane-based bubble inhibitors having a polysiloxane skeleton such as polydimethylsiloxane, and (meth)acrylic acid esters formed by polymerization of (meth)acrylate can be used. (Meth)acrylic-based air bubble suppressor with acetone skeleton, polyether-based bubble suppressor made by polymerizing vinyl ether, cyclic ether, etc., fluorine-based bubble suppressor made of fluorine-based compound having perfluoroalkyl group When added to an adhesive composition, it has an effect of reducing the surface tension of a bubble suppressant.

The bubble inhibitor preferably has a reactive group in the compound. In this case, when the polarizer and the transparent protective film are bonded together, the generation of lamination bubbles can be reduced. Examples of the reactive groups possessed by the bubble suppressor include polymerizable functional groups. Specifically, examples include radical polymerizable groups having ethylenic double bonds such as (meth)acrylic groups, vinyl groups, and allyl groups. Functional groups, epoxy groups such as glycidyl groups, cationically polymerizable functional groups such as oxetanyl groups, vinyl ether groups, cyclic ether groups, cyclic thioether groups, and lactone groups. 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)acryloyl group is more preferable.

In consideration of the lamination bubble suppressing effect and the adhesive improving effect, among the aforementioned bubble suppressors, a silicone-based bubble suppressor is preferable. In addition, when considering the adhesiveness of the adhesive layer, the bubble suppressor is preferably a bubble suppressor containing a urethane bond or a trimeric isocyanate ring structure in the main chain skeleton or side chain. As the polysiloxane-based bubble inhibitor, commercially available products can also be suitably used, and for example, "BYK-UV3505" (manufactured by BYK-Chemie Japan) which is an acryl-based modified polydimethylsiloxane is mentioned.

In order to have both the adhesive force of the obtained adhesive layer and the reduction effect of lamination bubbles, when the total amount of the adhesive composition is 100% by mass, the content of the bubble inhibitor is preferably 0.01 to 0.6% by mass.

In the adhesive composition used in the present invention, in addition to the curable component of the aforementioned radical polymerizable compound, an acrylic oligomer obtained by polymerizing a (meth)acrylic monomer may be contained. By including the acrylic oligomer in the adhesive composition, the curing shrinkage when the composition is irradiated with active energy rays and hardened can be reduced, and the adhesive, polarizer, transparent protective film and other adhered materials can be reduced The interface stress. As a result, the adhesion between the adhesive layer and the adherend can be suppressed from decreasing. 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, and more preferably 15% by mass or less relative to the total amount of the adhesive composition. When 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 cause poor curing. On the other hand, with respect to the total amount of the adhesive composition, the acrylic oligomer is preferably contained at 3% by mass or more, and more preferably at 5% by mass or more.

In consideration of workability or uniformity during coating, the adhesive composition should preferably have a low viscosity. Therefore, the acrylic oligomer formed by polymerizing (meth)acrylic monomers should also have a low viscosity. As the low-viscosity acrylic oligomer that can prevent the curing shrinkage of the adhesive layer, one having a weight average molecular weight (Mw) of 15,000 or less is preferable, one having a weight average molecular weight (Mw) of 10,000 or less is more preferable, and an acrylic oligomer is particularly preferably 5,000 or less. 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 particularly preferably 1500 or more. Specific examples of the (meth)acrylic monomer constituting the acrylic oligomer include: methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, (meth) ) Isopropyl acrylate, 2-methyl-2-nitropropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, secondary secondary (meth)acrylate , Tertiary butyl (meth)acrylate, n-pentyl (meth)acrylate, tertiary pentyl (meth)acrylate, 3-pentyl (meth)acrylate, 2,2-di (meth)acrylate Methyl butyl ester, n-hexyl (meth)acrylate, cetyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 4-(meth)acrylate (Meth)acrylic acid (carbon number 1-20) alkyl esters such as methyl-2-propylpentyl ester and n-octadecyl (meth)acrylate; and for example: (meth)acrylic acid cycloalkyl Ester (e.g. cyclohexyl (meth)acrylate, cyclopentyl (meth)acrylate, etc.), aralkyl (meth)acrylate (e.g. benzyl (meth)acrylate, etc.), polycyclic (formyl) Base) acrylate (e.g. 2-isobornyl (meth)acrylate, 2-norbornyl methyl (meth)acrylate, 5-norbornen-2-yl-methyl (meth)acrylate, ( (Meth) 3-methyl-2-norbornyl methyl acrylate, etc.), hydroxyl-containing (meth)acrylates (e.g. hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate) , (Meth)acrylate 2,3-dihydroxypropyl methyl butyl ester, etc.), alkoxy or phenoxy (meth)acrylates ((meth)acrylate-2-methoxyethyl) , 2-ethoxyethyl (meth)acrylate, 2-methoxymethoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, (meth) Ethyl carbitol acrylate, phenoxyethyl (meth)acrylate, etc.), epoxy-containing (meth)acrylates (such as glycidyl (meth)acrylate, etc.), halogen-containing (methyl) ) Acrylic esters (e.g. 2,2,2-trifluoroethyl (meth)acrylate, 2,2,2-trifluoroethyl ethyl (meth)acrylate, tetrafluoropropyl (meth)acrylate, Hexafluoropropyl (meth)acrylate, octafluoropentyl (meth)acrylate, heptafluorodecyl (meth)acrylate, etc.), alkylaminoalkyl (meth)acrylate (for example, (meth)acrylate Group) dimethylaminoethyl acrylate, etc.) and the like. These (meth)acrylates can be used individually or in combination of 2 or more types. Specific examples of acrylic oligomers include "ARUFON" manufactured by Toagosei Co., Ltd., "ACTFLOW" manufactured by Soken Chemical Co., Ltd., and "JONCRYL" manufactured by BASF Japan Ltd., etc.

(惟，L⁺ 表示任意的鎓陽離子；另外，X^- 表示選自於由PF₆ ^- 、SbF₆ ^- 、AsF₆ ^- 、SbCl₆ ^- 、BiCl₅ ^- 、SnCl₆ ^- 、ClO₄ ^- 、二硫胺基甲酸鹽陰離子、SCN^- 所構成群組中的相對陰離子)。The aforementioned adhesive composition may contain a photoacid generator. Compared with the case where the photoacid generator is not contained, when the above-mentioned adhesive composition contains the photoacid generator, the water resistance and durability of the adhesive layer can be greatly improved. The photoacid generator can be represented by the following general formula (5). General formula (5) [Chemical formula 10]

(However, L ⁺ represents an arbitrary cation; In addition, X ^- represents a group selected consisting of _{^{PF 6 -, SbF 6 -,}} AsF 6 -, SbCl 6 -, BiCl 5 -, SnCl 6 -, ClO 4 -, disulfide Carbamate anion, SCN ^- the relative anion in the group).

^{Next, the relative anion X-} in the general formula (5) will be described.

^{In principle, the relative anion X-} in the general formula (5) is not particularly limited, but it is preferably a non-nucleophilic anion. When the relative anion X is a non-nucleophilic anion, the nucleophilic reaction of the coexisting cations in the molecule or the various materials used in combination is not easily caused, so as a result, the photoacid generator represented by the general formula (5) can be improved by itself or by using it. The diachronic stability of the composition. The non-nucleophilic anion mentioned here refers to an anion with 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 -, an amine disulfide formate anion, SCN ^- and the like.

Specifically, "CYRACURE UVI-6992", "CYRACURE UVI-6974" (above, manufactured by Dow Chemical Japan Limited), "Adekaoptomer SP150", "Adekaoptomer SP152", "Adekaoptomer SP170", "Adekaoptomer SP172" (above, a joint-stock company ADEKA), "IRGACURE250" (manufactured by Ciba Specialty Chemicals Inc.), "CI-5102", "CI-2855" (above, manufactured by Nippon Soda Co., Ltd.), "San-Aid SI-60L", "San -Aid SI-80L", "San-Aid SI-100L", "San-Aid SI-110L", "San-Aid SI-180L" (above, manufactured by Sanshin Chemical Co., Ltd.), "CPI-100P", " "CPI-100A" (above, manufactured by San-Apro Ltd.), "WPI-069", "WPI-113", "WPI-116", "WPI-041", "WPI-044", "WPI-054" , "WPI-055", "WPAG-281", "WPAG-567", and "WPAG-596" (above, manufactured by Wako Pure Chemical Industries, Ltd.) can be cited as preferred specific examples of the photoacid generator of the present invention .

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

A photobase generator is a base that changes the molecular structure by irradiation of ultraviolet light, visible light, etc., or generates one or more kinds of bases that can act as a catalyst for the polymerization reaction of radical polymerizable compounds or epoxy resins by cleavage of molecules. Sexual compounds. Examples of basic substances include secondary amines and tertiary amines. As the photobase generator, for example, the above-mentioned α-aminoacetophenone compound, the above-mentioned oxime ester compound, or having an oxyimino group, N-methylated aromatic amine group, and N-acylated aromatic Compounds with substituents such as amine groups, nitrobenzyl carbamate groups, and alkoxybenzyl carbamate groups. Among them, oxime ester compounds are preferred.

As the compound having an oxyimino group, for example, O,O'-succinic acid benzophenone oxime, O,O'-succinic acid benzophenone acetophenone oxime, benzophenone oxime acrylate- Styrene copolymer.

Examples of compounds having N-formylated aromatic amine groups and N-formylated aromatic amine groups include di-N-(p-formylamino) diphenylmethane and di-N-( P-Acetylamino)diphenylmethane, bis-N-(p-benzylamino)diphenylmethane, 4-formamide stilbene, 4-acetamido stilbene, 2 , 4-Dimethyamino stilbene, 1-methyaminonaphthalene, 1-acetylaminonaphthalene, 1,5-dimethylaminonaphthalene, 1-methyaminonaphthalene, 1-methyaminonaphthalene Anthracene, 1,4-dimethylaminoanthracene, 1-acetylaminoanthracene, 1,4-dimethylaminoanthracene, 1,5-dimethylaminoanthraquinone, 3 ,3'-dimethyl-4,4'-dimethylamino biphenyl, 4,4'-dimethylamino diphenyl ketone.

Examples of compounds having a nitrobenzylcarbamate group and an alkoxybenzylcarbamate group include bis{{(2-nitrobenzyl)oxy}carbonyl}diaminodiphenyl Methyl methane, 2,4-bis{(2-nitrobenzyl)oxy}stilbene, bis{(2-nitrobenzyloxy)carbonyl}hexane-1,6-diamine, stubble Amine {{(2-nitro-4-chlorobenzyl)oxy}amide}.

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

As other photobase generators, WPBG-018 (trade name, 9-anthrylmethyl N,N'-diethylcarbamate (9-anthrylmethyl N,N'-diethylcarbamate)), WPBG- 027 (trade name, (E)-1-[3-(2-hydroxyphenyl)-2-propenoyl]piperidine ((E)-1-[3-(2-hydroxyphenyl)-2-propenoyl] piperidine)), WPBG-082 (trade name, guanidinium2-(3-benzoylphenyl)propionate), WPBG-140 (trade name, 1-(anthracene) Photobase generators such as quinone-2-yl) ethyl imidazole carboxylate (1-(anthraquinon-2-yl) ethyl imidazole carboxylate).

In the above-mentioned adhesive composition, a photoacid generator and a compound containing either an alkoxy group and an epoxy group may be used together in the adhesive composition.

In the case of using a compound having one or more epoxy groups in the molecule or a polymer (epoxy resin) having two or more epoxy groups in the molecule, it can be used in combination with two or more epoxy groups in the molecule that are reactive with epoxy groups The functional group of the compound. Among them, the functional group reactive with the epoxy group includes, for example, a carboxyl group, a phenolic hydroxyl group, a mercapto group, a primary or secondary aromatic amine group, and the like. Considering the three-dimensional hardenability, it is particularly preferable to have two or more of these functional groups in one molecule.

Examples of polymers having one or more epoxy groups in the molecule include epoxy resins, including bisphenol A type epoxy resins derived from bisphenol A and epichlorohydrin, and bisphenol F and epichlorohydrin. Derived bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol A novolac epoxy resin, bisphenol F novolac epoxy resin , Alicyclic epoxy resin, diphenyl ether type epoxy resin, hydroquinone type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, sulphur type epoxy resin, trifunctional epoxy resin, Polyfunctional epoxy resins such as 4-functional epoxy resins, glycidyl ester epoxy resins, glycidylamine epoxy resins, hydantoin epoxy resins, isocyanurate epoxy resins, Aliphatic chain epoxy resins, etc., these epoxy resins may be halogenated or hydrogenated. Examples of commercially available epoxy resin products include: JER code 828, 1001, 801N, 806, 807, 152, 604, 630, 871, YX8000, YX8034, YX4000, and EPICLON830 manufactured by DIC Co., Ltd. manufactured by Japan Epoxy Resin , EXA835LV, HP4032D, HP820, EP4100 series, EP4000 series, EPU series manufactured by ADEKA Co., Ltd., CELLOXIDE series manufactured by Daicel Chemical Industries, Ltd. (2021, 2021P, 2083, 2085, 3000, etc.), Epolead series, EHPE series, YD series, YDF series, YDCN series, YDB series, and phenoxy resins manufactured by Nippon Steel Chemical Company (which are polyhydroxy polyethers synthesized from bisphenols and epichlorohydrin and have epoxy groups at both ends; YP Series, etc.), Denacol series manufactured by Nagase ChemteX Corporation, Epolight series manufactured by Kyoeisha Chemical Co., Ltd., but not limited to these. These epoxy resins can be used in combination of two or more types.

The compound having an alkoxy group in the molecule is not particularly limited as long as it has one or more alkoxy group in the molecule, and a known compound can be used. As such a compound, a melamine compound, an amino resin, a silane coupling agent, etc. can be cited as a representative.

The blending amount of the compound containing either an alkoxy group or an epoxy group is usually 30% by mass or less with respect to the total amount of the adhesive composition. If the content of the compound in the composition is too large, the adhesiveness will be deteriorated. Decrease, and the impact resistance to the drop weight 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 compound should preferably be contained in the composition at 2% by mass or more, more preferably 5% by mass or more.

When the adhesive composition used in the present invention is active energy ray curable, the silane coupling agent is preferably an active energy ray curable compound, but even if it is not active energy ray curable, the same water resistance can be imparted.

Specific examples of the silane coupling agent include vinyl trichlorosilane, vinyl trimethoxysilane, vinyl triethoxysilane, and 2-(3,4 epoxycyclohexyl) which are active energy ray-curable compounds. ) Ethyl trimethoxy silane, 3-glycidoxy propyl trimethoxy silane, 3-glycidoxy propyl methyl diethoxy silane, 3-glycidoxy propyl triethyl Oxysilane, p-styrene trimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methylpropene Acrylic oxypropyl methyl diethoxy silane, 3-methacrylic oxy propyl triethoxy silane, 3-propenoxy propyl trimethoxy silane, etc.

Preferably, they are 3-methacryloxypropyl trimethoxysilane and 3-acryloxypropyl trimethoxysilane.

As a specific example of the inactive energy ray-curable silane coupling agent, a silane coupling agent having an amine group is preferable. Specific examples of the silane coupling agent having an amino group include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-Aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, γ-( 2-aminoethyl)aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)aminopropyl triethoxysilane, γ-(2-aminoethyl)amine Propylmethyl diethoxysilane, γ-(2-aminoethyl)aminopropyl triisopropoxysilane, γ-(2-(2-aminoethyl)aminoethyl) Aminopropyltrimethoxysilane, γ-(6-aminohexyl)aminopropyltrimethoxysilane, 3-(N-ethylamino)-2-methylpropyltrimethoxysilane, γ -Ureaylpropyl trimethoxysilane, γ-ureidopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethyl Oxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, N-cyclohexylaminomethyl triethoxysilane, N-cyclohexylaminomethyl diethoxymethyl Silane, N-phenylaminomethyltrimethoxysilane, (2-aminoethyl)aminomethyltrimethoxysilane, N,N'-bis[3-(trimethoxysilyl)propane Amino-containing silanes such as ethylenediamine; ketimine silanes such as N-(1,3-dimethylbutylene)-3-(triethoxysilyl)-1-propylamine.

The silane coupling agent which has an amine group may use only 1 type, and may use it in combination of multiple types. Among these, in order to ensure good adhesiveness, γ-aminopropyltrimethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, γ-(2-aminoethyl) Yl)aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)aminopropyl triethoxysilane, γ-(2-aminoethyl)aminopropylmethyl Diethoxysilane, N-(1,3-dimethylbutylene)-3-(triethoxysilyl)-1-propylamine.

Relative to the total amount of the adhesive composition, the blending amount of the silane coupling agent is preferably in the range of 0.01 to 20% by mass, more preferably 0.05 to 15% by mass, and more preferably 0.1 to 10% by mass. This is because when the blending amount is more than 20% by mass, the storage stability of the adhesive composition is deteriorated, and when it is less than 0.1% by mass, it is difficult to fully exhibit the effect of water-resistant adhesiveness.

As specific examples of non-active energy ray-curable silane coupling agents other than the above, 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyl Dimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis(triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane, imidazole silane, etc.

When the adhesive composition used in the present invention contains a compound having a vinyl ether group, the water resistance of the polarizer and the adhesive layer is improved, which is preferable. The reason for obtaining this effect is not clear, but one of the reasons is presumed to be that the vinyl ether group of the compound interacts with the polarizer to increase the adhesive force between the polarizer and the adhesive layer. In order to further improve the water resistance of the polarizer and the adhesive layer, the compound is preferably a radically polymerizable compound having a vinyl ether group. In addition, the content of the compound is preferably 0.1 to 19% by mass relative to the total amount of the adhesive composition.

The adhesive composition used in the present invention may contain a compound that produces keto-enol tautomerism. For example, in an adhesive composition containing a cross-linking agent or an adhesive composition that can be blended with a cross-linking agent, the aspect including the above-mentioned compound that produces keto-enol tautomerism can be suitably adopted. Thereby, the excessive viscosity increase or gelation of the adhesive composition after blending the organometallic compound, and the formation of microgels can be suppressed, and the effect of prolonging the pot life of the composition can be achieved.

As the above-mentioned compound that produces keto-enol tautomerism, various β-dicarbonyl compounds can be used. Specific examples include: acetone, 2,4-hexanedione, 3,5-heptanedione, 2-methylhexan-3,5-dione, 6-methylheptane-2,4- Β-diketones such as diketone, 2,6-dimethylheptan-3,5-dione; methyl acetylacetate, ethyl acetylacetate, isopropyl acetylacetate, tertiary butyl acetylacetate Acetyl acetate esters such as esters; Acetyl acetate esters such as methyl propylacetate, ethyl propylacetate, isopropyl propylacetate, tertiary butyl propylacetate, etc.; methyl isobutylacetate Esters, ethyl isobutyryl acetate, isobutyl isobutyryl acetate, tertiary butyl isobutyryl acetate and other isobutyryl acetates; malonic acid esters such as methyl malonate and ethyl malonate, etc. Among them, examples of suitable compounds include acetone and acetyl acetate. The keto-enol tautomerism-producing compound may be used alone or in combination of two or more kinds.

The amount of the compound that produces keto-enol tautomerism can be set to 0.05 parts by mass to 10 parts by mass relative to 1 part by mass of the organometallic compound, preferably 0.2 parts by mass to 3 parts by mass (for example, 0.3 parts by mass~ 2 parts by mass). If the usage amount of the above-mentioned compound is less than 0.05 parts by mass with respect to 1 part by mass of the organometallic compound, it may be difficult to exhibit sufficient usage effects. On the other hand, if the amount of the compound used is more than 10 parts by weight relative to 1 part by weight of the organometallic compound, it may interact excessively with the organometallic compound and it may become difficult to express the target water resistance.

Polyrotaxane may be contained in the adhesive composition of the present invention. The polyrotaxane has a cyclic molecule, a linear molecule penetrating the opening of the cyclic molecule, and an end block arranged at both ends of the linear molecule so that the cyclic molecule is not separated from the linear molecule base. The cyclic molecule preferably has a functional group hardenable by active energy rays.

The cyclic molecule is not particularly limited as long as it has a linear molecule in its opening that is enclosed in a thorn-like shape, can move on the linear molecule, and has an active energy ray polymerizable group. In addition, in this specification, the "cyclic" of the "cyclic molecule" means that it is substantially a "cyclic". That is, as long as it can move on a linear molecule, the cyclic molecule may not completely close the ring.

Specific examples of cyclic molecules include cyclic polymers such as cyclic polyethers, cyclic polyesters, cyclic polyetheramines, and cyclic polyamines, and α-cyclodextrin, β-cyclodextrin, Cyclodextrins such as γ-cyclodextrin. Among them, in view of the relatively easy availability and the ability to select most types of end-capping groups, cyclodextrins such as α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin are preferable. Two or more types 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. Thereby, the polyrotaxane reacts with the active energy ray-curable component, and an adhesive whose crosslinking point is movable even after curing can be obtained. The active energy ray polymerizable group possessed by the cyclic molecule may be a group capable of polymerizing with the above-mentioned active energy ray curable compound, and examples thereof include (meth)acryloyl and (meth)acryloyloxy groups. And other radical polymerizable groups.

In the case of using cyclodextrin as the cyclic molecule, it is preferable to introduce an active energy ray polymerizable group to the hydroxyl group of the cyclodextrin via any appropriate linker. The number of active energy ray polymerizable groups in one molecule of polyrotaxane is preferably 2 to 1280, more preferably 50 to 1000, and more preferably 90 to 900.

It is suitable to introduce a hydrophobic modifying group into the cyclic molecule. By introducing a hydrophobic modifying group, the compatibility with active energy ray-curable components can be improved. In addition, since the hydrophobicity is imparted, when used for a polarizing film, water can be prevented from entering the interface between the adhesive layer and the polarizing member, and the water resistance can be further improved. Examples of the hydrophobic modifying group include polyester chains, polyamide chains, alkyl chains, oxyalkylene chains, ether chains, and the like. As a specific example, the groups described in paragraphs [0027] to [0042] of WO2009/145073 can be cited.

A polarizing film using a polyrotaxane-containing resin composition as an adhesive has excellent water resistance. The reason why the water resistance of the polarizing film is improved has not yet been determined, but it is estimated as follows. That is, it is considered that the crosslinking point can move due to the mobility of the cyclic molecules of the polyrotaxane (the so-called pulley effect), thereby imparting flexibility to the cured adhesive, and adhering to the uneven surface of the polarizer. As a result, the intrusion of water into the interface between the polarizing member and the adhesive layer is prevented. In addition, it is thought that the hydrophobicity of the adhesive can be imparted to the adhesive by making the polyrotaxane have a hydrophobic modifying group, which also contributes to preventing water from entering the interface between the polarizer and the adhesive layer. The content of the polyrotaxane is preferably 2% by mass to 50% by mass relative to the resin composition.

In the present invention, in order to form the adhesive layer, a cationically polymerizable adhesive composition can be used. As the cationically polymerizable compound used in the cationically polymerizable adhesive composition, it can be classified into 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. The multifunctional cationic polymerizable compound. Since the liquid viscosity of the monofunctional cationically polymerizable compound is low, by containing it in the adhesive composition, the liquid viscosity of the adhesive composition can be reduced. In addition, monofunctional cationically polymerizable compounds often have functional groups that exhibit various functions. By including them in the adhesive composition, they can exhibit various functions in the adhesive composition and/or the cured product of the adhesive composition. Features. Since the polyfunctional cationically polymerizable compound can three-dimensionally crosslink the cured product of the adhesive composition, it is preferably contained in the adhesive composition. Regarding the ratio of the monofunctional cationic polymerizable compound to the polyfunctional cationic polymerizable compound, relative to 100 parts by mass of the monofunctional cationic polymerizable compound, the multifunctional cationic polymerizable compound is preferably mixed in the range of 10 parts by mass to 1000 parts by mass . Examples of the cationically polymerizable functional group include an epoxy group, an oxetanyl group, and a vinyl ether group. Examples of compounds having epoxy groups include aliphatic epoxy compounds, alicyclic epoxy compounds, and aromatic epoxy compounds. In terms of excellent curability and adhesiveness, it is particularly preferable to contain alicyclic epoxy compounds as The cationically polymerizable adhesive composition of the present invention. As the alicyclic epoxy compound, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 3,4-epoxycyclohexylmethyl-3,4-cyclic Caprolactone-modified product, trimethylcaprolactone-modified product, valerolactone-modified product of oxocyclohexane carboxylate, etc., specifically, CELLOXIDE 2021, CELLOXIDE 2021A, CELLOXIDE 2021P, CELLOXIDE 2081, CELLOXIDE 2083 , CELLOXIDE 2085 (the above is made by Daicel Chemical Industry Co., Ltd.), Cyracure UVR-6105, Cyracure UVR-6107, Cyracure 30, R-6110 (the above is made by Dow Chemical Japan Ltd.), etc. In view of the effects of improving the curability of the cationic polymerizable adhesive composition of the present invention and reducing the liquid viscosity of the composition, it is preferable to contain a compound having an oxetanyl group. Examples of the compound having an oxetanyl group include 3-ethyl-3-hydroxymethyloxetane and 1,4-bis[(3-ethyl-3-oxetanyl) Methoxymethyl]benzene, 3-ethyl-3-(phenoxymethyl)oxetane, bis[(3-ethyl-3-oxetanyl)methyl]ether, 3-Ethyl-3-(2-ethylhexyloxymethyl)oxetane, phenol novolac oxetane, etc., commercially available ARON OXETANE OXT-101, ARON OXETANE OXT-121, ARON OXETANE OXT-211, ARON OXETANE OXT-221, ARON OXETANE OXT-212 (the above are manufactured by Toagosei Co., Ltd.), etc. In view of the effects of improving the curability of the cationic polymerizable adhesive composition of the present invention and reducing the liquid viscosity of the composition, it is preferable to contain a compound having a vinyl ether group. Examples of compounds having a vinyl ether group include 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, and triethylene diethylene glycol. Alcohol divinyl ether, cyclohexane dimethanol divinyl ether, cyclohexane dimethanol monovinyl ether, tricyclodecane vinyl ether, cyclohexyl vinyl ether, methoxyethyl vinyl ether, ethyl Oxyethyl vinyl ether, neopentyl erythritol type tetravinyl ether, etc.

The cationic polymerizable adhesive composition contains as a curable component at least one compound selected from the group having an epoxy group, a compound having an oxetanyl group, and a compound having a vinyl ether group described above, and the These are all materials that are hardened by cationic polymerization, so a photocationic polymerization initiator is blended. The photocationic polymerization initiator generates cationic species or Lewis acid by irradiation with active energy rays such as visible light, ultraviolet rays, X-rays, and electron beams, thereby initiating the polymerization reaction of epoxy groups or oxetanyl groups. As a photocationic polymerization initiator, a photoacid generator and a photobase generator can be used, and the photoacid generator mentioned later can be used suitably. In addition, in the case of using the adhesive composition used in the present invention as the visible light curability, it is particularly suitable to use a photocationic polymerization initiator having high sensitivity to light of 380nm or more, but the photocationic polymerization initiator is usually around 300nm Or a compound that shows great absorption in a wavelength region shorter than it, so by blending a photosensitizer that shows great absorption in light of a longer wavelength region, specifically a wavelength longer than 380 nm, can be In response to light of a wavelength in the vicinity, the production of cationic species or acid derived from the photocationic polymerization initiator is promoted. Examples of photosensitizers include anthracene compounds, pyrene compounds, carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, halogen compounds, photoreducible dyes, etc. These may also be used Mix two or more kinds to use. In particular, anthracene compounds are excellent in photosensitizing effects, and specific examples include Anthracure UVS-1331 and Anthracure UVS-1221 (manufactured by Kawasaki Chemical Co., Ltd.). The content of the photosensitizer is preferably 0.1% by mass to 5% by mass, more preferably 0.5% by mass to 3% by mass,

、2,6-二-三及丁基-4-甲基苯酚等聚合抑制劑；聚合引發助劑；流平劑；潤濕性改良劑；界面活性劑；增塑劑；紫外線吸收劑；無機填充劑；顏料；染料等。In addition, various additives may be blended as other optional components in the aforementioned adhesive composition within a range that does not impair the purpose and effects of the present invention. Examples of the additives include epoxy resin, polyamide, polyamide imide, polyurethane, polybutadiene, polychloroprene, polyether, polyester, and styrene-butadiene. Polymers or oligomers such as block copolymers, petroleum resins, xylene resins, ketone resins, cellulose resins, fluorine-based oligomers, polysiloxane-based oligomers, and polysulfide-based oligomers;

, 2,6-Di-tri and butyl-4-methylphenol and other polymerization inhibitors; polymerization initiation aids; leveling agents; wettability modifiers; surfactants; plasticizers; ultraviolet absorbers; inorganic Fillers; pigments; dyes, etc.

When applying the adhesive composition on the surface of the transparent protective film with the convex part, in order to prevent bubbles from mixing into the periphery of the convex part, the viscosity of the adhesive composition during coating should be 0.5-100mPa･s, preferably 1-50mPa ･S. The viscosity of the adhesive composition at the time of application can be adjusted according to the curable component used, the acrylic oligomer, and the type or blending amount of additives. In addition, the temperature of the adhesive composition at the time of application may be adjusted, and the viscosity of the adhesive composition may be adjusted to the aforementioned range. In addition, the temperature of the adhesive composition during coating is not particularly limited, and it is preferably 15-40°C, more preferably 20-35°C.

＜Manufacturing method of polarizing film＞ Hereinafter, each step in the manufacturing method of the polarizing film of the present invention will be described.

The manufacturing method of the polarizing film of the present invention includes: a coating step of applying an adhesive composition on the surface of the transparent protective film having convex portions; a bonding step of bonding the polarizer and the transparent protective film; The bonding step of bonding the polarizer and the transparent protective film to the adhesive layer having a thickness of 1.6 μm or more obtained by curing the adhesive composition.

The manufacturing method of the polarizing film of the present invention preferably further includes a coating step of applying an easy-to-adhesive composition on the bonding surface of the aforementioned polarizer.

It is also possible to perform surface modification treatment on the polarizer and the transparent protective film before the coating step. It is particularly suitable to perform surface modification treatment on the surface of the polarizer. The surface modification treatment includes corona treatment, plasma treatment, excimer treatment, flame treatment, etc., and corona treatment is particularly preferable. By performing corona treatment, reactive functional groups such as carbonyl groups or amine groups are generated on the surface of the polarizer, and the adhesion to the adhesive layer is improved. In addition, the ashing effect can remove impurities on the surface, or reduce surface irregularities, and produce a polarizing film with excellent appearance characteristics.

＜The application procedure of easy-to-bond composition＞ As a method of applying the easy-adhesive composition to the bonding surface of the polarizing material, for example, a method of applying the easy-adhesive composition to the bonding surface of the polarizing material. The coating method is not particularly limited, and examples thereof include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and curtain coating.

When the easy-adhesive composition contains a solvent, after the easy-adhesive composition is applied to the bonding surface of the polarizer, a drying step may be performed as needed.

When the thickness of the easy-adhesive composition layer (after drying) obtained by coating the easy-adhesive composition is too thick, the cohesive force of the easy-adhesive layer obtained by hardening the easy-adhesive composition layer will decrease, and the easy adhesion effect will be reduced. Case. Therefore, the thickness of the easy-to-bond composition layer (after drying) is preferably 1000 nm or less, more preferably 800 nm or less, and more preferably 600 nm or less. On the other hand, in order for the easy-adhesive layer to fully exert its effect, the thickness of the easy-adhesive composition layer (after drying) is usually 50 nm or more, preferably 100 nm or more, and more preferably 200 nm or more.

<The application procedure of the adhesive composition> The method of applying the adhesive composition on the release side of the support of the transparent protective film is appropriately selected according to the viscosity or the target thickness of the adhesive composition. For example, a reverse coater, a gravure coater (direct, reverse or Indirect), bar-type reverse coater, roller coater, die coater, bar coater, rod coater, etc.

For the adhesive composition, the thickness of the adhesive layer obtained by curing the adhesive composition is 1.6 μm or more, 2 μm or more, 3 μm or more, or 5 μm or more according to the height of the convex portion of the aforementioned transparent protective film. Coated. In addition, when the easy-to-adhesive layer is formed on the bonding surface of the polarizer, the easy-to-adhesive layer becomes part of the adhesive layer. Therefore, it is applied so that the thickness of the adhesive layer including the easy-to-adhesive layer becomes 1.6 μm or more. Apply the adhesive composition.

＜Fixing Steps＞ I purchased the adhesive composition (and the easy-bonding composition layer) coated as described above, and bonded the polarizer and the transparent protective film. The bonding of the polarizer and the transparent protective film can be performed with a roll laminator or the like.

<Next steps> After bonding the polarizer and the transparent protective film, irradiating active energy rays (electron beams, ultraviolet rays, visible light, etc.) to harden the adhesive composition (and the easy-to-bond composition layer) to form the adhesive layer. The irradiation direction of active energy rays (electron beam, ultraviolet rays, visible light, etc.) can be irradiated from any appropriate direction. It should be irradiated from the side of the transparent protective film. If irradiated from the polarizer side, the polarizer may be degraded by active energy rays (electron beam, ultraviolet rays, visible light, etc.).

The irradiation conditions in the case of irradiating an electron beam may adopt any appropriate conditions as long as the above-mentioned adhesive composition can be cured. For example, the acceleration voltage of electron beam irradiation should be 5kV~300kV, more preferably 10kV~250kV. When the accelerating voltage is less than 5kV, the electron beam may not reach the adhesive and may become insufficiently hardened. If the accelerating voltage is greater than 300kV, the penetrating power through the sample may be too strong, which may cause damage to the transparent protective film and polarizer. Risk of injury. As the amount of radiation, it is 5-100kGy, preferably 10-75kGy. When the irradiation dose is less than 5kGy, the curing of the adhesive will be insufficient. If it is more than 100kGy, it will damage the transparent protective film or the polarizer, reduce the mechanical strength or yellow, and fail to obtain the predetermined optical properties.

The electron beam irradiation is usually carried out in an inert gas, and can be carried out in the atmosphere or under the condition of introducing a small amount of oxygen as necessary. Although it depends on the material of the transparent protective film, by properly introducing oxygen, the surface of the transparent protective film that is in contact with the first electron beam will be blocked by oxygen, which can prevent damage to the transparent protective film, and it is only effective for the adhesive. To irradiate the electron beam.

In the manufacturing method of the polarizing film of the present invention, as the active energy ray, it is preferable to use the active energy ray that includes the wavelength range of 380 nm to 450 nm, particularly the active energy ray that has the largest irradiation amount of visible light in the wavelength range of 380 nm to 450 nm. When using ultraviolet light, visible light, and using a transparent protective film (UV non-transmissive transparent protective film) that imparts ultraviolet absorbing energy, it will absorb light with a wavelength shorter than 380nm, so light with a wavelength shorter than 380nm will not reach The adhesive composition does not contribute to the polymerization reaction. In addition, light with 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 curling and wrinkles of the polarizing film. Therefore, in the present invention, when ultraviolet and visible light are used, it is advisable to use a device that does not emit light with a wavelength shorter than 380nm as the active energy ray generator. More specifically, the cumulative illuminance and wavelength range of the wavelength range of 380~440nm The cumulative illuminance ratio of 250~370nm should be 100:0~100:50, more preferably 100:0~100:40. In the manufacturing method of the polarizing film of the present invention, the active energy rays are preferably a metal halide lamp containing gallium and an LED light source emitting light in the wavelength range of 380 to 440 nm. Or you can use 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, excimer Light sources containing ultraviolet and visible light, such as lasers or sunlight, can also be used after blocking ultraviolet rays with a wavelength shorter than 380 nm with a band-pass filter. In order to improve the bonding performance of the adhesive layer between the polarizer and the transparent protective film, and to prevent the polarizing film from curling, it is advisable to use a metal halide lamp encapsulated with gallium, and use a lamp that can block light with a shorter wavelength than 380nm. Active energy rays obtained by a band-pass filter, or active energy rays with a wavelength of 405 nm obtained by using an LED light source.

It is advisable to heat the adhesive composition before irradiating ultraviolet or visible light (heating before irradiation). In this case, it is better to heat to 40°C or higher, more preferably to 50°C or higher. In addition, it is also preferable to heat the active energy ray-curable adhesive composition after irradiating ultraviolet rays or visible light (heating after irradiation). In this case, heating to 40°C or higher is preferable, more preferably 50°C or higher.

The adhesive composition used in the present invention can be suitably used particularly when forming an adhesive layer for bonding a polarizer and a transparent protective film with a light transmittance of less than 5% at a wavelength of 365 nm. Here, the adhesive composition used in the present invention contains the photopolymerization initiator of the general formula (3), and can be cured by irradiating ultraviolet rays through a transparent protective film having UV absorbing energy to form an adhesive layer. Therefore, even for a polarizing film in which a transparent protective film having UV absorbing energy is layered on both areas of the polarizer, the adhesive layer can be hardened. However, of course, it is also possible to harden the adhesive layer for a polarizing film laminated with a transparent protective film that does not have UV absorbing energy. In addition, a transparent protective film with UV absorption energy refers to a transparent protective film with a transmittance of less than 10% to 380 nm light.

As a method of imparting UV absorbing energy to the transparent protective film, a method of containing an ultraviolet absorber in the transparent protective film and a method of containing a surface treatment layer of the ultraviolet absorber in the surface area of the transparent protective film can be cited.

系化合物等。Specific examples of ultraviolet absorbers include, for example, conventionally known oxybenzophenone-based compounds, benzotriazole-based compounds, salicylate-based compounds, benzophenone-based compounds, and cyanoacrylate-based compounds. Compounds, nickel complex salt compounds, three

Department of compounds and so on.

When the polarizing film of the present invention is manufactured by a continuous production line, the production line speed will vary depending on the curing time of the adhesive composition, preferably 1~500m/min, more preferably 5~300m/min, more preferably 10~100m /minute. If the production line speed is too small, the productivity will decrease, and the damage to the transparent protective film will increase. When the line speed is too high, the curing of the adhesive composition may become insufficient, and the target adhesiveness may not be obtained.

In order to produce a polarizing film without dot whitening defects and no local swelling on the surface of the transparent protective film, the thickness of the adhesive layer (including the easy bonding layer) must be 1.6 μm or more, preferably 2 μm or more, more preferably 3 μm or more, More preferably, it is 5 μm or more. In addition, the upper limit of the thickness of the adhesive layer (including the easy-adhesion layer) is not particularly limited. From the viewpoint of the curability of the adhesive layer, it is preferably 10 μm or less, more preferably 7 μm or less.

＜Optical film＞ The polarizing film of the present invention can be used in the form of an optical film laminated with other optical films in actual use. The optical layer is not particularly limited. For example, retardation films (including 1/2 or 1/4 wavelength plates), visual compensation films, brightness enhancement films, reflective plates, or anti-transmission plates can be used in liquid crystal display devices. Such as the optical layer used at the time of formation.

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

Examples of the retardation plate include: a birefringent film obtained by uniaxially or biaxially stretching a polymer material, an oriented film of a liquid crystal polymer, and a retardation plate obtained by supporting an oriented layer of a liquid crystal polymer with a film Wait. The thickness of the retardation film is also not particularly limited, and it is generally about 20 to 150 μm.

As the retardation film, it can be used to meet the reverse wavelength dispersion-type retardation film by the following formula (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) (where, Re[450] and Re[550] are 450nm and 550nm at 23℃, respectively The in-plane retardation value of the retardation film measured by the light, Δn is the in-plane birefringence when the refractive index of the retardation film in the slow axis direction and the fast axis direction are set to nx and ny, respectively, NZ It is the ratio of the thickness direction birefringence (that is, nx-nz) to the in-plane birefringence (that is, nx-ny) when nz is the refractive index in the thickness direction of the retardation film.

The aforementioned polarizing film or the optical film in which at least one layer of polarizing film is laminated may be provided with an adhesive layer for bonding with other members such as a liquid crystal cell. The adhesive forming the adhesive layer is not particularly limited. For example, acrylic polymers, silicone polymers, polyesters, polyurethanes, polyamides, polyethers, fluorine-based or rubber-based polymers can be appropriately selected. It is used as a base polymer. It is particularly suitable to use acrylic adhesives that are excellent in optical transparency, exhibit moderate wettability, adhesion properties of aggregation and adhesiveness, and are excellent in weather resistance or heat resistance.

The adhesive layer can be arranged on one side or both sides of the polarizing film or the optical film in the form of an overlapping layer of different compositions or types. In addition, when it is provided on both sides, adhesive layers of different compositions, types, thicknesses, etc. may be formed on the front and back surfaces of the polarizing film or optical film. The thickness of the adhesive layer can be appropriately determined according to the purpose of use, adhesion, etc., and is usually 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 by a separator for the purpose of preventing its contamination and so on until it is put into actual use. This can prevent contact with the adhesive layer in a normal processing state. As a separator, in addition to the aforementioned thickness conditions, suitable release agents such as polysiloxane-based or long-chain alkyl-based, fluorine-based, or molybdenum sulfide can be used as needed for plastic films, rubber sheets, paper, cloth, nonwovens, etc. Cloth, net, foamed sheet, metal foil, these laminates, and other suitable thin-layered bodies are those obtained by coating them, and other conventionally prescribed suitable materials.

＜Video display device＞ The polarizing film or optical film of the present invention can be suitably used for the formation of various devices such as liquid crystal display devices. The formation of the liquid crystal display device can be performed according to a 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 as necessary constituent members such as an illumination system, and incorporating a driving circuit, etc., but in the present invention, in addition to the use of the present invention It is not particularly limited except for the polarizing film or optical film, and it can be carried out according to a conventional method. Regarding the liquid crystal cell, any type such as TN type, STN type, and π type can be used.

It can be formed into a liquid crystal display device in which a polarizing film or an optical film is arranged on one side or both sides of a liquid crystal cell, or an appropriate liquid crystal display device such as a backlight or a reflector used in an illumination system. In this case, the polarizing film or optical film of the present invention may be arranged on one side or both sides of the liquid crystal cell. When polarizing films or optical films are provided on both sides, these may be the same or different. Furthermore, when the liquid crystal display device is formed, one layer or two or more layers such as diffuser, anti-glare layer, anti-reflection film, protective plate, prism array, lens array sheet, light diffuser, and backlight can be arranged at an appropriate position. And other appropriate components. Example

Examples of the present invention are described below, but the embodiments of the present invention are not limited to these.

＜Polarizers＞ First, a laminate with a 9μm-thick PVA layer formed on an amorphous PET substrate was stretched by air-assisted stretching at a stretching temperature of 130°C to form a stretched laminate. Next, the stretched laminate was dyed to form a colored laminate. Further, the colored laminate was stretched in an aqueous solution of boric acid at a stretching temperature of 65 degrees to form an optical film including a PVA layer with a thickness of 5μm, and stretched integrally with the amorphous PET substrate so that the total stretching ratio became 5.94 times. Layered body. By such two-stage extension, an optical film laminate including a PVA layer with a thickness of 5 μm to form a thin polarizer can be obtained. The thin polarizer is formed on an amorphous PET substrate. The PVA molecule of the PVA layer is formed. Highly oriented, and iodine adsorbed by dyeing is highly oriented in one direction in the form of polyiodide ion complexes. The moisture content of the thin polarizer (PVA layer) is 10% by mass.

＜Transparent protective film＞ As the transparent protective film, a 25 μm-thick cellulose triacetate film (manufactured by Konica Minolta: KC2UA) was used. The film is produced by a solution casting film forming method, and the surface of the film on the side (support peeling surface) after the film-forming support is peeled off has scars or scratches on the surface of the aforementioned film-forming support Convex portions caused by recesses such as through holes.

<Active energy rays> Visible light (metal halide lamp enclosed with gallium) is used as active energy rays. Irradiation device: Light HAMMER10 manufactured by Fusion UV Systems, Inc., valve: V valve, peak illuminance: 1600 mW/cm ² , cumulative irradiation The amount is 1000/mJ/cm ² (wavelength 380~440nm). In addition, the Sola-Check system manufactured by Solarell was used to measure the illuminance of visible light.

＜Preparation of easy bonding composition＞ 50 parts by mass of acrylomorpholine (manufactured by KJ Chemical Company, trade name "ACMO", SP value: 22.9) and 0.9 parts by mass of 3-acrylamidophenylboronic acid (manufactured by Junsei Chemical Company) were mixed to obtain The mixture was stirred at 25°C for 30 minutes, and 48.3 parts by mass of water and 0.8 parts by mass of a leveling agent (manufactured by Nissin Chemical Industry Co., Ltd., trade name "Olfine EXP. 4123") were further mixed in the mixture, and stirred at 25°C. In 10 minutes, the easy-to-bond composition was prepared.

(通式(3)中記載的化合物、商品名「KAYACURE DETX-S」、日本化藥公司製)1.5質量份、及作為光聚合引發劑的2-甲基-1-(4-甲硫基苯基)-2-嗎啉丙-1-酮(通式(4)中記載的化合物、商品名「Omnirad907」、IGM RESINS公司製)2.5質量份混合，在50℃下攪拌1小時，藉此調製了接著劑組成物。使用E型黏度計(東機產業公司製、TVE22LT)，測定調製出的接著劑組成物在25℃下的黏度，結果為15.3mPa･s。Example 1 <Preparation of Adhesive Composition> 45 parts by mass of acrylomorpholine (manufactured by KJ Chemical Co., Ltd., trade name "ACMO", SP value: 22.9), 1,9-nonanediol diacrylate (product Name "LIGHT ACRYLATE 1.9ND-A", manufactured by Kyoeisha Chemical Co., Ltd.) 41 parts by mass, acrylic oligomer (trade name "ARUFON UG4010", Nichia Koeisha Chemical Co., Ltd.) polymerized from (meth)acrylic monomers Preparation) 10 parts by mass, diethyl 9-oxysulfur as a photoinitiator

(The compound described in the general formula (3), the trade name "KAYACURE DETX-S", manufactured by Nippon Kayaku Co., Ltd.) 1.5 parts by mass, and 2-methyl-1-(4-methylthio) as a photopolymerization initiator Phenyl)-2-morpholin-1-one (the compound described in the general formula (4), trade name "Omnirad907", manufactured by IGM RESINS) 2.5 parts by mass was mixed and stirred at 50°C for 1 hour, thereby The adhesive composition was prepared. 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 the result was 15.3 mPa･s.

＜Production of polarizing film＞ In a continuous production line, a gravure roll coating method with a gravure roll is used to coat the prepared easy-adhesive composition on the PVA surface of the optical film laminate containing a PVA layer with a thickness of 5 μm to form a coating with a thickness of 1100 nm. Then, the coating film was dried using a dryer to form an easy-adhesive composition layer with a thickness of 550 nm. On the other hand, in other continuous production lines, a gravure roll coating method with a gravure roll is used to coat the prepared adhesive composition (25°C) on the release surface (surface with convex portions) of the support of the transparent protective film. ), and an adhesive composition layer with a thickness of 1500 nm was formed. Next, using a roller, the bonding surface of the optical film laminate on which the easy-adhesive composition layer is formed and the bonding surface of the transparent protective film on which the adhesive composition layer is formed are bonded. Then, the above-mentioned visible light was irradiated from the side of the laminated transparent protective film by an active energy ray irradiation device to allow the polarizer and the transparent protective film to pass through the adhesive layer (including the easy-to-adhesive layer), followed by hot air at 70°C for 3 minutes After drying and peeling off the amorphous PET substrate, a polarizing film having a transparent protective film on one side of the polarizer was obtained. The thickness of the adhesive layer (including the easy-to-bond layer) is 2050 nm.

Example 2 ＜Preparation of adhesive composition＞ The adhesive composition was prepared by the same method as in Example 1.

＜Production of polarizing film＞ In a continuous production line, a gravure roll coating method with a gravure roll is used to coat the prepared easy-adhesive composition on the PVA surface of the optical film laminate containing a PVA layer with a thickness of 5μm to form a thickness of 950nm The coating film was then dried using a dryer to form an easy-adhesive composition layer with a thickness of 475 nm. On the other hand, in other continuous production lines, a gravure roll coating method with a gravure roll is used to coat the prepared adhesive composition (25°C) on the release surface (surface with convex portions) of the support of the transparent protective film. ), and an adhesive composition layer with a thickness of 1500 nm was formed. Then, a polarizing film was obtained by the same method as in Example 1. The thickness of the adhesive layer (including the easy-adhesive layer) is 1975 nm.

Example 3 ＜Preparation of adhesive composition＞ According to the raw materials and blending amounts described in Table 2, the adhesive composition was prepared by the same method as in Example 1. 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 the result was 42 mPa･s. In addition, LIGHT ACRYLATE DCP-A in Table 2 is dimethylol tricyclodecane diacrylate (trade name "LIGHT ACRYLATE DCP-A", manufactured by Kyoeisha Chemical Co., Ltd.).

＜Production of polarizing film＞ In a continuous production line, a gravure roll coating method with a gravure roll is used to coat the prepared easy-adhesive composition on the PVA surface of the optical film laminate containing a PVA layer with a thickness of 5 μm to form a coating with a thickness of 950 nm. Then, the coating film was dried using a dryer to form an easy-adhesive composition layer with a thickness of 475 nm. On the other hand, in other continuous production lines, a gravure roll coating method with a gravure roll is used to coat the prepared adhesive composition (25°C) on the release surface (surface with convex portions) of the support of the transparent protective film. ), and an adhesive composition layer with a thickness of 1500 nm was formed. Then, a polarizing film was obtained by the same method as in Example 1. The thickness of the adhesive layer (including the easy-adhesive layer) is 1975 nm.

Comparative example 1 ＜Preparation of adhesive composition＞ The adhesive composition was prepared by the same method as in Example 1.

＜Production of polarizing film＞ In a continuous production line, a gravure roll coating method with a gravure roll is used to coat the prepared easy-adhesive composition on the PVA surface of the optical film laminate containing a PVA layer with a thickness of 5 μm to form a coating with a thickness of 950 nm. Then, the coating film was dried using a dryer to form an easy-adhesive composition layer with a thickness of 475 nm. On the other hand, in other continuous production lines, a gravure roll coating method with a gravure roll is used to coat the prepared adhesive composition (25°C) on the release surface (surface with convex portions) of the support of the transparent protective film. ), and an adhesive composition layer with a thickness of 1100 nm was formed. Then, a polarizing film was obtained by the same method as in Example 1. The thickness of the adhesive layer (including the easy-to-bond layer) is 1575 nm.

Reference example 1 ＜Preparation of adhesive composition＞ According to the raw materials and blending amounts described in Table 2, the adhesive composition was prepared by the same method as in Example 1. The viscosity of the prepared adhesive composition at 25°C was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., TVE22LT), and the result was 109 mPa･s. In addition, LIGHT ACRYLATE DCP-A in Table 2 is dimethylol tricyclodecane diacrylate (trade name "LIGHT ACRYLATE DCP-A", manufactured by Kyoeisha Chemical Co., Ltd.).

＜Production of polarizing film＞ In a continuous production line, a gravure roll coating method with a gravure roll is used to coat the prepared easy-adhesive composition on the PVA surface of the optical film laminate containing a PVA layer with a thickness of 5 μm to form a coating with a thickness of 950 nm. Then, the coating film was dried using a dryer to form an easy-adhesive composition layer with a thickness of 475 nm. On the other hand, in other continuous production lines, a gravure roll coating method with a gravure roll is used to coat the prepared adhesive composition (25°C) on the release surface (surface with convex portions) of the support of the transparent protective film. ), and an adhesive composition layer with a thickness of 1500 nm was formed. Then, a polarizing film was obtained by the same method as in Example 1. The thickness of the adhesive layer (including the easy-adhesive layer) is 1975 nm.

(Evaluation of spot whitening defects) Using a xenon lamp light source (manufactured by Hamamatsu Photonics, model: L8425-01), the obtained polarizing film was transmitted and projected onto a white screen 1 m away from the light source. Then, observe the projected image on the screen, and count the number of white-spotted defects within the projected image range equivalent to the 1m×1m range of the polarizing film. In addition, the evaluation is carried out in a dark room. The results are shown in Table 2.

(Evaluation of the swelling of the transparent protective film surface) Under a fluorescent lamp, light is irradiated on the transparent protective film side of the obtained polarizing film, and the surface shape is observed based on the reflected light reflected on the surface of the polarizing film. Then, in the range of 1 m×1 m on the surface of the polarizing film, the number of positions where convex swelling exists among the positions that appear as white dots in the evaluation of the whitening defect described above is counted. In addition, the evaluation is carried out in a dark room. The results are shown in Table 2.

(Assessment of bubbles) The appearance of the obtained polarizing film was observed with an optical microscope, and the number of bubbles with 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 is 0 is evaluated as ○, and the case where there is one or more bubbles is evaluated as ×. The results are shown in Table 2.

[Table 2]

Industrial availability The polarizing film of the present invention can be used in image display devices such as liquid crystal display devices (LCD), organic EL display devices, CRTs, PDPs, etc., alone or in the form of optical films formed by laminating them.

(no)

Claims (16)

A polarizing film is provided with a transparent protective film on at least one side of a polarizer via an adhesive layer. The characteristics of the polarizing film are: One surface of the aforementioned transparent protective film is a surface with convex portions, The adhesive layer is disposed on the convex surface of the transparent protective film, and The thickness of the aforementioned adhesive layer is 1.6 μm or more. The polarizing film according to claim 1, wherein the convex surface of the transparent protective film is the peeling surface of the support after the support for forming the film is peeled off, and The convex portion is formed by the concave portion on the surface of the thin film forming support. The polarizing film of claim 1 or 2, wherein the transparent protective film is a cellulose 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, wherein an easy-adhesive layer is provided on the bonding surface of the polarizer, and the easy-adhesive layer is a part of the adhesive layer. The polarizing film of claim 5, wherein the easy-adhesive composition, which is the forming material of the aforementioned easy-adhesive layer, contains: a compound represented by the following general formula (1): [Chemical formula 1]

(However, X is a functional group containing a reactive group, R ¹ and R ² each independently represent a hydrogen atom, an aliphatic hydrocarbon group, an aryl group, or a heterocyclic group that may have a substituent); and/or a MO bond in the structural formula (M is silicon, titanium, aluminum or zirconium, O is an oxygen atom) organometallic compound. The polarizing film of claim 6, wherein the compound represented by the aforementioned general formula (1) is a compound represented by the following general formula (1'): [Chemical formula 2]

(However, Y is an organic group, and X, R ¹ and R ^{2 are the} same as above). The polarizing film of claim 6 or 7, wherein the reactive group of the compound represented by the general formula (1) is selected from the group consisting of α, β-unsaturated carbonyl, vinyl, vinyl ether, epoxy, At least one reactive group in the group consisting of an oxetanyl group, an amino group, an aldehyde group, a mercapto group, and a halogen group. The polarizing film according to any one of claims 6 to 8, wherein the aforementioned easy-to-bond composition contains ^{polymerizability with an SP value of 21.0 (MJ/m 3} ) ^1/2 or more and 26.0 (MJ/m ³ ) ^1/2 or less Compound X. A method for manufacturing a polarizing film, the polarizing film is provided with a transparent protective film via an adhesive layer on at least one side of a polarizing member; The manufacturing method is characterized by: One surface of the aforementioned transparent protective film is a surface with convex portions; And the manufacturing method includes the following steps: The coating step is to coat the adhesive composition on the convex surface of the aforementioned transparent protective film; The laminating step is laminating the aforementioned polarizer and the aforementioned transparent protective film; and The next step is to bond the polarizer and the transparent protective film through the adhesive layer having a thickness of 1.6 μm or more, wherein the adhesive layer is obtained by curing the adhesive composition. The method of manufacturing a polarizing film according to claim 10, wherein the surface having the convex portion of the transparent protective film is the peeling surface of the support after the support for forming the film is peeled, and The convex portion is formed by the concave portion on the surface of the thin film forming support. The method for manufacturing a polarizing film of claim 10 or 11, wherein the viscosity of the aforementioned adhesive composition during coating is 0.5-100 mPa·s. The method for manufacturing a polarizing film according to any one of claims 10 to 12, which includes a coating step of applying an easy-to-adhesive composition on the bonding surface of the aforementioned polarizer, wherein the aforementioned easy-to-adhesive composition contains: The following general formula (1) The compound shown: [Chemical formula 3]

(However, X is a functional group including a reactive group, and R ¹ and R ² each independently represent a hydrogen atom, an aliphatic hydrocarbon group that may have a substituent, an aryl group, or a heterocyclic group); and/or have MO in the structural formula Bond (M is silicon, titanium, aluminum, or zirconium, O is an oxygen atom) organometallic compound. The method for manufacturing a polarizing film according to claim 13, wherein the easily bonding composition 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.} 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.