TW201609389A - Polarizing film and method for producing same - Google Patents

Abstract

In this polarizing film, in which a transparent protective film is laminated to at least one surface of a polarizer with an adhesive therebetween, the adhesive layer is formed from a cured product obtained by radiating active energy rays at an active-energy-ray-curable adhesive composition, the active-energy-ray-curable adhesive composition contains component A, which has a logPow-representing an octanol/water distribution coefficient-of -1 to 1, and component B, which has a logPow of 2 to 7. Furthermore, the concentration of component A is higher at the polarizer side in the adhesive layer. The polarizing film exhibits high adhesive strength when the polarizer and transparent protective film are laminated, and is provided with an adhesive layer having superior water resistance.

Description

Polarized film and method of manufacturing same Technical field

The present invention relates to a polarizing film in which a transparent protective film is laminated on at least one side of a polarizing member through an adhesive, and a method of manufacturing the same. The polarizing film can be formed into an optical film alone or in an optical film to form an image display device such as a liquid crystal display (LCD), an organic EL display device, a CRT, or a PDP.

Background technique

In clocks, mobile phones, PDAs, notebook computers, PC screens, DVD players, TVs, etc., liquid crystal display devices are rapidly expanding in the market. The liquid crystal display device visualizes the polarization state by the conversion of the liquid crystal, and the polarizing member can be used from the display principle. In particular, in applications such as TV, high brightness, high contrast, and wide viewing angle are increasingly required, and high transmittance, high polarization, high color reproducibility, and the like are increasingly required for polarizing films.

The polarizer has a high transmittance and a high degree of polarization. For example, an iodine-based polarizer having a structure in which iodine is adsorbed on polyvinyl alcohol (hereinafter, simply referred to as "PVA") is most widely used. In general, polarized film is used A transparent protective film is bonded to both sides of the polarizing material by a so-called water-based adhesive in which a polyvinyl alcohol-based material is dissolved in water (see Patent Document 1 and Patent Document 2 below). As the transparent protective film, cellulose triacetate or the like having a high moisture permeability can be used. When the water-based adhesive is used (that is, a wet laminate), after the polarizer and the transparent protective film are bonded, a drying step is required.

On the other hand, an active energy ray-curing type adhesive has been proposed in place of the above-mentioned water-based adhesive. When a polarizing film is produced using an active energy ray-curable adhesive, the productivity of the polarizing film can be improved because a drying step is not required. For example, the inventors of the present invention have proposed a radical polymerization type active energy ray-curable adhesive using an N-substituted amine-based monomer as a curable component (Patent Documents 3 and 4).

Prior technical literature Patent literature

Patent Document 1: Japanese Patent Laid-Open No. 2006-220732

Patent Document 2: Japanese Patent Laid-Open Publication No. 2001-296427

Patent Document 3: Japanese Patent Laid-Open Publication No. 2012-052000

Patent Document 4: Japanese Patent Laid-Open Publication No. 2012-068593

Summary of invention

The adhesive layer formed using the active energy ray-curable adhesive described in Patent Documents 3 and 4 is sufficient to be tested for water resistance by, for example, evaluation of fading in warm water of 60 ° C for 6 hours. However, in recent years, it has been more important to improve the water resistance of the adhesive for polarizing film. The degree of more severe water resistance test with or without peeling at the end stripping after evaluation of water immersion (saturation), for example. Therefore, in addition to the active energy ray-curable adhesives described in Patent Documents 3 and 4, the adhesive for polarizing film which has been reported so far has practically improved room for water resistance.

However, in recent years, there are many requirements for organic polymer materials to have antibiotic characteristics, but the actual situation is that it is difficult to satisfy the required characteristics with a single organic polymer material. In order to meet the requirements of the two-dimensional characteristics, a technique for adding a heterogeneous material having different properties to an organic polymer material has been proposed in various fields. Next, in the technical aspect, for example, when two different types of objects are attached, it is conceivable to form the adhesive layer into a two-layer structure in order to improve the adhesion between the respective objects. However, when the adhesive layer is formed into a two-layer structure, stress is concentrated on the interface thereof so that the adhesion force of the adhesive layer is lowered. In particular, in recent years, the adhesive used for the polarizing film which is required to be thinned is not easy to establish a technique in which the adhesive layer is formed into a two-layer structure. As far as the inventors know, there is no such report.

As described above, in the field of the adhesive used for the polarizing film which is required to be thinner, when the polarizer and the transparent protective film are attached to each other, it is difficult to develop a technique for improving the adhesion and improving the water resistance.

The present invention has been made in order to solve the above problems, and an object of the invention is to provide a polarizing film which exhibits a high adhesion force and has an adhesive layer excellent in water resistance when a polarizing element and a transparent protective film are laminated, and a method for producing the same.

The polarizing member and the transparent protective film as the polarizing film member exhibit different characteristics, for example, from the viewpoint of hydrophilicity, and thus will be used for such a function. The method of forming a two-layer structure by the adhesive layer of the volume layer is advantageous from the viewpoint of improving the adhesion force between the two substrates, but as described above, the interface peeling in the adhesive layer is reversed. The strength of the decline.

As a result of intensive research on the above-mentioned problems, the present inventors have found that it is possible to form a composition gradient structure without increasing the concentration of the hydrophilic component of the adhesive layer on the side of the polarizer without forming the adhesive layer as a two-layer structure. Thereby, the adhesion to the polarizer can be improved and the water resistance of the adhesive layer can be improved. The present invention has been completed based on the findings, and has the following configuration.

In other words, the present invention relates to a polarizing film which is obtained by laminating at least one of the polarizing members through a layer of a transparent protective film, wherein the adhesive layer is irradiated with active energy by an active energy ray-curable adhesive composition. The active energy ray-curable adhesive composition includes an A component having a logPow of -1 to 1 and an octal alcohol/water distribution coefficient of -1 to 1 and a B component having a log Pow of 2 to 7. Further, the concentration of the component A on the side of the polarizer on the side of the polarizer is high.

The adhesive layer of the polarizing film of the present invention is formed by irradiating an active energy ray to an active energy ray-curable adhesive composition, and the active energy ray-curable adhesive composition contains An A component having an octanol/water distribution coefficient of -1 to 1 and a B component having a logPow of 2 to 7. The polarizer as the adherend layer of the adhesive layer, particularly the polyvinyl alcohol-based polarizer, exhibits hydrophilicity, and the concentration of the component A on the polarizer side of the adhesive layer of the present invention is high, and the log Pow of the component A is -1. ~1, showing high hydrophilicity. Therefore, the A component which is particularly strong in affinity with the polarizer and exhibits hydrophilicity is often deposited on the polarizer side interface of the adhesive layer, and the adhesive is allowed to be used. The layer closely follows the polarizer. On the other hand, since the adhesive layer of the polarizing film of the present invention has a composition gradient structure in which the concentration of the component A on the polarizer side is high, the concentration of the component A on the polarizer side is high, and vice versa. The logPow is 2 to 7 and the concentration of the B component which exhibits high hydrophobicity becomes high. The transparent protective film is hydrophobic compared to the polarizing member, so that the adhesive layer of the polarizing film of the present invention and the transparent protective film are closely followed, and the water resistance is improved.

In addition, as for the adhesive layer which the polarizing film which is required to reduce thickness is required in recent years, there is no example which employs the component gradient structure which makes the density of the hydrophilic component of the polarizer side high.

In the adhesive layer of the polarizing film of the present invention, the concentration of the component A on the polarizer side is increased, and further, the component gradient structure having the concentration of the component A on the polarizer side is high, and the time-of-flight type II can be utilized. Confirmed by Time of Flight Secondary Ion Mass Spectrometry (TOF-SIMS). The principle of TOF-SIMS is to illuminate the sample with an initial ion beam (for example, 1E12 ions/cm ² or less) under ultra-high vacuum, and only release secondary ions from the outermost surface of the sample (about Å in depth). An iontophoresis time-of-flight (TOF type) mass spectrometer is available for mass spectrometry. Using this principle, information on the chemical composition of the elemental composition or compound present on the outermost surface of the sample can be obtained. Further, in the present invention, it is confirmed that the concentration of the component A on the polarizer side becomes high, and further, it is confirmed that the adhesive layer has a component gradient structure in which the concentration of the component A on the polarizer side becomes high, and the cluster ion etching can be utilized. law.

Hereinafter, the "cluster ion etching method" will be described. When a single atomic ion beam (Ar ⁺ , Cs ^{+ ,} etc.) is used as a general etching method for etching ions, when the surface of the adhesive layer is etched, the molecular structure of the surface of the adhesive layer is destroyed to form a damaged layer. At this time, even if the mass spectrum of the surface is to be obtained by TOF-SIMS, the correct mass spectrum of the surface of the adhesive layer cannot be measured due to the influence of the damaged layer. On the other hand, when the "cluster ion etching method" using "Ar gas cluster ions (Arn ⁺ )" as an etching ion is used, the damage to the surface of the adhesive layer after etching is lowered, and the damaged layer cannot be formed, so after etching The surface of the layer of the agent is then maintained with the molecular structure of the surface prior to etching. Therefore, the mass spectrum of the surface of the adhesive layer can be accurately measured by using TOF-SIMS.

Fig. 1 is a schematic view showing a method of evaluating the concentration of the component A on the polarizer side by the TOF-SIMS evaluation of the adhesive layer. (I) of Fig. 1 shows an example of a polarizing film of the present invention which is formed by laminating a transparent protective film 2 through the adhesive layer 3 on both surfaces of the polarizing member 1. First, the transparent protective film 2 (the upper transparent protective film 2 in (I) of FIG. 1) of the polarizing film shown in (I) is horizontally cut by a slicer, and the transparent protective film which is in contact with the adhesive layer 3 is thinned. Thickness of 2 ((II)). Next, as shown in (III), the mass spectrum of the surface of the thin transparent protective film 2 was measured by TOF-SIMS to analyze the composition of the surface. Further, as shown in (IV), the surface of the thin transparent protective film 2 was etched by a "cluster ion etching method", and the composition of the surface was analyzed by TOF-SIMS. Then, as shown in (V), the surface of the transparent protective film 2 was etched by "cluster ion etching" to precipitate the side surface of the transparent protective film 2 of the adhesive layer 3, and the composition of the surface was analyzed by TOF-SIMS. Thereafter, the etching treatment by the "cluster ion etching method" is repeated, and the composition of the surface of the deposited adhesive layer 3 is analyzed by TOF-SIMS, and the etching treatment is continued and then The analysis of the surface composition of the agent layer 3 (even the polarizer 1) reaches the surface of the polarizer until the end. According to the method described above, it was confirmed that the concentration of the component A on the polarizer side of the adhesive layer became high, and even the component gradient structure having the concentration of the component A on the polarizer side became high.

In the polarizing film, when the active energy ray-curable adhesive composition contains a (meth) acrylamide derivative as the component A, and the active energy ray-curable adhesive composition contains a polyfunctional (methyl) When the acrylate is used as the component B, the adhesion between the adhesive layer and the polarizer and the transparent protective film and the water resistance can be further improved.

In the polarizing film, the active energy ray-curable adhesive composition preferably contains an acrylic oligomer obtained by polymerizing a (meth)acrylic monomer. Further, in the polarizing film, the active energy ray-curable adhesive composition preferably contains a hydroxyl group-containing photopolymerization initiator. When the active energy ray-curable adhesive composition contains an acrylic oligomer obtained by polymerizing a non-polymerizable (meth)acrylic monomer, the composition of the adhesive composition between the polarizing member and the transparent protective film is easy. The concentration of the component A in the adhesive layer tends to be higher on the side of the polarizer. In addition, when a photopolymerization initiator containing a hydroxyl group is contained as a polymerization initiator, the solubility in the adhesive layer having a high concentration of the component A on the polarizer side is increased, and the hardenability of the adhesive layer is increased. As a result, it is preferable that the adhesive layer and the polarizer and the transparent protective film are further improved in adhesion and water resistance.

In the polarizing film, the active energy ray-curable adhesive composition preferably contains at least one organometallic compound selected from the group consisting of metal alkoxides and metal chelates.

When the polarizing film in which the transparent protective film is laminated on the polarizer through the adhesive layer is exposed to a dew condensation environment, particularly one of the mechanisms of peeling off between the adhesive layer and the polarizer, it is presumed as follows. First, the moisture penetrating the protective film diffuses in the adhesive layer, and the moisture diffuses to the polarizer interface side. Here, in the case of the conventional polarizing film, hydrogen bonding and/or ionic bonding greatly contribute to the adhesion between the adhesive layer and the polarizing member, but the moisture diffused to the interface side of the polarizing member causes the interface to be Hydrogen bonding and ionic bonding dissociation, and as a result, the adhesion of the adhesive layer to the polarizing member is lowered. Therefore, there is a case where peeling occurs between the adhesive layer and the polarizer in a dew condensation environment.

On the other hand, in the polarizing film of the present invention, the active energy ray-curable adhesive composition contains at least one organometallic compound selected from the group consisting of metal alkoxides and metal chelates. The organometallic compound becomes an active metal species by inclusion of moisture, and as a result, the organometallic compound closely interacts with both the polarizer and the active energy ray-curable component constituting the adhesive layer. Thereby, even if moisture is present at the interface between the polarizer and the adhesive layer, the molecules will closely interact with each other through the organometallic compound, so that the subsequent water resistance between the polarizer and the adhesive layer will rise leaping forward.

In the polarizing film, the metal of the organometallic compound contained in the active energy ray-curable adhesive composition is preferably titanium.

In the polarizing film, the active energy ray-curable adhesive composition preferably contains the metal alkoxide as the organometallic compound, and the metal alkoxide has an organic group having a carbon number of 6 on.

In the polarizing film, the active energy ray-curable adhesive composition preferably contains the metal chelate compound as the organometallic compound, and the organic group of the metal chelate compound preferably has a carbon number of 4 or more.

The polarizing film should preferably contain a viscosity of 15 mPa. An alkoxyalkylene group-containing compound above s. The active energy ray-curable adhesive composition forming the adhesive layer contains a viscosity of 15 mPa. When the alkoxyalkylene group-containing compound is s or more, the reason for the subsequent water resistance between the polarizer and the adhesive layer is increased, and it is as follows. When the moisture penetrates the protective film and moisture diffuses to the adhesive layer, at the interface between the polarizer and the adhesive layer, the alkoxyalkyl group of the compound has a sterol group due to inclusion of moisture, and a hydroxyl group present on the surface of the polarizer. A functional group such as a carboxyl group forms a covalent bond. In addition, the viscosity of the alkoxyalkyl group-containing compound is 15 mPa. When s or higher (high molecular weight), the fluidity is maintained in the pre-polymerization stage of the adhesive composition, and in the intermediate stage of polymerization of the composition, the binder composition being polymerized and the alkoxyalkyl group-containing compound are moderately produced. The incompatibility is more likely to be biased at the interface of the object than the alkoxyalkylene group having a low viscosity (low molecular weight). Therefore, even if the blending amount is set low, the viscosity is 15mPa. The alkoxyalkyl group-containing compound above s is still deposited on the surface side of the polarizer, whereby more hydrogen bonding and/or ionic bonding, or even covalent bonding, can be formed between the polarizing member and the adhesive layer. The subsequent water resistance between the polarizer and the adhesive layer will rise leaps forward.

In the polarizing film, the main chain of the alkoxyalkyl group-containing alkyl compound is preferably an acrylic polymer structure.

In the polarizing film, the active energy ray-curable adhesive composition is cured, and the adhesive layer obtained at 25 ° C preferably has a storage elastic modulus of 1.0 × 10 ⁷ Pa or more.

The polarizing film of the present invention can be produced, for example, by a manufacturing method comprising the steps of: coating the active energy ray-curable adhesive composition on at least one of the polarizer and the transparent protective film; And bonding the polarizer and the transparent protective film; and subsequently, the polarizer and the transparent protective film are subsequently passed through the adhesive layer, wherein the adhesive layer is from the surface of the polarizer or the transparent protective film The active energy ray is irradiated to the surface side to cure the active energy ray-curable adhesive composition. In the method for producing a polarizing film of the present invention, the temperature of the active energy ray-curable adhesive composition is adjusted to 15 to 40 ° C between the coating step and the subsequent step, and the adhesive layer is further provided. It is preferable that the concentration of the component A is likely to be higher on the side of the polarizer. In order to adjust the temperature of the active energy ray-curable adhesive composition to 15 to 40 ° C, the temperature of the film to which the adhesive composition is applied can be adjusted by, for example, adjusting the room temperature at which the film is conveyed, the temperature of the guide roll, and the like. Adjustment.

The polarizing film of the present invention is characterized in that the concentration of the component A on the side of the polarizer on the side of the adhesive layer formed after the subsequent step is high. The polarizing film of the present invention can be produced, for example, by a manufacturing method in which at least one of the polarizing members is laminated with a transparent protective film through the adhesive, and the manufacturing method is characterized in that the adhesive layer is borrowed. a cured layer formed by irradiating an active energy ray-curable adhesive composition with an active energy ray, and the manufacturing method package In the first coating step, the first active energy ray-curable adhesive composition containing the component A is applied to the bonding surface of the polarizer, and the log Pow of the octanol/water distribution coefficient of the component A is -1~1; a second application step of applying a second active energy ray-curable adhesive composition containing a component B having a log Pow of 2 to 7 on the bonding surface of the transparent protective film; The polarizer and the transparent protective film; and a subsequent step of: transmitting the polarizer and the transparent protective film through the adhesive layer, wherein the adhesive layer is irradiated from the surface of the polarizer or the surface of the transparent protective film The active energy ray is obtained by curing the active energy ray-curable adhesive composition, and the concentration of the component A on the polarizer side of the adhesive layer formed after the subsequent step is high.

Further, as described above, when the adhesive layer is formed into a two-layer structure, stress is concentrated on the interface thereof, and the adhesion of the adhesive layer is lowered. On the other hand, according to the manufacturing method, the first active energy ray-curable adhesive composition and the second active energy ray-curable adhesive composition are bonded together in a fluid state, so that the two layers are subjected to a certain degree. Since the two phases are not formed, a composition gradient structure in which the concentration of the A component exhibiting high hydrophilicity is increased on the side of the polarizer is formed. Therefore, no interfacial peeling occurs between the first active energy ray-curable adhesive composition and the second active energy ray-curable adhesive composition, and the polarizer and the transparent protective film have good adhesion, and the polarizing film has good water resistance. Sex.

In the method for producing a polarizing film, the active energy ray-curable adhesive composition preferably contains at least one organometallic compound selected from the group consisting of a metal alkoxide and a metal chelate.

In the method for producing a polarizing film, the first active energy ray-curable adhesive composition preferably contains the organometallic compound.

In the method for producing a polarizing film, the metal of the organometallic compound contained in the active energy ray-curable adhesive composition is preferably titanium.

In the method for producing a polarizing film, the active energy ray-curable adhesive composition preferably contains the metal alkoxide as the organometallic compound, and the metal alkoxide preferably has an organic carbon number of 6 or more.

In the method for producing a polarizing film, the active energy ray-curable adhesive composition preferably contains the metal chelate compound as the organometallic compound, and the metal chelate compound preferably has an organic group carbon number of 4 or more.

In the method for producing the polarizing film, it is preferred to have a viscosity of 15 mPa. An alkoxyalkylene group-containing compound above s.

In the method for producing a polarizing film, the main chain of the alkoxyalkyl group-containing alkyl compound is preferably an acrylic polymer structure.

In the method for producing a polarizing film, the storage elastic modulus of the adhesive layer obtained by curing the active energy ray-curable adhesive composition at 25 ° C is preferably 1.0 × 10 ⁷ Pa or more.

1‧‧‧ polarizer

2‧‧‧Transparent protective film

3‧‧‧ adhesive layer

1(I) to (V) are schematic views showing a method of evaluating the composition gradient structure of the adhesive layer using TOF-SIMS.

Form for implementing the invention

The polarizing film of the present invention is characterized in that at least one of the polarizing members is laminated with a transparent protective film through the adhesive, and the adhesive layer is obtained by irradiating the active energy ray-curable adhesive composition with an active energy ray. The layer is formed.

The active energy ray-curable adhesive composition can be roughly classified into an electron beam curing type, an ultraviolet curing type, a visible light curing type, and the like. Further, the ultraviolet curable type and visible light curing type adhesive can be classified into a radical polymerization curing type adhesive and a cationic polymerization type adhesive. In the present invention, an active energy ray having a wavelength range of less than 10 nm to 380 nm is referred to as ultraviolet light, and an active energy ray having a wavelength range of 380 nm to 800 nm is referred to as visible light.

The compound constituting the radical polymerization hardening type adhesive is exemplified by a radical polymerizable compound. The radically polymerizable compound may be exemplified by a compound having a radical polymerizable functional group having a carbon-carbon double bond such as a (meth)acryl fluorenyl group or a vinyl group. As the curable component, any of a monofunctional radical polymerizable compound or a difunctional or higher polyfunctional radical polymerizable compound can be used. In addition, these radically polymerizable compounds may be used alone or in combination of two or more. The radically polymerizable compound is preferably a compound having, for example, a (meth)acrylonitrile group. The main component of the active energy ray-curable adhesive composition used in the present invention preferably contains a compound having a (meth) acrylonitrile group, specifically, a total amount of active energy ray-curable adhesive composition. When it is 100% by weight, it is preferred to contain 50% by weight or more of the compound having a (meth)acryl fluorenyl group, and it is preferably 80% by weight or more. Further, in the present invention, the (meth)acryl fluorenyl group is an acryl fluorenyl group and/or a methacryl fluorenyl group, the following "(A Base) is the same meaning.

<Monofunctional radical polymerizable compound>

The monofunctional radically polymerizable compound may, for example, be a (meth)acrylamide derivative having a mercaptoamine (meth)acrylate group. The (meth)acrylamide derivative is preferred because it can ensure adhesion to a polarizer or various transparent protective films, and has a high polymerization rate and excellent productivity. Specific examples of the (meth) acrylamide derivative may, for example, be N-methyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl N-alkyl group such as (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N-hexyl (meth) acrylamide (meth) acrylamide derivatives; N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-methylol-N-propane (methyl) N-hydroxyalkyl-containing (meth) acrylamide derivatives such as acrylamide; N-aminoalkyl groups such as aminomethyl (meth) acrylamide, amine ethyl (meth) acrylamide a (meth) acrylamide derivative; an N-alkoxy-containing (meth) acrylamide derivative such as N-methoxymethyl acrylamide or N-ethoxymethyl decylamine; A (meth) acrylamide derivative containing an N-fluorenylalkyl group such as methyl (meth) acrylamide or decyl (meth) acrylamide. Further, the heterocyclic ring-containing (meth) acrylamide derivative in which the nitrogen atom of the (meth)acrylic acid amide group forms a hetero ring may, for example, be an N-propylene fluorenyl group. Porphyrin, N-propylene hydrazinopiperidine, N-methyl propylene piperidine, N-propylene decyl pyrrolidine, and the like.

In the above (meth) acrylamide derivative, it is preferable to use an N-hydroxyalkyl group-containing (meth) acrylamide derivative from the viewpoint of adhesion to a polarizer or various transparent protective films. The monofunctional radically polymerizable compound may be a variety of (meth)acrylic acid derivatives having a (meth)acrylenyloxy group. example. Specific examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and 2-methyl (meth)acrylate. Base-2-nitropropyl ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tert-butyl (meth)acrylate, (methyl) N-amyl acrylate, third amyl (meth)acrylate, 3-pentyl (meth)acrylate, 2,2-dimethylbutyl (meth)acrylate, n-hexyl (meth)acrylate, (A) Hexyl acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 4-methyl-2-propylamyl (meth)acrylate, (meth)acrylic acid (Meth)acrylic acid (carbon number 1-20) alkyl esters such as n-octadecyl ester.

Further, examples of the (meth)acrylic acid derivative include a cycloalkyl (meth) acrylate such as cyclohexyl (meth) acrylate or cyclopentyl (meth) acrylate; and a benzyl group (methyl). Aralkyl (meth) acrylate such as acrylate; 2-iso Base (meth) acrylate, 2-lower Methyl (meth) acrylate, 5-nor Alk-2-yl-methyl (meth) acrylate, 3-methyl-2-lower Methyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, Polycyclic (meth) acrylate; 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-methoxymethoxyethyl ( Methyl) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, alkyl phenoxy poly An alkoxy group or a phenoxy group-containing (meth) acrylate such as ethylene glycol (meth) acrylate.

Further, the (meth)acrylic acid derivative may, for example, be 2-hydroxyl Ethyl ethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxy butyl Base (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxydodecyl ( Hydroxyalkyl (meth) acrylate such as methyl) acrylate, or [4-(hydroxymethyl)cyclohexyl] methacrylate, cyclohexanedimethanol mono(meth) acrylate, 2-hydroxy- Hydroxy-containing (meth) acrylate such as 3-phenoxypropyl (meth) acrylate; epoxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate epoxy propyl An epoxy group-containing (meth) acrylate such as ether; 2,2,2-trifluoroethyl (meth) acrylate, 2,2,2-trifluoroethyl ethyl (meth) acrylate, Tetrafluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, 3-chloro-2 a halogen-containing (meth) acrylate such as hydroxypropyl (meth) acrylate; dimethylaminoethyl ( Alkylaminoalkyl (meth) acrylate such as methyl) acrylate; 3-oxetanylmethyl (meth) acrylate, 3-methyl-oxetanylmethyl ( Methyl) acrylate, 3-ethyl-oxetanylmethyl (meth) acrylate, 3-butyl-oxetanylmethyl (meth) acrylate, 3-hexyl- a (meth) acrylate containing an oxo group such as oxetanylmethyl (meth) acrylate; a heterocyclic ring such as tetrahydrofuran methyl ester (meth) acrylate or butyrolactone (meth) acrylate; (meth) acrylate, hydroxytrimethylacetic acid neopentyl glycol (meth) acrylate adduct, p-phenyl phenol (meth) acrylate, and the like.

Further, examples of the monofunctional radically polymerizable compound include (meth)acrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, and Ikon. a carboxyl group-containing monomer such as acid, maleic acid, fumaric acid, crotonic acid or isocrotonic acid.

Further, examples of the monofunctional radically polymerizable compound include an internal guanamine-based vinyl monomer such as N-vinylpyrrolidone, N-vinyl-ε-caprolactam, and methylvinylpyrrolidone; and ethylene; Pyridine, ethylenepiperidone, vinylpyrimidine, vinylpiper , vinylpyrazine, vinylpyrrole, vinylimidazole, ethylene Azole, ethylene A vinyl monomer having a nitrogen-containing hetero ring or the like.

Further, the monofunctional radically polymerizable compound can be used as a radically polymerizable compound of an active methylene group. The radically polymerizable compound having an active methylene group is a compound having an active methylene group such as a (meth)acrylic group at the terminal or molecule and having an active methylene group. The active methylene group may, for example, be an ethyl acetonitrile group, an alkoxy propylene group or a cyanoethenyl group. The aforementioned active methylene group is preferably an ethyl acetonitrile group. Specific examples of the radically polymerizable compound having an active methylene group include, for example, 2-ethyl oxime oxiranyl (meth) acrylate and 2-ethyl acetoxypropyl (meth) acrylate. Ethyl ethoxylated (meth) acrylate such as 2-acetamethylene-1-methylethyl (meth) acrylate; 2-ethoxypropyl decyl oxyethyl ( Methyl) acrylate, 2-cyanoacetoxyethyl (meth) acrylate, N-(2-cyanoacetoxyethyl) acrylamide, N-(2-propenyl ethoxylated) Butyl) acrylamide, N-(4-acetamethyleneoxymethylbenzyl) acrylamide, N-(2-acetamidoethyl) acrylamide, and the like. The radically polymerizable compound having an active methylene group is preferably acetoxycarbonyl (meth) acrylate.

<Polyfunctional radical polymerizable compound>

Further, examples of the difunctional or higher polyfunctional radical polymerizable compound include tripropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and 1,6-hexanediol II ( Methyl) acrylate, 1,9-decanediol di(meth) acrylate, 1,10-decanediol diacrylate, 2-ethyl-2-butylpropane diol di(methyl Acrylate, bisphenol A di(meth) acrylate, bisphenol A ethylene oxide adduct di(meth) acrylate, bisphenol A propylene oxide adduct di(meth) acrylate, Bisphenol A diglycidyl ether di(meth) acrylate, neopentyl glycol di(meth) acrylate, tricyclodecane dimethanol di(meth) acrylate, cyclic trimethylolpropane Formal (meth) acrylate, two Alkanol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentane Esterified product of (meth)acrylic acid and polyhydric alcohol, such as tetraol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, EO modified diglycerol tetra (meth) acrylate, 9, 9-Bis[4-(2-(methyl)acrylenyloxyethoxy)phenyl]indole. Specific examples include ARONIX M-220 (manufactured by Toagosei Co., Ltd.), Light Acrylate 1, 9ND-A (LogPow; 3.68) (manufactured by Kyoeisha Chemical Co., Ltd.), and 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.), and the like. Further, various epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, or various (meth) acrylate monomers, etc. may be mentioned as needed. For example.

The adhesive layer of the present invention has a high concentration of the component A on the side of the polarizer. Further, in the adhesive layer, when the component gradient structure is to be realized with respect to the component A, the active energy ray-curable adhesive composition contains an octanol/water distribution. The coefficient of the logPow is -1 to 1 component A and the logPow is 2 to 7 component B.

The octanol/water distribution coefficient (logPow) is an index indicating the lipophilicity of a substance, and means the logarithm of the partition coefficient of octanol/water. The high logPow is oleophilic, meaning that the water absorption rate is low. The log Pow value can be obtained by measurement (the flask shake method described in JIS-Z-7260), and can also be calculated by calculation. In the present specification, the log Pow value calculated by Chem Draw Ultra manufactured by Cambridge Soft Co., Ltd. is used.

In the radically polymerizable compound described above, the logPow is a compound having a logPow of -1 to 1, and the hydroxyethyl acrylamide (product name) is exemplified. HEAA", manufactured by Xingren Co., Ltd., LogPow; -0.56), N-vinylformamide (trade name "BEAMSET 770", manufactured by Arakawa Chemical Co., Ltd., LogPow; -0.25), acryloylmorpholine (trade name "ACMO") , Xingren Co., Ltd., LogPow; -0.20), γ-butyrolactone acrylate (trade name "GBLA", Osaka Organic Chemical Industry Co., Ltd., LogPow; 0.19), acrylic acid 2 (trade name "β-CEA", DAICEL, LogPow; 0.2), N-vinylpyrrolidone (trade name "NVP", manufactured by Japan Catalyst Co., Ltd., LogPow; 0.24), acetamethylene ethoxyethyl methacrylate (trade name "AAEM", Manufactured by Nippon Synthetic Chemical Co., Ltd., LogPow; 0.27), 2-hydroxyethyl acrylate (trade name "HEA", manufactured by Osaka Organic Chemical Industry Co., Ltd., LogPow; 0.28), and epoxy methacrylate (trade name "LIGHT" ACRYLATE G", Co., Ltd., LogPow; 0.57), dimethyl methacrylate (trade name "DMAA", Xingrenshe , LogPow =; 0.58), a large amount of tetrahydrofuran, methyl alcohol acrylate esters (trade name "VISCOAT # 150D," manufactured by Osaka Organic Chemical Industry Co., LogPow; 0.60), 4- hydroxy butylacrylate Ester (trade name "4-HBA", manufactured by Osaka Organic Chemical Industry Co., Ltd., LogPow; 0.68), acrylic acid (trade name "Acrylic", manufactured by Mitsubishi Chemical Corporation, LogPow; 0.69), triethylene glycol diacrylate (trade name) "Light Acrylate 3EG-A", manufactured by Kyoeisha Chemical Co., Ltd., LogPow; 0.72). Among these, the logPow of the present invention is a component A of -1 to 1, preferably using a (meth) acrylamide derivative, and more preferably using hydroxyethyl acrylamide, acryloyl morpholine, or dimethyl Acrylamine is preferred. In addition to the (meth)acrylamide derivative, 4-butyl hydroxyacrylate is preferably used.

In order to increase the adhesion and water resistance of the adhesive layer, when the total amount of the active energy ray-curable adhesive composition is 100% by weight, the content of the A component having a log Pow of -1 to 1 is preferably 5 to 50% by weight. And preferably from 10 to 45% by weight.

LogPow is a component B of 2 to 7, and a compound having a log Pow of 2 to 7 among the radically polymerizable compounds described above can be used arbitrarily, and specific examples thereof include dicyclopentenyl acrylate (trade name "FANCRYL". FA-511AS", manufactured by Hitachi Chemical Co., Ltd., LogPow; 2.26), butyl acrylate (trade name "Butyl Acrylate", manufactured by Mitsubishi Chemical Corporation, LogPow; 2.35), 1,6-hexanediol diacrylate (trade name) "Light Acrylate 1.6HX-A", manufactured by Kyoeisha Chemical Co., Ltd., LogPow; 2.43), dicyclopentanyl acrylate (trade name "FANCRYL FA-513AS", manufactured by Hitachi Chemical Co., Ltd., LogPow; 2.58), dihydroxy Methyl-tricyclodecane diacrylate (trade name "Light Acrylate DCP-A", manufactured by Kyoeisha Chemical Co., Ltd., LogPow; 3.05), Acrylate (trade name "Light Acrylate IB-XA", manufactured by Kyoeisha Chemical Co., Ltd., LogPow; 3.27), hydroxytrimethylacetic acid neopentyl glycol acrylic acid adduct (trade name "Light Acrylate HPP-A", Co., Ltd., LogPow; 3.35), 1,9-decanediol diacrylate (trade name "Light Acrylate 1, 9ND-A", manufactured by Kyoeisha Chemical Co., Ltd., LogPow; 3.68), o- Phenylphenol EO modified acrylate (trade name "FANCRYL FA-301A", manufactured by Hitachi Chemical Co., Ltd., LogPow; 3.98), 2-ethylhexyloxy oxime (trade name "ARON OXETANE OXT-212", manufactured by Toagosei Co., Ltd. , LogPow; 4.24), bisphenol-A-diglycidyl ether (trade name "JER828", manufactured by Mitsubishi Chemical Corporation, LogPow; 4.76), bisphenol A EO6 Moer modified diacrylate (trade name "FA"-326A", manufactured by Hitachi Chemical Co., Ltd., LogPow; 4.84), bisphenol AEO4 Moer modified diacrylate (trade name "FA-324A", manufactured by Hitachi Chemical Co., Ltd., LogPow; 5.15), bisphenol A PO2 Moer Diacrylate (trade name "FA-P320A", manufactured by Hitachi Chemical Co., Ltd., LogPow; 6.10), bisphenol A PO3 molar modified diacrylate (trade name "FA-P323A", Hitachi Chemical Co., Ltd., LogPow; 6.26), bisphenol A PO4 molar modified diacrylate (trade name "FA-P324A", manufactured by Hitachi Chemical Co., Ltd., LogPow; 6.43). Among these, the log Pow of the present invention is a B component of 2 to 7, preferably using a polyfunctional (meth) acrylate, more preferably 1,6-hexanediol diacrylate), or a dimethylol group. Tricyclodecane diacrylate, hydroxytrimethylacetic acid neopentyl glycol acrylic acid adduct, 1,9-nonanediol diacrylate, 2-ethylhexyloxyanthracene, bisphenol-A-diepoxide Propyl ether, bisphenol A EO6 Moer modified diacrylate, bisphenol A EO4 Moer modified diacrylate, bisphenol A PO2 Moter modified diacrylate, bisphenol A PO3 Moter modified diacrylate Ester, or bisphenol A PO4 molar modified diacrylate.

In order to improve the adhesion and water resistance of the adhesive layer, When the total amount of the strand curing adhesive composition is 100% by weight, the content of the component B having a log Pow of 2 to 7 is preferably 30 to 95% by weight, and preferably 40 to 80% by weight.

When the active energy ray-curable adhesive composition is an active energy ray using an electron beam or the like, the active energy ray-curable adhesive composition does not necessarily contain a photopolymerization initiator, but ultraviolet rays or visible rays are used as active energy rays. It is preferred to include a photopolymerization initiator.

<Photopolymerization initiator>

The photopolymerization initiator used in the case of using a radical polymerizable compound is appropriately selected depending on the active energy ray. When hardened by ultraviolet light or visible light, a photopolymerization initiator is used by ultraviolet light or visible light splitting. The photopolymerization initiator may, for example, be a diphenyl ketone such as benzyl, diphenyl ketone, benzhydryl benzoic acid or 3,3'-dimethyl-4-methoxydiphenyl ketone. a compound; 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)one, α-hydroxy-α,α'-dimethylacetophenone, 2-methyl-2-hydroxyl An aromatic ketone compound such as ethyl phenyl ketone or α-hydroxycyclohexyl benzophenone; methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy Acetophenone-based compound such as acetophenone or 2-methyl-1-[4-(methylthio)-phenyl]-2-morpholinopropane-1; benzoin methyl ether, benzoin Ethyl ether, benzoin isopropyl ether, benzoin methyl ether, fenyl aryl methyl ether and other benzoin ether compounds; ketal ketal and other aromatic ketal compounds; 2-naphthalene An aromatic sulfonyl chloride compound such as sulfonyl chloride; a photoactive lanthanide compound such as 1-keto-1,1-propanedione-2-(o-ethoxycarbonyl)anthracene; 9-oxosulfur 2-chloro 9-oxosulfur 2-methyl 9-oxosulfur 2,4-dimethyl 9-oxosulfur Isopropyl 9-oxosulfur 2,4-dichloro 9-oxosulfur 2,4-diethyl 9-oxosulfur 2,4-diisopropyl 9-oxosulfur Twelve base 9-oxosulfur 9-oxosulfur a compound; camphorquinone; a halogenated ketone; a mercaptophosphine oxide; a mercaptophosphonate.

When the total amount of the active energy ray-curable adhesive composition is 100% by weight, the amount of the photopolymerization initiator blended is 20% by weight or less. The blending amount of the photopolymerization initiator is preferably 0.01 to 20% by weight, more preferably 0.05 to 10% by weight, still more preferably 0.1 to 5% by weight.

Further, in the case of using a curable adhesive for a polarizing film of the present invention, when a visible light curing type containing a radical polymerizable compound as a curable component is used, a photopolymerization initiator having a high sensitivity to light of 380 nm or more is used. good. A photopolymerization initiator having a high sensitivity to light of 380 nm or more will be described later.

The photopolymerization initiator is used alone as the compound represented by the following formula (1);

(wherein R ¹ and R ² represent -H, -CH ₂ CH ₃ , -iPr or Cl, and R ¹ and R ² may be the same or different), or a compound represented by the formula (1) may be used in combination with the latter. A photopolymerization initiator having a high sensitivity to light of 380 nm or more is preferred. When the compound represented by the formula (1) is used, the photopolymerization initiator having high sensitivity to light of 380 nm or more is excellent in adhesion. In the compound of the formula (1), diethyl 9-oxosulfuric acid wherein R ¹ and R ² are -CH ₂ CH ₃ Very good. The composition ratio of the compound represented by the formula (1) in the composition of the second embodiment is preferably 0.1 to 5 parts by weight, preferably 0.5 to 4 parts by weight, based on 100 parts by weight of the total amount of the curable component. ~3 parts by weight is more preferred.

Further, it is preferred to add a polymerization starting aid as needed. The polymerization initiation aid may, for example, be triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, 4 Ethyl dimethylamino benzoate, isoamyl 4-dimethylaminobenzoate, etc., particularly preferably ethyl 4-dimethylaminobenzoate. When the polymerization initiator is used, the amount thereof is usually 0 to 5 parts by weight, preferably 0 to 4 parts by weight, and most preferably 0 to 3 parts by weight, based on 100 parts by weight of the total amount of the curable component. .

Further, a well-known photopolymerization initiator can be used as needed. The transparent protective film having UV absorption energy does not allow light of 380 nm or less to penetrate, and therefore the photopolymerization initiator is preferably a photopolymerization initiator having high sensitivity to light of 380 nm or more. Specifically, for example, 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamino-1 -(4-morpholinylphenyl)-butanone-1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4- Phenyl)phenyl]-1-butanone, 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzylidene) -phenylphosphine oxide, bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium Wait.

In particular, the photopolymerization initiator is a compound represented by the following formula (2) in addition to the photopolymerization initiator of the formula (1); [Chemical 2]

(wherein R ³ , R ⁴ and R ⁵ represent -H, -CH ₃ , -CH ₂ CH ₃ , -iPr or Cl, and R ³ , R ⁴ and R ⁵ may be the same or different). As the compound represented by the formula (2), commercially available 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropan-1-one (trade name: IRGACURE 907) can be preferably used. Manufacturer: BASF). Others, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1 (trade name: IRGACURE369 manufacturer: BASF), 2-(dimethylamine Base]-2-[(4-methylphenyl)methyl]-1-[4-(4- Phenyl)phenyl]-1-butanone (trade name: IRGACURE 379 Manufacturer: BASF) has a high sensitivity and is therefore preferred.

In the present invention, it is preferred to use a photopolymerization initiator containing a hydroxyl group as the photopolymerization initiator. When the active energy ray-curable adhesive composition contains a hydroxyl group-containing photopolymerization initiator as a polymerization initiator, the solubility in the adhesive layer having a high concentration of the component A on the polarizer side is high, and the adhesive layer is hardenable. rise. The photopolymerization initiator having a hydroxyl group may, for example, be 2-methyl-2-hydroxyethyl phenyl ketone (trade name "DAROCUR 1173", manufactured by BASF Corporation) or 1-hydroxycyclohexyl phenyl ketone (trade name " IRGACURE 184", manufactured by BASF Corporation), 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (trade name "IRGACURE 2959", BASF Manufactured, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propenyl)-benzyl]phenyl}-2-methyl-propan-1-one (commodity) Name "IRGACURE127", manufactured by BASF Corporation). In particular, 1-hydroxycyclohexyl phenyl ketone is preferred because it has excellent solubility in an adhesive layer having a high concentration of component A.

<A radically polymerizable compound having an active methylene group and having hydrogen scavenging Functional free radical polymerization initiator >

In the active energy ray-curable adhesive composition, when a radically polymerizable compound having an active methylene group is used as the radical polymerizable compound, it is preferably used in combination with a radical polymerization initiator having a hydrogen abstracting action. With this configuration, in particular, even after being taken out from a high-humidity environment or water (non-dry state), the adhesion of the adhesive layer having a polarizing film is remarkably improved. The reason is not clear, but it is considered to be the following reason. That is, the radically polymerizable compound having an active methylene group is polymerized with another radical polymerizable compound constituting the adhesive layer, and is pulled into the main chain and/or the side chain of the matrix polymer in the adhesive layer to form a subsequent Agent layer. In the polymerization process, when a radical polymerization initiator having a hydrogen abstracting action is present, a matrix polymer constituting the adhesive layer is formed, and a radically polymerizable compound having an active methylene group is extracted from hydrogen. Methylene groups generate free radicals. Further, a methylene group having a radical generated reacts with a hydroxyl group of a polarizer such as PVA to form a covalent bond between the adhesive layer and the polarizer. As a result, even in a non-dry state, it is presumed that the adhesion of the adhesive layer having a polarizing film is remarkably improved.

In the present invention, a radical polymerization initiator having a hydrogen abstracting action is exemplified by 9-oxosulfur A radical polymerization initiator, a diphenylketone radical polymerization initiator, etc. are mentioned as an example. The aforementioned radical polymerization initiator, with 9-oxo sulfur A radical polymerization initiator is preferred. 9-oxygen sulfur The radical polymerization initiator is exemplified by the compound represented by the above formula (1). Specific examples of the compound represented by the formula (1) include, for example, 9-oxosulfur Dimethyl 9-oxosulfur Diethyl 9-oxosulfur Isopropyl 9-oxosulfur Chlorine 9-oxosulfur Wait. In the compound of the formula (1), diethyl 9-oxosulfuric acid wherein R ¹ and R ² are -CH ₂ CH ₃ Very good.

When the active energy ray-curable adhesive composition contains a radically polymerizable compound having an active methylene group and a radical polymerization initiator having a hydrogen abstracting action, it is preferred to contain a total amount of the curable component of 100% by weight. In the case of %, it is 1 to 50% by weight of the radically polymerizable compound having an active methylene group, and 0.1 to 10 parts by weight of a radical polymerization initiator based on 100 parts by weight of the total amount of the curable component.

As described above, in the present invention, in the presence of a radical polymerization initiator having a hydrogen abstracting action, a methylene group of a radically polymerizable compound having an active methylene group generates a radical, and the methylene group is The hydroxyl group of the polarizer such as PVA reacts to form a covalent bond. Therefore, in order to generate a radical in the methylene group of the radically polymerizable compound having an active methylene group, the covalent bond is sufficiently formed, and when the total amount of the curable component is 100% by weight, it is preferable to contain an active sub The methyl radical polymerizable compound is preferably from 1 to 50% by weight, preferably from 3 to 30% by weight. In order to sufficiently improve the water resistance and improve the adhesion in a non-dry state, it is preferred to set the radically polymerizable compound having an active methylene group to 1% by weight or more. On the other hand, when it is more than 50% by weight, there is a case where hardening failure of the adhesive layer occurs. Further, the radical polymerization initiator having a hydrogen abstracting action is preferably contained in an amount of 0.1 to 10 parts by weight, based on 100 parts by weight of the total amount of the curable component, and preferably 0.3 to 9 parts by weight. In order to sufficiently carry out the hydrogen abstraction reaction, the radical polymerization initiator is preferably used in an amount of 0.1 part by weight or more. On the other hand, when it is more than 10 parts by weight, there is a case where the composition is not completely dissolved.

<Cationic Polymerization Curing Adhesive>

A hardening component of a cationic polymerization hardening adhesive, which may be epoxy A compound of a thiol or oxo group is exemplified. The epoxy group-containing compound is not particularly limited as long as it has at least two epoxy groups in the molecule, and various generally known curable epoxy compounds can be used. Preferred examples of the epoxy compound include a compound having at least two epoxy groups and at least one aromatic ring in the molecule (aromatic epoxy compound), or at least two epoxy groups in the molecule, and at least One compound (alicyclic epoxy compound) or the like which forms between two adjacent carbon atoms of the alicyclic ring. However, in the adhesive layer, in order to realize the component gradient structure with respect to the component A, even when a cationic polymerization hardening type adhesive is used, the active energy ray-curable adhesive composition needs to contain a log Pow indicating that the octanol/water distribution coefficient is - The A component of 1~1 and the log component of logPow are 2-7.

<Photocationic polymerization initiator>

The curable component of the cationically polymerizable adhesive contains the epoxy compound and the oxonium compound described above, and since these are all cured by cationic polymerization, the photocationic polymerization initiator is blended. The photocationic polymerization initiator can be irradiated with an active energy ray such as visible light, ultraviolet light, X-rays, or electron beam to generate a cationic species or a Lewis acid to initiate polymerization of an epoxy group or an oxon group.

<selected from at least one organometallic compound selected from the group consisting of metal alkoxides and metal chelate compounds>

The metal alkoxide is a compound in which at least one or more alkoxy groups as an organic group are bonded to a metal, and the metal chelate compound is a compound which is bonded to or coordinated with an organic group through an oxygen atom. The metal is preferably titanium, aluminum or zirconium. Among them, aluminum and zirconium are more reactive than titanium, and the pot life of the adhesive composition is applicable. It is shortened, and then the effect of improving the water resistance is lowered. Therefore, it is preferable to use titanium as the metal of the organometallic compound from the viewpoint of improving the subsequent water resistance of the adhesive layer.

When the hardening type adhesive composition for a polarizing film of the present invention contains a metal alkoxide as the organometallic compound, it is preferred to use a metal alkoxide having an organic group having 4 or more carbon atoms, and preferably 6 or more. When the carbon number is 3 or less, the pot life of the adhesive composition becomes short, and the effect of improving the water resistance is lowered. An organic group having 6 or more carbon atoms is exemplified by an octyloxy group. Examples of preferred metal alkoxides include, for example, tetraisopropyl titanate, tetra-n-butyl titanate, butyl titanate dimer, tetraoctyl titanate, and third amyl titanium. Acid ester, tetra-tert-butyl titanate, tetrastearyl strontium titanate, zirconium tetraisopropoxide, tetra-n-butadiene zirconia, tetra-octyl zirconia, tetra-butadiene zirconia, tetra-propoxide zirconia, Aluminum dibutoxide, aluminum aluminum ethoxide, aluminum isopropoxide, aluminum butoxide, aluminum diisopropoxide, aluminum dibutoxide, and aluminum monobutylbutoxide diisopropoxide. Among them, tetraoctyl titanate is also preferred.

When the hardenable adhesive composition for a polarizing film of the present invention contains a metal chelate compound as the organometallic compound, it is preferred to contain a metal chelate compound having an organic group having 4 or more carbon atoms. When the carbon number is 3 or less, the pot life of the adhesive composition becomes short, and the effect of improving the water resistance is lowered. The organic group having 4 or more carbon atoms may, for example, be an ethyl acetoxyacetone group, an ethyl acetoacetate group, an isostearyl group or an octa Among these, from the viewpoint of improving the subsequent water resistance of the adhesive layer, the organic group is preferably an ethyl acetoxyacetone group or an ethyl acetoacetate group. Examples of preferred metal chelates include, for example, titanium acetacetate, titanium oxyacetate, and Tetraethyl acetonate titanium, ethyl acetonitrile acetate titanium, polyhydroxystearic acid titanium, dipropoxy-bis(acetonitrile) titanium, dibutoxy titanium-bis(octene glycolic acid), two Titanium titanate-bis(ethylacetamidine acetate), titanium lactate, titanium diethanolamine, titanium triethanolamine, dipropoxy titanium-bis(lactic acid), dipropoxy titanium-bis(triethanolamine), Di-n-butoxytitanium-bis(triethanolamine), tri-n-butoxytitanium mono-stearic acid, diisopropoxy. Bis(ethylacetamidine acetate) titanium, diisopropoxy. Bis(ethinyl acetate) titanium, diisopropoxy. Bis(acetylacetone)titanium, titanium phosphate compound, titanium ammonium lactate, titanium-1,3-propanedioxybis(ethylacetamidine acetate), titanium dodecylbenzenesulfonate, amine B Base aminoethanol ester titanium, tetraethylguanidinium acetone zirconium, zirconium acetonate, zirconium acetonide, zirconium acetoacetate, ethyl zirconium acetate, zirconium acetate, zirconium acetate, tri-n-butoxyethyl Zirconium acetate, zirconium di-n-butoxy bis(ethylacetamidine acetate), zirconium n-butoxy oxy (ethyl acetoacetate), cerium (n-propyl acetamidine acetate) Zirconium, lanthanum (ethionylacetate) zirconium, lanthanum (ethyl acetoacetate) zirconium, aluminum ethyl acetonitrile acetate, aluminum ethane acetoacetate, acetoacetate aluminum double Ethylacetamidine acetate, aluminum diisopropoxyethylacetate acetate, aluminum diisopropoxyacetamidine, aluminum isopropoxide bis(ethylacetamidine acetate), isopropyl Oxygen bis(acetamidineacetone) aluminum, ginseng (ethyl acetoacetate) aluminum, ginseng (acetonitrile) aluminum, monoethyl acetonide. Bis(ethylacetamidine acetate) aluminum. Among them, titanium acetonitrile acetone and titanium ethyl acetonitrile acetate are preferred.

The organometallic compound which can be used in the present invention may, for example, be an organic carboxylic acid metal salt such as zinc octylate, zinc laurate, zinc stearate or tin octylate, zinc acetonate chelate or benzamidine. A zinc chelate compound such as an acetone zinc chelate compound, a benzhydrylmethane zinc chelate compound or an ethyl acetate ethyl zinc chelate compound.

<Other ingredients>

The active energy ray-curable adhesive composition of the present invention may further contain the following components.

<The viscosity is 15mPa. Above alkoxyalkylene containing compounds>

The viscosity is 15mPa. For the above alkoxyalkylene group-containing compound, a lower molecular weight compound having a higher alkoxyalkyl group-containing alkyl group may be used as a compound having a high molecular weight, and it may preferably be used in the side chain and/or the terminal of the molecule to contain an alkoxyalkyl group. A polymer or oligomer type alkoxyalkylene containing compound.

The polymer having an alkoxyalkylalkyl group in the side chain and/or the molecular end may preferably be a structure in which the main chain is a (meth)acrylic polymer structure. Examples of the (meth)acrylic monomer constituting the acrylic polymer include (meth)acrylic acid; methyl (meth)acrylate; ethyl (meth)acrylate; and n-propyl (meth)acrylate; Isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-amyl (meth)acrylate, (methyl) N-hexyl acrylate, cyclohexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate Ester, decyl (meth) acrylate, isodecyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, (meth) acrylate Ester, dicyclopentanyl (meth)acrylate, dodecyl (meth)acrylate, phenyl (meth)acrylate, phenylacetate (meth)acrylate, benzyl (meth)acrylate, (A) 2-methoxyethyl acrylate, 3-methoxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylic acid (meth) acrylate such as lipoester ester or isobutyl methacrylate. In the present invention, (meth)acrylic acid means acrylic acid and/or methacrylic acid, and the following "(meth)" is the same.

The viscosity of the polymer containing alkoxyalkylalkyl group at the side chain and / or molecular end is 15mPa. Above s, preferably 10000 mPa. Above s, the better is 100000mPa. s above. The upper limit of the viscosity is not particularly limited, but when considering the workability, etc., it is 2000000 mPa. The following is better.

The oligomer-type alkoxyalkylene group-containing compound is exemplified by a hydrolysis-condensation product of a low molecular weight alkoxyalkylene group-containing compound. A commercially available product can be suitably used as the hydrolysis-condensation product of the low molecular weight alkoxyalkyl group-containing alkyl compound. For example, X-41-1059A, X-24-9590, KR-516, and X manufactured by Shin-Etsu Chemical Co., Ltd. -41-1805, KR513, X-40-9296, KR-511, KR-500, X-40-9225, X-40-9246, X-40-9250, KR-401N, X-40-9227, KR -510, KR-9218, KR-213, etc.

The oligomer-type alkoxyalkyl group-containing compound has a viscosity of 15 mPa. Above s, preferably 20mPa. Above s, the better is 25mPa. s above. The upper limit of the viscosity is not particularly limited, but when it is considered to be workability, etc., it is 100000 mPa. The following is better.

In the present invention, the viscosity is 15 mPa. The content ratio of the above alkoxyalkylene group-containing compound is preferably in the range of 0.2 to 15 parts by weight, and preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the total amount of the active energy ray-curable component. More preferably 5 parts by weight. When the blending amount is more than 15 parts by weight, the storage stability of the adhesive composition is poor, and the ratio of the composition of the polarizer or the protective film is relatively insufficient to cause a decrease in the adhesiveness. Moreover, when it is less than 0.2 part by weight, the effect of sufficiently exhibiting water resistance is obtained.

<Acrylic oligomer>

The active energy ray-curable adhesive composition used in the present invention may contain an acrylic resin obtained by polymerizing a (meth)acrylic monomer in addition to the curable component of the radical polymerizable compound or the cationic polymerization hardening adhesive. Oligomer. When the active energy ray-curable adhesive composition contains an acrylic oligomer formed by polymerizing a non-polymerizable (meth)acrylic monomer, the composition of the adhesive composition between the polarizing member and the transparent protective film is easy. The partial gradient makes it easier to obtain a composition gradient structure in which the concentration of the A component on the polarizer side becomes high. Therefore, it is preferable to further improve the adhesion and water resistance of the adhesive layer to the polarizer and the transparent protective film. In addition, the active energy ray-curable adhesive composition contains an acrylic oligomer component, which can reduce the active energy ray to the composition. Hardening shrinkage at the time of hardening, and lowering the interfacial stress of the adherend with the polarizer and the transparent protective film. As a result, a decrease in the adhesion between the adhesive layer and the adherend can be suppressed. In order to more reliably obtain the composition gradient structure of the cured layer (adhesive layer) and more sufficiently suppress the hardening shrinkage, when the total amount of the active energy ray-curable adhesive composition is set to 100% by weight, acrylic acid is preferably used. The content of the oligomer is preferably 5 to 30% by weight, and preferably 10 to 20% by weight.

Considering the workability and uniformity at the time of coating, the active energy ray-curable adhesive composition preferably has a low viscosity, so that the acrylic oligomer (A) formed by polymerizing a (meth)acrylic monomer is also low. The viscosity is good. The low-viscosity acrylic oligomer preferably has a weight average molecular weight (Mw) of 15,000 or less, more preferably 10,000 or less, and most preferably 5,000 or less. On the other hand, in order to further deviate the component of the adhesive composition between the polarizer and the transparent protective film, the weight average molecular weight (Mw) of the acrylic oligomer (A) is preferably 500 or more, and more preferably 1,000 or more. Preferably, it is particularly preferably 1500 or more. Specific examples of the (meth)acrylic monomer constituting the acrylic oligomer (A) include methyl (meth)acrylate, ethyl (meth)acrylate, and n-propyl (meth)acrylate. Isopropyl methacrylate, 2-methyl-2-nitropropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, S-(meth) acrylate Butyl ester, tert-butyl (meth)acrylate, n-amyl (meth)acrylate, third amyl (meth)acrylate, 3-pentyl (meth)acrylate, 2,2 (meth)acrylate - dimethyl butyl ester, n-hexyl (meth) acrylate, hexadecyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylate (meth)acrylic acid (carbon number 1-20) alkyl esters such as 4-methyl-2-propylamyl ester and N-octadecyl (meth)acrylate, and more preferably, for example, (meth)acrylic acid a cycloalkyl ester (for example, cyclohexyl (meth)acrylate, cyclopentyl (meth)acrylate), arylalkyl (meth)acrylate (for example, benzyl (meth)acrylate, etc.), polycyclic (meth) acrylate (for example, 2-(meth)acrylic acid) Ester, 2-(meth)acrylic acid Methyl ester, (meth)acrylic acid 5-nor Alkene-2-yl-methyl ester, 3-methyl-2-northylmethyl (meth)acrylate, etc.), hydroxyl group-containing (meth) acrylate (for example, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth)acrylate, 2,3-dihydroxypropylmethyl-butyl (meth)acrylate, etc.), alkoxy or phenoxy-containing (meth) acrylate (2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-methoxymethoxyethyl (meth)acrylate, 3-methoxy (meth)acrylate Butyl ester, ethyl carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, etc.), epoxy group-containing (meth) acrylates (for example, (meth) acrylate propylene Ester, etc., halogen-containing (meth) acrylates (for example, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate , (tetra) propyl (meth) acrylate, hexafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptafluorodecyl (meth) acrylate, etc., (meth) acrylate An aminoalkylalkyl ester (for example, dimethylamine ethyl (meth)acrylate, etc.) or the like. These (meth) acrylates may be used alone or in combination of two or more. Specific examples of the acrylic oligomer (A) include "ARUFON" manufactured by Toagosei Co., Ltd., "ACTFLOW" manufactured by Soken Chemical Co., Ltd., and "JONCRYL" manufactured by BASF JAPAN Co., Ltd., for example.

When the acrylic oligomer (A) is a liquid, it is preferably used because it does not require consideration of the solubility to the adhesive composition. The acrylic oligomer (A) is a general liquid when the glass transition temperature (Tg) is less than 25 °C. Moreover, it is preferable that the acrylic oligomer (A) contains a polar functional group in order to achieve compatibility with the adhesive composition and the deposition of components in the adhesive layer. The polar functional group may, for example, be a hydroxyl group, an epoxy group, a carboxyl group, an alkoxythio group or the like. Specifically, for example, "ARUFON UH Series", "ARUFON UC Series", "ARUFON UF Series", "ARUFON UG Series", and "ARUFON US Series" (all manufactured by Toagos Corporation) are exemplified. Among them, it is preferable to contain an epoxy group from the viewpoint that it is expected that the interaction with the polarizing member will enhance the adhesion. Specifically, "ARUFON UG-4000" and "ARUFON UG-4010" (all manufactured by Toagosei Co., Ltd.) are exemplified.

<Photoacid generator>

The active energy ray-curable adhesive composition may contain a photoacid generator. When the photo-acid generator is contained in the active energy ray-curable resin composition, the water resistance and durability of the adhesive layer can be improved stepwise compared to the case where the photo-acid generator is not contained. The photoacid generator can be represented by the following formula (3) Show.

General formula (3) [Chemical 3] L ⁺ X ^-

(However, L + represents a cation and any of, X ^-. Selected from the group consisting represents _{^{PF6 6 -, SbF 6 -,}} AsF 6 -, SbCl 6 -, BiCl 5 -, SnCl 6 -, ClO 4 -, two thiamin a relative anion in the group of formate anions and SCN-.).

Among the anions exemplified above, the relative anion X- in the formula (3) is preferably PF ₆ ^- , SbF ₆ ^- and AsF ₆ ^- , and particularly preferably PF ₆ ^- or SbF ₆ ^- .

Therefore, specific examples of the phosphonium salt constituting the photoacid generator which can be used in the present invention include "Cyracure UVI-6992", "Cyracure UVI-6974" (above, manufactured by DOW Chemical Japan Co., Ltd.), and "ADEKA". OPTOMER SP150", "ADEKA OPTOMER SP152", "ADEKA OPTOMER SP170", "ADEKA OPTOMER SP172" (above, ADEKA Co., Ltd.), "IRGACURE250" (manufactured by Chiba Specialty Chemicals), "CI-5102", "CI -2855" (above, manufactured by Japan Soda Corporation), "SAN-AID SI-60L", "SAN-AID SI-80L", "SAN-AID SI-100L", "SAN-AID SI-110L", "SAN -AID SI-180L (above, Sanshin Chemical Co., Ltd.), "CPI-100P", "CPI-100A" (above, SAN-APRO Co., Ltd.), "WPI-069", "WPI-113" "WPI-116", "WPI-041", "WPI-044", "WPI-054", "WPI-055", "WPAG-281", "WPAG-567", "WPAG-596" (above, Wako Pure Chemical Industries, Ltd.) is a preferred specific example of the photoacid generator of the present invention.

The content of the photoacid generator is 10 parts by weight or less, preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, even more preferably 0.1 to 3 parts by weight per 100 parts by weight of the total amount of the curable component. .

<Compound containing either alkoxy group or epoxy group>

In the active energy ray-curable adhesive composition, a photoacid generator and a compound containing either an alkoxy group or an epoxy group may be used in combination.

(epoxy-based compounds and polymers)

When 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 is used, two or more molecules having an epoxy group may be used in combination. Reactive functional group compound. Here, the functional group having reactivity with an epoxy group may, for example, be a carboxyl group, a phenolic hydroxyl group, a mercapto group, a primary or secondary aromatic group or the like. It is considered that the third-order hardening property is particularly preferable in that one or more of these functional groups are contained in one molecule.

a polymer having one or more epoxy groups in the molecule, and an epoxy resin as an example, a bisphenol A type epoxy resin derived from bisphenol A and epichlorohydrin, and a bisphenol F and epichlorohydrin Derivatized bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolac Epoxy resin, alicyclic epoxy resin, diphenyl ether epoxy resin, hydroquinone epoxy resin, naphthalene epoxy resin, biphenyl epoxy resin, fluorene epoxy resin, trifunctional Polyfunctional epoxy resin such as epoxy resin or 4-functional epoxy resin, epoxy propyl ester epoxy resin, epoxy propyl amine epoxy resin, intramethylene urea resin, heterotrimerization A cyanic acid type epoxy resin, an aliphatic chain epoxy resin, or the like, which may be halogenated or hydrogenated. Commercially available epoxy resin products, for example, JER COAT 828, 1001, 801N, 806, 807, 152, 604, 630, 871, YX8000, YX8034, YX4000, DIC Corporation, manufactured by Japan Epoxy Resins Co., Ltd. Epikuron 830, EXA835LV, HP4032D, HP820, ADEKA EP4100 series, EP4000 series, EPU series, Celloxide series (2021, 2021P, 2083, 2085, 3000, etc.) manufactured by DAICEL Chemical Co., Ltd., Epolead series, EHPE series, YD series manufactured by Nippon Steel Chemical Co., Ltd., YDF series, YDCN series, YDB series, phenoxy resin (polyhydroxy polyether synthesized from bisphenols and epichlorohydrin and having epoxy groups at both ends; YP series, etc.), Denacol series manufactured by Nagase ChemteX Co., Ltd. The Epolight series made by Chemical Society, etc., is not limited to this. Two or more of these epoxy resins may be used in combination.

(Alkoxy compound and polymer)

The compound having an alkoxy group in the molecule is not particularly limited as long as it has one or more alkoxy groups in the molecule, and any well-known one can be used. As such a compound, a melamine compound, an amine resin, a decane coupling agent or the like can be typically exemplified.

The blending amount of the compound containing any of the alkoxy group and the epoxy group is usually 30 parts by weight or less based on 100 parts by weight of the total amount of the curable component, and when the content of the compound in the composition is too large, the adhesion is decreased. The situation in which the resistance to fall of the drop test deteriorated. The content of the compound in the composition is preferably 20 parts by weight or less. On the other hand, from the viewpoint of water resistance, the composition It is preferable to contain 2 parts by weight or more of the compound, and it is preferable to contain 5 parts by weight or more.

<decane coupling agent>

When the active energy ray-curable curing type is used for the curable adhesive for a polarizing film of the present invention, the decane coupling agent is preferably a compound having active energy ray curability, but it can be imparted even if it is not active energy ray curability. The same water resistance.

Specific examples of the decane coupling agent, and the active energy ray-curable compound may, for example, be vinyl trichloromethane, vinyl trimethoxy decane, vinyl triethoxy decane, or 2-(3,4 epoxycyclohexyl). Ethyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 3-glycidoxypropyltriethyl Oxy decane, p-styryl trimethoxy decane, 3-methyl propylene methoxypropyl methyl dimethoxy decane, 3-methyl propylene oxypropyl trimethoxy decane, 3-methyl propylene醯 丙基 propyl methyl diethoxy decane, 3-methyl propylene oxypropyl triethoxy decane, 3- propylene oxypropyl trimethoxy decane, and the like.

Preferably, 3-methacryloxypropyltrimethoxydecane or 3-propenyloxypropyltrimethoxydecane is used.

A specific example of the inactive energy ray-curable decane coupling agent is preferably an amine-based decane coupling agent (D1). Specific examples of the amino group-containing decane coupling agent (D1) include, for example, γ-aminopropyltrimethoxydecane, γ-aminopropyltriethoxydecane, and γ-aminopropyltriisopropyl. Oxydecane, γ-aminopropylmethyldimethoxydecane, γ-aminopropylmethyldiethoxydecane, γ-(2-aminoethyl)aminopropyltrimethoxydecane , γ-(2-aminoethyl)aminopropylmethyldimethoxydecane, γ-(2-aminoethyl)aminopropyl Triethoxy decane, γ-(2-aminoethyl)aminopropylmethyldiethoxydecane, γ-(2-aminoethyl)aminopropyltriisopropoxydecane, γ -(2-(2-Aminoethyl)aminoethyl)aminopropyltrimethoxydecane, γ-(6-aminohexyl)aminopropyltrimethoxydecane, 3-(N-B Amino)-2-methylpropyltrimethoxydecane, γ-ureidopropyltrimethoxydecane, γ-ureidopropyltriethoxydecane, N-phenyl-γ-aminopropyl Trimethoxydecane, N-benzyl-γ-aminopropyltrimethoxydecane, N-vinylbenzyl-γ-aminopropyltriethoxydecane, N-cyclohexylaminomethyltriethyl Oxydecane, N-cyclohexylaminomethyldiethoxymethyldecane, N-phenylaminomethyltrimethoxydecane, (2-aminoethyl)aminomethyltrimethoxydecane, N,N Amino-containing decane such as '-bis[3-(trimethoxyindolyl)propyl]ethylenediamine; N-(1,3-dimethylbutylene)-3-(triethoxyindenyl) a ketimine-type decane such as 1-propanamine.

The amine-based decane coupling agent (D1) may be used alone or in combination of plural kinds. In order to ensure good adhesion, γ-aminopropyltrimethoxydecane, γ-(2-aminoethyl)aminopropyltrimethoxydecane, γ-(2-aminoethyl B) Aminopropylmethyldimethoxydecane, γ-(2-aminoethyl)aminopropyltriethoxydecane, γ-(2-aminoethyl)aminopropylmethyl Diethoxydecane, N-(1,3-dimethylbutylidene)-3-(triethoxyindolyl)-1-propanamine is preferred.

The blending amount of the decane coupling agent is preferably in the range of 0.01 to 20 parts by weight, more preferably 0.05 to 15 parts by weight, still more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the total amount of the curable component. This is because when the blending amount is more than 20 parts by weight, the storage stability of the adhesive is deteriorated, and when it is less than 0.1 part by weight, the water-resistant adhesion effect is not sufficiently exhibited.

Specific examples of the active energy ray-curable decane coupling agent other than the above may, for example, be 3-ureidopropyltriethoxydecane, 3-chloropropyltrimethoxydecane or 3-mercaptopropylmethyl Dimethoxydecane, 3-mercaptopropyltrimethoxydecane, bis(triethoxydecylpropyl) tetrasulfide, 3-isocyanatepropyltriethoxydecane, imidazolium, and the like.

<Compound with vinyl ether group>

When the curable adhesive composition for a polarizing film of 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. Although the reason why this effect can be obtained is not clear, it is presumed that one of the reasons is that the vinyl ether group having a compound having a vinyl ether group interacts with a polarizer to increase the adhesion between the polarizer and the adhesive layer. In order to further improve the subsequent water resistance of the polarizer and the adhesive layer, the compound having a vinyl ether group is preferably a radical polymerizable compound having a vinyl ether group. Further, the content of the compound having a vinyl ether group is preferably 0.1 to 19 parts by weight based on 100 parts by weight of the total amount of the curable component.

<Compounds which produce keto-enol tautomerism>

The curable adhesive composition for a polarizing film of the present invention may contain a compound which produces a keto-enol tautomerism. For example, in the use of an adhesive composition obtained by blending an adhesive composition containing a crosslinking agent or a crosslinking agent, a form containing a compound which produces the aforementioned keto-enol tautomerism can be preferably used. Thereby, it is possible to suppress an excessive increase in viscosity or gelation of the blending of the organometallic compound and a composition of the microgel, and to achieve an effect of prolonging the pot life of the composition.

a compound which produces the aforementioned keto-enol tautomerism Various β-dicarbonyl compounds are used. Specific examples include acetamidine acetone, 2,4-hexanedione, 3,5-heptanedione, 2-methylhexane-3,5-dione, and 6-methylheptane-2. Β-diketones such as 4-dione and 2,6-dimethylheptane-3,5-dione; methyl ethyl acetate, ethyl acetate, isopropyl acetate, acetonitrile Ethyl acetate such as butyl butyl; ethyl propyl sulfonate, ethyl propyl sulfonate, isopropyl propyl thioacetate, butyl propyl thioglycolate, etc.; Butyric acid ethyl acetate, isobutyl decyl ethyl acetate, isobutyl thioglycolic acid isopropyl, isobutyl decyl acetic acid, tert-butyl and the like, isobutyl decyl acetate; malonic acid methyl ester, malonic acid ethyl ester and the like malonic esters, etc. . Preferred examples of the compound include acetamidineacetone and acetamidine acetate. The compound which produces a keto-enol tautomerism may be used singly or in combination of two or more.

The amount of the compound which produces the keto-enol tautomerism is, for example, 0.05 parts by weight to 10 parts by weight based on 1 part by weight of the organometallic compound, and is 0.2 parts by weight to 3 parts by weight (for example, 0.3 parts by weight). ~2 parts by weight) is preferred. When the amount of the compound used is less than 0.05 part by weight based on 1 part by weight of the organometallic compound, the effect of use may not be sufficiently exhibited. On the other hand, when the compound is used in an amount of more than 10 parts by weight based on 1 part by weight of the organometallic compound, the organometallic compound excessively interacts, and the water resistance of the object is not easily exhibited.

<Additives other than the aforementioned>

Further, various additives may be blended as other optional components in the active energy ray-curable adhesive composition used in the present invention within the range not impairing the object and effect of the present invention. The additive may, for example, be an epoxy resin. Polyamide, polyamidimide, polyurethane, polybutadiene, polychloroprene, polyether, polyester, styrene-butadiene block copolymer, petroleum resin, II a polymer or oligomer such as a toluene resin, a ketone resin, a cellulose resin, a fluorine-based oligomer, an anthrone-based oligomer, or a polysulfide-based oligomer; thiodiphenylamine, 2,6-di-third Polymerization inhibitors such as 4-methylphenol; polymerization initiator; leveling agent; wettability improver; surfactant; plasticizer; ultraviolet absorber; inorganic filler; pigment; dye, etc.

The additive is usually 0 to 10 parts by weight, preferably 0 to 5 parts by weight, based on 100 parts by weight of the total amount of the curable component, and most preferably 0 to 3 parts by weight.

<Adhesive viscosity>

The active energy ray-curable adhesive composition used in the present invention contains the curable component, and the adhesiveness of the adhesive composition is preferably 100 cp or less at 25 ° C from the viewpoint of coatability. On the other hand, when the curable adhesive for a polarizing film of the present invention is more than 100 cp at 25 ° C, the temperature of the adhesive at the time of application can be controlled and adjusted to 100 cp or less. The preferred range of viscosity is from 1 to 80 cp, preferably from 10 to 50 cp. The viscosity can be measured using an E-type viscometer TVE22LT manufactured by Toki Sangyo Co., Ltd.

Further, from the viewpoint of safety, in the active energy ray-curable adhesive composition used in the present invention, the curable component is preferably a material which uses low skin irritation. Skin irritation can be judged by the index of P.I.I. P.I.I is widely used as a measure of skin irritation and measured by Draize. The measured value is displayed in the range of 0 to 8. The smaller the value is, the lower the irritancy is judged, and the error of the measured value is large, so it is used as a reference value. good. P.I.I is preferably 4 or less, preferably 3 or less, and most preferably 2 or less.

The polarizing film of the present invention has a transparent protective film laminated on at least one of the polarizing members through the adhesive, and is characterized in that the concentration of the component A on the polarizer side is high. The concentration distribution in the thickness direction of the subsequent layer can be analyzed by, for example, etching using cluster ions repeatedly and TOF-SIMS measurement. Specifically, a specific secondary ion is selected from each component of the adhesive composition, and by comparing the intensity ratio of the secondary ion in the thickness direction, the component which is located in the thickness direction portion can be specified. The evaluation was performed by calculating the ratio of the A component of the adhesive layer at the polarizer side interface when the ratio of the A component having a log Pow of -1 to 1 in the center portion in the thickness direction of the adhesive layer was 1. When the ratio of the component A of the adhesive layer to the polarizer side interface is more than 1, it means that the concentration of the component A on the polarizer side is high. The ratio of the component A at the side of the polarizer is preferably 1.05 or more, preferably 1.10 or more, and most preferably 1.20 or more.

<Binder layer>

The thickness of the adhesive layer formed by the active energy ray-curable adhesive composition is preferably controlled to 0.1 to 3 μm. The thickness of the subsequent layer is preferably from 0.3 to 2 μm, more preferably from 0.5 to 1.5 μm. When the thickness of the adhesive layer is 0.1 μm or more, it is preferable because the occurrence of defective defects due to the cohesive force of the adhesive layer or the occurrence of poor appearance (bubbles) during lamination can be suppressed. On the other hand, when the adhesive layer is thicker than 3 μm, the polarizing film cannot satisfy the durability.

Further, the active energy ray-curable adhesive composition preferably has a Tg of 60 ° C or more selected from the adhesive layer formed thereon, preferably 70 ° C or higher, more preferably 75 ° C or higher, and 100. Above °C is better, then Above 120 ° C is preferred. On the other hand, when the Tg of the adhesive layer is too high, the flexibility of the polarizing film is lowered. Therefore, the Tg of the adhesive layer is preferably 300 ° C or less, more preferably 240 ° C or less, and still more preferably 180 ° C or less. Tg (glass transition temperature) can be measured under the following measurement conditions using a dynamic viscoelasticity measuring device RSAIII manufactured by TA Instrument.

Sample size: width 10 mm, length 30 mm, clamping distance 20 mm, measurement mode: stretching, frequency: 1 Hz, heating rate: 5 ° C / min.

The dynamic viscoelasticity measurement was performed and used as the peak top temperature Tg of tan δ.

Further, the active energy ray-curable adhesive composition is preferably designed such that the storage elastic modulus of the adhesive layer formed therefrom is 1.0 × 10 ⁶ Pa or more in a field of 70 ° C or less. More preferably at least 1.0 × 10 ⁷ Pa. The storage elastic modulus of the subsequent layer will affect the crack of the polarizer when the polarizing film is thermally circulated (-40 ° C to 80 ° C, etc.), and when the storage elastic modulus is low, the polarizing member crack is likely to occur. The temperature range with a high storage modulus of elasticity is preferably 80 ° C or less, and preferably 90 ° C or less. The storage elastic modulus can be measured simultaneously with the Tg (glass transition temperature) using the TA Instrument dynamic viscoelasticity measuring device RSAIII under the same measurement conditions. The measurement of dynamic viscoelasticity was carried out using the value of the storage elastic modulus (E').

The polarizing film of the present invention can be produced, for example, by a polarizing film manufacturing method comprising the steps of: applying a reactive energy ray-curable adhesive composition to at least one of a polarizing member and a transparent protective film; and a bonding step; And bonding the polarizing member and the transparent protective film; and subsequently, the polarizing member and the transparent protective film are passed through the adhesive layer, and the connecting The primer layer is obtained by irradiating the active energy ray from the surface side of the polarizer or the surface side of the transparent protective film to harden the active energy ray-curable adhesive composition.

However, in the adhesive layer of the present invention, in order to increase the concentration of the component A on the polarizer side, it is preferred to adjust the temperature of the active energy ray-curable adhesive composition to 15 after the coating step to the subsequent step. ~40 ° C. The reason why the temperature condition is set to be preferable is as follows.

In the subsequent layer, in order to increase the concentration of the component A on the polarizer side, a phase is formed between the coating step and the bonding step, that is, in the stage where the adhesive composition is composed of the monomer components before the polymerization starts. Component gradient structure of component and component B. In general, when the temperature of the composition containing two or more components is high, the components are easily dissolved, and as a result, the component gradient structure is not easily obtained. Therefore, in the method for producing a polarizing film of the present invention, the temperature of the active energy ray-curable adhesive composition between the coating step and the subsequent step is adjusted to 15 to 40 ° C, and the components A and B become Incompletely compatible, as a result, a component gradient structure of the A component and the B component is easily formed. In order to more reliably form the component gradient structure of the component A and the component B, the temperature of the active energy ray-curable adhesive composition after the coating step to the subsequent step is preferably adjusted to 20 to 35 ° C, preferably adjusted to 23 ~32 ° C is better.

In addition, the method of setting the temperature of the active energy ray-curable adhesive composition in the above range is exemplified as a method in which the gas ambient temperature at the time of performing each step is set within the above range.

Moreover, the polarizing film of the present invention can also be produced by the following manufacturing method; a method for producing a polarizing film which is obtained by laminating at least one of the polarizing members through a layer of a transparent protective film; The manufacturing method is characterized in that the adhesive layer is formed of a cured layer obtained by irradiating an active energy ray-curable adhesive composition with an active energy ray, and the manufacturing method includes the following steps: first coating a step of applying a first active energy ray-curable adhesive composition containing the component A to the bonding surface of the polarizer, wherein the log component of the octanol/water distribution coefficient of the component A is -1 to 1; the second coating a second active energy ray-curable adhesive composition containing a component B having a log Pow of 2 to 7 applied to the bonding surface of the transparent protective film; and a bonding step of bonding the polarizing member and the transparent protective film And a step of: subsequently applying the polarizer and the transparent protective film through the adhesive layer, wherein the adhesive layer is irradiated with active energy rays from the surface of the polarizer or the surface of the transparent protective film to cause the active energy The composition of the wire-curable adhesive composition is cured; and the concentration of the component A on the polarizer side of the adhesive layer formed after the subsequent step is high.

The manufacturing method includes a first coating step of applying a first active energy ray-curable adhesive composition containing an A component to a bonding surface of the polarizing member, wherein the log component of the octanol/water distribution coefficient of the component A is In the second coating step, a second active energy ray-curable adhesive composition containing a component B having a log Pow of 2 to 7 is applied to the bonding surface of the transparent protective film. Thereby, the concentration of the A component on the polarizer side of the adhesive layer formed after the subsequent step becomes higher, and the component gradient structure in which the A component concentration on the polarizer side becomes higher is more surely obtained. In order to form the gradient structure of the component more reliably, when the total amount of the first active energy ray-curable adhesive composition applied to the bonding surface of the polarizer is 100% by weight, logPow is preferably -1~ 1 of A The content of the component is preferably 50 to 95% by weight, and preferably 60 to 80% by weight. Similarly, when the total amount of the second active energy ray-curable adhesive composition applied to the bonding surface of the transparent protective film is 100% by weight, it is preferable to set the content of the B component having a log Pow of 2 to 7. It is preferably from 50 to 95% by weight, preferably from 60 to 80% by weight. Further, the ratio of the first active energy ray-curable adhesive composition to the second active energy ray-curable adhesive composition is preferably 5:95 to 50:50, and 10:10 for each coating thickness ratio. 90~40:60 is better.

In the method for producing a polarizing film of the present invention, the polarizing member and the transparent protective film may be subjected to surface modification treatment before applying the active energy ray-curable adhesive composition. Specific treatments can be exemplified by corona treatment, plasma treatment, treatment by saponification treatment, and the like.

The coating method of the active energy ray-curable adhesive composition can be appropriately selected depending on the viscosity of the composition or the thickness of the intended object. Examples of the coating method include a reverse coater, a gravure coater (direct, reverse or lithographic), a rod reverse coater, a roll coater, a die coater, a bar coater, a bar coater, and the like. Others, a method such as a dipping method can be suitably used for coating.

The polarizing member and the transparent protective film are bonded through the active energy ray-curable adhesive composition coated as described above. The bonding of the polarizing member and the transparent protective film can be carried out by roll bonding or the like.

The active energy ray-curable adhesive composition preferably contains at least one organometallic compound selected from the group consisting of metal alkoxides and metal chelates. Further, the first active energy ray-curing type is continued The agent composition preferably contains the aforementioned organometallic compound. Further, the metal of the organometallic compound contained in the active energy ray-curable adhesive composition is preferably titanium.

The active energy ray-curable adhesive composition preferably contains the metal alkoxide as the organometallic compound, and the organic alkoxide of the metal alkoxide preferably has 6 or more carbon atoms, and the active energy ray-curable type is followed by The agent composition preferably contains the metal chelate compound as the organometallic compound, and the organic group of the metal chelate compound preferably has 4 or more carbon atoms.

The adhesive layer obtained by curing the active energy ray-curable adhesive composition at 25 ° C preferably has a storage elastic modulus of 1.0 × 10 ⁷ Pa or more.

<hardening of adhesive>

The active energy ray-curable adhesive composition used in the present invention can be used in an electron beam curing type, an ultraviolet curing type, or a visible light curing type. From the viewpoint of productivity, the visible light-curable adhesive composition is preferably an active energy ray-curable adhesive composition.

In the active energy ray-curable adhesive composition, after bonding the polarizer and the transparent protective film, the active energy ray (electron beam, ultraviolet ray, visible light, etc.) is irradiated, and the active energy ray-curable adhesive composition is cured to form an adhesive. Floor. The irradiation direction of the active energy rays (electron beam, ultraviolet light, visible light, etc.) can be irradiated from any appropriate direction. It is preferred to irradiate from the side of the transparent protective film. When the light is irradiated from the polarizer side, the polarizer may be deteriorated by the active energy ray (electron beam, ultraviolet ray, visible light, or the like).

In the electron beam curing type, the irradiation conditions of the electron beam may be any suitable conditions as long as the conditions for curing the active energy ray-curable adhesive composition are hardened. For example, in the case of electron beam irradiation, the acceleration voltage is preferably 5 kV to 300 kV, and more preferably 10 kV to 250 kV. When the accelerating voltage is less than 5 kV, the electron beam fails to reach the adhesive, and there is insufficient hardening. When the accelerating voltage is greater than 300 kV, the penetration force of the sample is too strong, which may cause damage to the transparent protective film or the polarizing member. The amount of illumination line is 5~100kGy, and more preferably 10~75kGy. When the amount of irradiation line is less than 5 kGy, the adhesive will be insufficiently hardened. When it is more than 100 kGy, the transparent protective film or the polarizing member is damaged, the mechanical strength is lowered or yellowing is caused, and predetermined optical characteristics are not obtained.

The electron beam irradiation is usually carried out in an inert gas, but it may be carried out in the atmosphere or with a small amount of oxygen introduced as needed. Depending on the material of the transparent protective film, by appropriately introducing oxygen, oxidative damage is generated on the surface of the transparent protective film which the electron beam first hits, and the damage of the transparent protective film by the electron beam can be prevented, and only efficient. The electron beam is irradiated to the adhesive.

In the method for producing a polarizing film of the present invention, the active energy ray is a visible light ray having a wavelength range of 380 nm to 450 nm, and particularly preferably an active energy ray having the largest amount of visible light irradiation in a wavelength range of 380 nm to 450 nm. In the ultraviolet curing type and the visible light curing type, when a transparent protective film (ultraviolet-opaque transparent protective film) having ultraviolet absorbing energy is used, light having a shorter wavelength than 380 nm is absorbed, and light having a shorter wavelength than 380 nm cannot be used. Reaching the active energy ray hardening type of adhesive does not help the polymerization should. Further, light of a short wavelength of 380 nm absorbed by the transparent protective film is converted into heat, and the transparent protective film itself generates heat, which causes a problem such as curling of the polarizing film and texture. Therefore, in the case of using an ultraviolet curing type or a visible light curing type in the present invention, it is preferable to use a device that does not emit light having a shorter wavelength than 380 nm as an active energy ray generating device, and more specifically, an integrated illuminance in a wavelength range of 380 to 440 nm. The ratio of the illuminance to the integrated wavelength range of 250 to 370 nm is preferably 100:0 to 100:50, and preferably 100:0 to 100:40. The active energy ray of the present invention is preferably a gallium-containing metal halide lamp or an LED light source having a wavelength range of 380 to 440 nm. Alternatively, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, an incandescent lamp, a xenon lamp, a halogen lamp, a carbon arc lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, a gallium lamp, or an excimer laser or For ultraviolet light and visible light sources such as sunlight, a band pass filter can also be used to block ultraviolet light having a shorter wavelength than 380 nm. In order to improve the adhesion properties of the adhesive layer between the polarizer and the transparent protective film, and to prevent the polarizing film from being curled, the following active energy ray should be used: a gallium-containing metal halide lamp is used and the rupturable wavelength is shorter than 380 nm. The active energy ray obtained by the bandpass filter of the light or the active energy ray of 405 nm obtained using the LED light source.

In the ultraviolet curable or visible light curing type, it is preferred to apply an ultraviolet ray or visible light to heat the active energy ray-curable adhesive (warming after irradiation). In this case, it is preferred to increase the temperature to 40 ° C or higher. It is preferred to heat to 50 ° C or higher.

The active energy ray-curable adhesive of the present invention is particularly suitable for use in forming a polarizing member and a light transmittance of less than 5% at a wavelength of 365 nm. An adhesive layer of a transparent protective film. Here, the active energy ray-curable adhesive of the present invention can be cured to form an adhesive layer by irradiating ultraviolet rays through a transparent protective film having UV absorbing energy by containing the photopolymerization initiator of the above formula (1). Therefore, in the polarizing film having a transparent protective film of UV absorbing energy in the two-layer layer of the polarizing member, the adhesive layer can be hardened. However, it is a matter of course that the adhesive layer can be cured in a polarizing film having a transparent protective film having no UV absorbing property. Further, the transparent protective film having UV absorption energy means a transparent protective film having a transmittance of light of 380 nm of less than 10%.

The method of imparting UV absorption energy to the transparent protective film may be exemplified by a method of containing an ultraviolet absorber in the transparent protective film or a method of including a surface treatment layer of the ultraviolet absorber on the surface layer of the transparent protective film.

Specific examples of the ultraviolet absorber include, for example, a conventional oxydiphenyl ketone compound, a benzotriazole compound, a salicylate compound, a diphenyl ketone compound, and a cyanoacrylate. Compound, nickel-salt compound, three A compound or the like.

After bonding the polarizer and the transparent protective film, the active energy ray (electron beam, ultraviolet ray, visible light, etc.) is irradiated, and the active energy ray-curable adhesive is cured to form an adhesive layer. When the polarizer and the transparent protective film are bonded, the moisture content of the polarizer is usually 1% or more, preferably 3% or more, more preferably 5% or more. Further, when the moisture content of the polarizer is too high, the moisture in the polarizer moves toward the moving adhesive layer, and the B component of the binder composition having a log POW of 2 to 7 is separated, resulting in poor appearance, so good. The moisture content of the polarizer is preferably 18% or less, preferably 15% or less. The best is less than 12%. The moisture content of the polarizer was cut out from the obtained polarizer by a sample of 180 mm × 500 mm, and the initial weight (W (g)) was measured. After the sample was placed in a dryer at 120 ° C for 6 hours, the weight after drying (D (g)) was measured. From these measured values, the water content was determined by the following formula.

Moisture content (%) = {(W-D) / W} × 100

The irradiation direction of the active energy rays (electron beam, ultraviolet light, visible light, etc.) can be irradiated from any appropriate direction. It is preferred to irradiate from the side of the transparent protective film. When the light is irradiated from the polarizer side, the polarizer may be deteriorated by the active energy ray (electron beam, ultraviolet ray, visible light, or the like).

When the polarizing film of the present invention is produced on a continuous production line, depending on the hardening time of the adhesive, the production line speed is preferably from 1 to 500 m/min, preferably from 5 to 300 m/min, and more preferably from 10 to 30. 100m/min. When the line speed is too slow, the productivity is poor, or the damage to the transparent protective film is too large, and a polarizing film which can pass the durability test or the like cannot be produced. When the line speed is too fast, the hardening of the adhesive becomes insufficient, and there is a case where the intended adhesion is not obtained.

Further, in the polarizing film of the present invention, the polarizing member and the transparent protective film are bonded through an adhesive layer formed by the cured layer of the active energy ray-curable adhesive, but between the transparent protective film and the adhesive layer Easy to connect layers can be set. The easy-adhesive layer may have, for example, a polyester skeleton, a polyether skeleton, a polycarbonate skeleton, a polyurethane skeleton, an anthrone, a polyamine skeleton, a polyimine skeleton, a polyvinyl alcohol skeleton, or the like. Various resins are formed. These polymer resins may be used alone or in combination of two or more. Further, other additives may be added to the formation of the easy adhesion layer. Specifically In other words, stabilizers such as an adhesion promoter, an ultraviolet absorber, an antioxidant, and a heat stabilizer can be further used.

Usually, an easy-adhesion layer is provided in advance on the transparent protective film, and the easy-contact layer side of the transparent protective film and the polarizing member are bonded by an adhesive layer. The formation of the easy-adhesion layer can be carried out by applying a coating of an easy-adhesion layer to a transparent protective film by a well-known technique and drying it. The thickness of the dried layer, the smoothness of the coating, and the like are usually considered to be a solution which is diluted to a suitable concentration. The thickness of the easy-to-adhere layer after drying is preferably 0.01 to 5 μm, preferably 0.02 to 2 μm, more preferably 0.05 to 1 μm. Further, although a plurality of layers may be provided, it is preferable that the total thickness of the easily-adhesive layer is within the above range.

<polarizer>

The polarizer is not particularly limited, and various polarizers can be used. The polarizer may be, for example, a dichroic material such as iodine or a dichroic dye adsorbed on a polyvinyl alcohol film, a partially formalized polyvinyl alcohol film, or ethylene. The vinyl acetate copolymer is a hydrophilic polymer film such as a partially saponified film, and is uniaxially stretched, that is, a polyene-based oriented film such as a dehydrated material of polyvinyl alcohol or a dehydrochlorinated product of polyvinyl chloride. Among these, a polarizing member composed of a polyvinyl alcohol-based film and a dichroic material such as iodine is preferred. The thickness of the polarizers is not particularly limited, but is generally about 80 μm or less.

The polarizing material in which the polyvinyl alcohol-based film is dyed with iodine and which is mono-extended can be produced by, for example, immersing polyvinyl alcohol in an aqueous solution of iodine, and extending it to 3 to 7 times the original length. If necessary, it may be immersed in an aqueous solution such as boric acid or potassium iodide. It can also be used as needed before dyeing. The enol film is immersed in water and washed. By washing the polyvinyl alcohol-based film with water, the polyvinyl alcohol-based film can be swollen in addition to the dirt and the anti-caking agent on the surface of the polyvinyl alcohol-based film, and the effect of preventing unevenness in dyeing unevenness can be obtained. The extension can be carried out after dyeing with iodine, or it can be extended on one side of the dye or after iodine. It can also be extended in an aqueous solution such as boric acid or potassium iodide or in a water bath.

Further, when the active energy ray-curable adhesive composition used in the present invention uses a thin polarizing member having a thickness of 10 μm or less as a polarizing member, the effect can be remarkably exhibited (accepting optical durability in a severe environment under high temperature and high humidity) Sex). The polarizer having a thickness of 10 μm or less is relatively more affected by moisture than the polarizer having a thickness of more than 10 μm, and the optical durability is insufficient in an environment of high temperature and high humidity, and the transmittance is likely to increase or the degree of polarization is lowered. . In other words, when the polarizer of the above-described adhesive layer of the present invention has a polarizing member of 10 μm or less, the movement of water of the polarizing member in a severe high-temperature and high-humidity environment is suppressed, whereby the transmittance of the polarizing film can be remarkably suppressed from increasing. The deterioration of optical durability such as a decrease in the degree of polarization. From the viewpoint of thinning, the thickness of the polarizing member is preferably 1 to 7 μm. Such a thin polarizer has a small thickness unevenness, is excellent in visibility, and has little dimensional change, and is preferably a thickness of a polarizing film from the viewpoint of achieving a reduction in thickness.

A representative thin polarizing member is exemplified by Japanese Patent Laid-Open No. 51-069644, Japanese Patent Laid-Open No. 2000-338329, No. WO2010/100917, and PCT/JP2010/001460, and Japanese Patent. A thin polarizing film described in the specification of Japanese Patent Application No. 2010-263692 or the specification of Japanese Patent Application No. 2010-263692. Such thin bias The light film can be obtained by a method comprising the steps of stretching a layer of a polyvinyl alcohol-based resin (hereinafter also referred to as a PVA-based resin) and a resin substrate for stretching in a state of a laminate, and a step of dyeing. According to this production method, even if the PVA-based resin layer is thin, it can be extended by the support of the resin substrate for stretching without defects such as breakage due to elongation.

The thin polarizing film is formed by a step of extending in a state including a laminate and a dyeing step, and is capable of extending at a high magnification to improve polarizing performance, as in the manual of WO2010/100917, PCT/JP2010/001460. The method of the step of extending in an aqueous solution of boric acid described in the specification of Japanese Patent Application No. 2010-269002 or the specification of Japanese Patent Application No. 2010-263692 is preferred, in particular, Japanese Patent Application No. 2010-269002 The method described in the specification or the Japanese Patent Application No. 2010-263692, which is incorporated in the boric acid aqueous solution, is preferably carried out by a method of performing the step of extending the air before the extension.

The thin high-performance polarizing film described in the above-mentioned PCT/JP2010/001460 is a thin high-performance polarizing film having a thickness of 7 μm or less which is formed of a PVA-based resin which is formed by integrally forming a resin substrate and having a dichroic material oriented. It has an optical property of a monomer transmittance of 42.0% or more and a degree of polarization of 99.95% or more.

The thin high-performance polarizing film can be produced by coating a PVA-based resin on a resin substrate having a thickness of at least 20 μm and drying it to form a PVA-based resin layer, and immersing the formed PVA-based resin layer in a dichroic substance. In the dyeing solution, the dichroic substance is adsorbed to the PVA-based resin layer, and the PVA-based resin layer to which the dichroic substance is adsorbed is added to the aqueous boric acid solution. Extending with the resin substrate to a total stretch ratio of more than 5 times the original length.

Further, there is a method for producing a laminate film comprising a thin high-performance polarizing film which has been oriented to dichroic substances, and a method for producing the same, comprising the steps of: forming a laminate film comprising a resin substrate having a thickness of at least 20 μm and a PVA-based resin layer formed by coating an aqueous solution containing a PVA-based resin on one surface of the resin substrate and drying the mixture; and forming a resin substrate and forming the adsorption step The laminated film of the PVA-based resin layer on one surface of the resin substrate is immersed in a dyeing liquid containing a dichroic substance, and the PVA-based resin layer contained in the laminated film is adsorbed to the dichroic substance; The laminate film comprising a PVA-based resin layer to which a dichroic substance is adsorbed is extended in a boric acid aqueous solution to a total stretching ratio of 5 times or more of the original length; and the step of producing a laminate film is performed by adsorbing dichroism The PVA-based resin layer of the substance is extended together with the resin substrate, and the thickness of the PVA-based resin layer which is oriented by the dichroic substance is one surface of the resin substrate. A thin high-performance polarizing film having an optical transmittance of 42.0% or more and a degree of polarization of 99.95% or more, which is not more than μm, and can be produced by the above-described manufacturing method.

The thin polarizing film of the above-mentioned Japanese Patent Application No. 2010-269002 or Japanese Patent Application No. 2010-263692 is a continuous web polarizing film composed of a PVA resin having a dichroic material oriented. Extending by a two-stage extension step consisting of an extension of the air support and extension of the boric acid water, including film formation in the amorphous ester system The laminate of the PVA-based resin layer of the thermoplastic resin substrate has a thickness of 10 μm or less. When the thin polarizing film has a monomer transmittance of T and a polarization degree of P, it satisfies P>-(100.929T-42.4-1)×100 (however, T<42.3), and P≧99.9. The optical properties of the conditions (however, T≧42.3) are preferred.

Specifically, the thin polarizing film can be produced by a method for producing a thin polarizing film comprising the following steps: by subjecting a PVA-based resin layer formed on a continuous network of amorphous ester-based thermoplastic resin substrate to high temperature in the air Extending to form an extended intermediate product composed of the oriented PVA-based resin layer; by adsorbing the dichroic substance to the extended intermediate product, generating a dichroic substance (using iodine or iodine and an organic dye) The mixture is preferably a step of forming a colored intermediate product of the oriented PVA-based resin layer; and by stretching the colored intermediate product in boric acid water to form a PVA-based resin layer having a dichroic material oriented and A step of a polarizing film having a thickness of 10 μm or less.

In the production method, the total stretching ratio of the PVA-based resin layer formed on the amorphous ester-based thermoplastic resin substrate by stretching in the air at a high temperature and extending in boric acid water is preferably 5 times or more. The liquid temperature of the boric acid aqueous solution extended in boric acid water can be set to 60 ° C or more. It is preferred to carry out the insolubilization treatment on the colored intermediate product before extending the colored intermediate product in the aqueous boric acid solution. In this case, it is preferred to immerse the colored intermediate product in a boric acid aqueous solution having a liquid temperature of not more than 40 °C. The amorphous ester-based thermoplastic resin substrate may be a copolymerized polyethylene terephthalate copolymerized with isophthalic acid or a copolymerized polyparaphenylene copolymerized with cyclohexane dimethanol. Ethylene dicarboxylate or amorphous polyethylene terephthalate containing other copolymerized polyethylene terephthalate, preferably composed of a transparent resin, the thickness of which may be a film forming PVA system The thickness of the resin layer is 7 times or more. Further, the stretching ratio in the air high temperature extension is preferably 3.5 times or less, and the stretching temperature in the air high temperature stretching is higher than the glass transition temperature of the PVA resin, and specifically, it is preferably in the range of 95 ° C to 150 ° C. When the high-temperature extension in the air is carried out by uniaxial stretching at the free end, the total stretching ratio of the PVA-based resin layer formed on the amorphous ester-based thermoplastic resin substrate is preferably 5 times or more and 7.5 times or less. Further, when the high-temperature extension in the air is performed by the uniaxial stretching at the fixed end, the total stretching ratio of the PVA-based resin layer formed on the amorphous ester-based thermoplastic resin substrate is preferably 5 times or more and 8.5 times or less.

More specifically, a thin polarizing film can be produced by the following method.

A continuous network substrate in which ethylene oxide copolymerized polyethylene terephthalate (amorphous PET) having 6 mol% of isophthalic acid was copolymerized was produced. The glass transition temperature of the amorphous PET was 75 °C. A laminate comprising a continuous network of amorphous PET substrate and a polyvinyl alcohol (PVA) layer was produced as follows. Further, the glass transition temperature of PVA was 80 °C.

An amorphous PET substrate having a thickness of 200 μm was prepared, and a PVA aqueous solution having a concentration of 4 to 5% of PVA powder having a degree of polymerization of 1,000 or more and a degree of saponification of 99% or more was dissolved in water. Next, a PVA aqueous solution was applied to a 200 μm-thick amorphous PET substrate, and dried at a temperature of 50 to 60° C. to obtain a laminate having a 7 μm-thick PVA layer formed on an amorphous PET substrate.

By extending the air subsidy extension and the extension of the boric acid water In the following steps of the stretching step, a laminate system comprising a 7 μm thick PVA layer was used to form a thin high-performance polarizing film of 3 μm thick. The laminate of the PVA layer having a thickness of 7 μm was stretched together with the amorphous PET substrate by the air-assisted extension step of the first stage to form an extended laminate including a PVA layer having a thickness of 5 μm. Specifically, the extended laminated body is an extension device that places a laminated body including a PVA layer of 7 μm thick in an oven equipped with an extended temperature environment set to 130 ° C, and then uniaxially extends to a stretching ratio of 1.8 times at the free end. By. By this stretching treatment, the PVA layer contained in the extended laminated body was changed into a 5 μm thick PVA layer in which the PVA molecules were oriented.

Next, iodine is adsorbed to the 5 μm thick PVA layer which has been oriented by the PVA molecule by a dyeing step to form a colored layered body. Specifically, the coloring layer system immerses the extended laminated body in a dyeing liquid containing iodine and potassium iodide at a liquid temperature of 30 ° C for any time so that the monomer permeability of the PVA layer constituting the finally formed high functional polarizing film is 40 to 44%, whereby iodine is adsorbed to the PVA layer contained in the extended laminate. In this step, the dyeing liquid contains water as a solvent, and the iodine concentration is in the range of 0.12 to 0.30% by weight, and the potassium iodide concentration is set to be in the range of 0.7 to 2.1% by weight. The concentration ratio of iodine to potassium iodide is 1 to 7. Further, in order to dissolve iodine in water, potassium iodide is required. More specifically, the extended laminate was immersed in a dyeing liquid having an iodine concentration of 0.30% by weight and a potassium iodide concentration of 2.1% by weight for 60 seconds to form a colored layered body in which an iodine was adsorbed on a PVA layer having a thickness of 5 μm which was oriented in the PVA molecule.

Further, by the step of extending the boric acid water in the second stage, the colored layered product and the amorphous PET substrate were further extended to form an optical film layered body including a PVA layer constituting a high functional polarizing film having a thickness of 3 μm. Specifically In other words, the optical film laminate is formed by placing the colored laminate in an extension device provided in the processing apparatus, and then extending at a free end uniaxially to a stretching ratio of 3.3 times, and the treatment device is set to contain boric acid and potassium iodide. And a boric acid aqueous solution having a liquid temperature range of 60 to 85 °C. In more detail, the liquid temperature of the aqueous boric acid solution was 65 °C. Further, the boric acid content was 4 parts by weight based on 100 parts by weight of water, and the potassium iodide content was 5 parts by weight based on 100 parts by weight of water. In this step, the colored layered body having the adjusted iodine adsorption amount is first immersed in an aqueous boric acid solution for 5 to 10 seconds. Thereafter, the colored layered body was directly passed between the multiple array rolls having different peripheral speeds of the stretching device provided in the processing apparatus, and uniaxially extended at the free end for 30 to 90 seconds until the stretching ratio was 3.3 times. By this stretching treatment, the PVA layer contained in the colored layered body was changed into a 3 μm-thick PVA layer in which the adsorbed iodine was highly unidirectionally oriented with the iodonium ion complex. The PVA layer will constitute a high-performance polarizing film of an optical film laminate.

Although it is not necessary for the production of the optical film laminate, the optical film laminate is taken out from the aqueous boric acid solution by the washing step, and the 3 μm thick PVA formed on the amorphous PET substrate is washed with a potassium iodide aqueous solution. Boric acid adhered to the surface of the layer is preferred. Thereafter, the washed optical film laminate was dried by a drying step of a warm air of 60 °C. Further, the washing step is a step for removing appearance defects such as precipitation of boric acid.

Similarly, although it is not necessary for the production of the optical film laminate, a 3 μm thick PVA layer formed by applying an adhesive to an amorphous PET substrate by a bonding and/or transfer step may be used. On the surface, after adhering a 80 μm thick cellulose triacetate film, the amorphous PET substrate was peeled off, and a 3 μm thick PVA layer was transferred to a 80 μm thick cellulose triacetate thin film. membrane.

[other steps]

The method for producing the above-mentioned thin polarizing film may include other steps in addition to the above steps. Other steps may be exemplified by an insolubilization step, a crosslinking step, a drying (adjustment of moisture content) step, and the like. Other steps can be performed at any suitable time.

A typical insolubilization step can be carried out by immersing the PVA-based resin layer in an aqueous boric acid solution. By performing the insolubilization treatment, the water resistance of the PVA-based resin layer can be imparted. The concentration of the aqueous boric acid solution is preferably from 1 part by weight to 4 parts by weight per 100 parts by weight of water. The liquid temperature of the insolubilizing bath (aqueous boric acid solution) is preferably 20 ° C to 50 ° C. It is preferred to carry out the insolubilization step after the production of the laminate, the dyeing step or the water stretching step.

A typical crosslinking step can be carried out by immersing the PVA-based resin layer in an aqueous boric acid solution. The water resistance of the PVA-based resin layer can be imparted by performing the crosslinking treatment. The concentration of the aqueous boric acid solution is preferably from 1 part by weight to 4 parts by weight per 100 parts by weight of water. Further, when the crosslinking step is carried out after the dyeing step, it is preferred to incorporate an iodide. By doping the iodide, elution of iodine adsorbed to the PVA-based resin layer can be suppressed. The amount of the iodide blended is preferably from 1 part by weight to 5 parts by weight per 100 parts by weight of the water. Specific examples of the iodide are as described above. The liquid temperature of the crosslinking bath (aqueous boric acid solution) is preferably 20 ° C to 50 ° C. It is preferred to carry out the crosslinking step before the step of extending the second boric acid water. In a preferred embodiment, the dyeing step, the crosslinking step, and the second boric acid water extending step are sequentially performed.

<Transparent protective film>

The material for forming the transparent protective film provided on one surface or both surfaces of the polarizing member is preferably excellent in transparency, mechanical strength, thermal stability, water resistance, and isotropic properties. For example, a polyester polymer such as polyethylene terephthalate or polyethylene naphthalate, a cellulose polymer such as diethyl cellulose or cellulose triacetate, or a polymethyl methyl group. Acrylic polymer such as acrylate, polystyrene or acrylonitrile. A styrene-based polymer such as a styrene copolymer (AS resin) or a polycarbonate-based polymer. Also, polyethylene, polypropylene, with ring or drop A polyolefin structure such as ethylene. A polyolefin polymer such as a propylene copolymer, a vinyl chloride polymer, a guanamine polymer such as nylon or an aromatic polyamine, a quinone polymer, a fluorene polymer, or a polyether fluorene polymer , polyetheretherketone polymer, polyphenylene sulfide polymer, vinyl alcohol polymer, vinylidene chloride polymer, vinyl butyral polymer, aryl ester polymer, polyoxymethylene The base polymer, the epoxy polymer, or a blend of the above polymers, and the like can also be exemplified as the polymer forming the transparent protective film. One or more suitable additives may be optionally contained in the transparent protective film. Examples of the additives include ultraviolet absorbers, antioxidants, slip agents, plasticizers, mold release agents, coloring inhibitors, flame retardants, nucleating agents, charging inhibitors, pigments, colorants, and the like. The content of the thermoplastic resin in the transparent protective film is preferably from 50 to 100% by weight, more preferably from 50 to 99% by weight, still more preferably from 60 to 98% by weight, and particularly preferably from 70 to 97% by weight. When the content of the thermoplastic resin in the transparent protective film is 50% by weight or less, there is a fear that the high transparency and the like of the thermoplastic resin are not sufficiently exhibited.

Moreover, the transparent protective film is Japanese Patent Laid-Open No. 2001-343529 The polymer film described in the publication (WO 01/37007) may, for example, contain (A) a thermoplastic resin having a substituted and/or unsubstituted quinone imine group in a side chain, and (B) having a substitution in a side chain. And/or a resin composition of a non-substituted phenyl and nitrile-based thermoplastic resin. Specific examples include an alternating copolymer composed of isobutylene and N-methylbutyleneimine, and acrylonitrile. A film of a resin composition of a styrene copolymer is exemplified. As the film, a film composed of a mixed extrusion of a resin composition or the like can be used. Since the phase difference between the films is small and the photoelastic coefficient is small, it is possible to remove the unevenness caused by the variability of the polarizing film, and since the moisture permeability is small, the humidifying durability is excellent.

In the polarizing film, the transparent protective film preferably has a moisture permeability of 150 g/m ² /24 h or less. According to this configuration, moisture in the air is less likely to enter the polarizing film, and the moisture content of the polarizing film itself can be suppressed. As a result, curling or dimensional change of the polarizing film due to the preservation environment can be suppressed.

The material for forming the transparent protective film provided on one side or both sides of the polarizing member is preferably excellent in transparency, mechanical strength, thermal stability, water resistance, isotropic property, etc., particularly in a moisture permeability of 150 g/m ² / 24h or less are preferred to 140g / m ² / 24h or less are particularly preferred to 120g / m ² / 24h or less more preferably. The moisture permeability can be determined by the method described in the examples.

A material for forming the transparent protective film having a low moisture permeability, for example, a polyester resin such as polyethylene terephthalate or polyethylene naphthalate; a polycarbonate resin; an aryl ester resin; nylon or A phthalamide resin such as aromatic polyamine; such as polyethylene, polypropylene, ethylene. Polypropylene polymer of propylene copolymer, with ring system or drop A cyclic olefin-based resin having an olefin structure, a (meth)acrylic resin, or a mixture thereof. Among the above resins, a polycarbonate resin, a cyclic polyolefin resin, or a (meth)acrylic resin is preferred, and a cyclic polyolefin resin or a (meth)acrylic resin is particularly preferred.

The thickness of the transparent protective film can be appropriately determined, and is generally about 1 to 100 μm in view of workability such as strength and handleability, and thin layer properties. It is preferably 1 to 80 μm, more preferably 3 to 60 μm.

Further, when a transparent protective film is provided on both surfaces of the polarizer, a transparent protective film made of the same polymer material may be used on the front and back surfaces, and a transparent protective film made of a different polymer material or the like may be used. From the viewpoint of moisture permeability, the combination of the transparent protective film is a polyethylene terephthalate film, a cyclic polyolefin resin film, a (meth)acrylic resin film, and a cyclic polyolefin resin film. A combination of a (meth)acrylic resin film and a (meth)acrylic resin film is preferred. By providing a transparent protective film having a small moisture permeability on both sides of the polarizing member, moisture is less likely to enter the polarizing film, and a polarizing film having particularly excellent water resistance can be obtained.

A functional layer such as a hard coat layer, an antireflection layer, an anti-adhesion layer, a diffusion layer or an anti-glare layer may be provided on the surface of the polarizer that does not follow the transparent protective film. Further, the functional layer such as the hard coat layer, the antireflection layer, the anti-adhesion layer, the diffusion layer or the anti-glare layer may be provided separately from the transparent protective film itself, or may be separately provided as an object different from the transparent protective film. .

<Optical film>

In practical use, the polarizing film of the present invention can be used as an optical film laminated with other optical layers. The optical layer is not particularly limited, but may be For example, an optical layer for forming a liquid crystal display device such as a reflector, a semi-transmissive plate, a retardation plate (including a 1/2 or 1/4 wavelength plate), a viewing angle compensation film, or the like can be used. . In particular, it is preferable that the polarizing film of the present invention has a reflective polarizing film or a semi-transmissive polarizing film which is formed by laminating a reflecting plate or a semi-transmissive reflecting plate, and an elliptically polarizing film which is formed by laminating a phase difference plate of the polarizing film or A circular polarizing film, a wide viewing angle polarizing film formed by a multilayer viewing angle compensation film on a polarizing film, or a polarizing film formed by further coating a brightness enhancement film on a polarizing film.

The optical film in which the optical layer is laminated on the polarizing film may be formed by sequentially laminating in a manufacturing process such as a liquid crystal display device. However, if the optical film is laminated in advance, the quality is excellent, the assembly work is excellent, and the liquid crystal can be improved. The advantages of manufacturing steps such as display devices. As the laminate, an appropriate bonding method such as an adhesive layer can be used. When the polarizing film or other optical film is used, the optical axes can be appropriately arranged at an appropriate angle depending on the phase difference characteristics of the object.

In the optical film in which at least one of the polarizing film or the polarizing film is laminated, an adhesive layer for adhering to another member such as a liquid crystal cell may be provided. Although the adhesive for forming the adhesive layer is not particularly limited, for example, an acrylic polymer, an anthrone polymer, a polyester, a polyurethane, a polyamine, a polyether, or a fluorine-based compound can be appropriately selected and used. Or a polymer such as a rubber system as a matrix polymer. In particular, it is preferable to use an excellent optical transparency such as an acrylic adhesive, an appropriate wettability, an adhesive property of adhesion and adhesion, and excellent weather resistance and heat resistance.

The adhesive layer can be used as a superposed layer of different composition or type. On one or both sides of the polarizing film or optical film. Further, when it is provided on both sides, it may be used as an adhesive layer having a different composition, type, or thickness on the front and back surfaces of the polarizing film or the optical film. The thickness of the adhesive layer is appropriately determined depending on the purpose of use or the adhesion force, and is generally 1 to 500 μm, preferably 1 to 200 μm, particularly preferably 1 to 100 μm.

The exposed surface of the adhesive layer is temporarily provided with an insulating member for covering for the purpose of preventing contamination or the like before the actual use. Thereby, it is possible to prevent contact with the adhesive layer in a normal state. The spacer member may be used in a conventional manner in addition to the above-described thickness conditions, for example, a plastic film, a rubber sheet, a paper, a cloth, a non-woven fabric, a net, a foamed sheet or a metal foil, or the like, or the like, if necessary. A suitable sheet is coated with a suitable release agent such as an anthrone, a long-chain alkyl group, a fluorine-based or a molybdenum sulfide.

<Image display device>

The polarizing film or optical film of the present invention is suitable for formation of various devices such as liquid crystal display devices. The formation of the liquid crystal display device can be performed in accordance with the past. In other words, the liquid crystal display device can be generally formed by appropriately assembling a liquid crystal cell, a polarizing film or an optical film, and an optional illumination system, and the like, and is incorporated in a driving circuit or the like. In the present invention, the polarizing film of the present invention is used. The optical film is not particularly limited, and can be carried out in a conventional manner. As the liquid crystal cell, for example, a TN type, an STN type, a π type or the like can be used.

A liquid crystal display device in which a polarizing film or an optical film is disposed on one side or both sides of a liquid crystal cell, or a liquid crystal display device such as a backlight or a reflector used in an illumination system can be formed. At this time, it can be used in liquid crystal The polarizing film or optical film of the present invention is disposed on one side or both sides of the cell. When a polarizing film or an optical film is provided on both sides, the same may be the same or different. Further, when forming a liquid crystal display device, for example, a suitable layer such as a diffusion plate, an anti-glare layer, an anti-reflection film, a protective plate, a ruthenium array, a lens array sheet, a light diffusion plate, and a backlight may be disposed in one layer or two. Above the layer at the appropriate location.

[Examples]

The embodiments of the present invention are described below, but the embodiments of the present invention are not limited by the above.

Manufacturing example 1

<Production of Polyvinyl Alcohol Polarizer X>

A polyvinyl alcohol film having an average degree of polymerization of 2400 and a saponification degree of 99.9 mol% and a thickness of 75 μm was immersed in warm water of 30 ° C for 60 seconds to be expanded. Subsequently, it was immersed in an aqueous solution of 0.3% by weight of iodine/potassium iodide (weight ratio = 0.5/8), extended to 3.5 times, and the film was dyed. Thereafter, the solution was extended to a total stretching ratio of 6 times in an aqueous solution of borate ester at 65 °C. After stretching, it was dried in an oven at 40 ° C for 3 minutes to obtain a polyvinyl alcohol-based polarizing member X (thickness: 23 μm).

Manufacturing Example 2

<Production of Polyvinyl Alcohol Thin Translucent Y>

In order to produce the thin polarizer Y, first, a laminate having a PVA layer of 24 μm thick is formed on an amorphous PET substrate by an extension of an extension temperature of 130 ° C to form an extended laminate, followed by dyeing. Extending the layered body to form a colored layered body, and then extending the temperature to 65 degrees of boric acid water In the middle extension, the colored laminate was stretched together with the amorphous PET substrate to a total stretch ratio of 5.94 times to form an optical film laminate including a 10 μm thick PVA layer. An optical film layered body comprising a PVA layer having a thickness of 10 μm constituting the polyvinyl alcohol-based thin polarizing member Y can be produced, and the polyvinyl alcohol-based thin polarizing member Y has been formed into a film by the two-stage stretching. The PVA molecules of the PVA layer of the crystalline PET substrate are highly oriented, and the dyed adsorbed iodine is highly oriented in a unidirectional manner with the polyiodide ion complex.

<Transparent protective film>

The transparent protective film A: 100 parts by weight of the ruthenium iodide resin described in Production Example 1 of JP-A-2010-284840, and the third 0.62 part by weight of a UV absorber (trade name: T-712, manufactured by Adeka Co., Ltd.) was mixed at 220 ° C in a 2-axis kneader to prepare resin pellets. The obtained resin pellets were dried at 100.5 kPa and 100 ° C for 12 hours, and extruded from a T-die at a mold temperature of 270 ° C in a uniaxial extruder to form a film (thickness: 160 μm). The film was further extended (thickness 80 μm) in a gas atmosphere of 150 ° C in the direction of conveyance, and then an easy adhesion agent of the aqueous urethane resin was applied, and then 150 ° C in a direction perpendicular to the film transport direction. The film was extended in a gas atmosphere to obtain a transparent protective film A having a thickness of 40 μm (moisture permeability: 58 g/m ² /24 h).

Transparent protective film B: A corona treatment was carried out using a cyclic polyolefin film (manufactured by Nippon Zeon Co., Ltd.: ZEONOR, moisture permeability: 11 g/m ² /24 h) having a thickness of 55 μm.

Transparent protective film C: A PET film (manufactured by Toyobo Co., Ltd., moisture permeability: 13 g/m ² /24 h) was used for the bonding surface, and a urethane resin was used for the bonding surface.

<Transparency of transparent protective film>

The moisture permeability was measured in accordance with the moisture permeability test (cylinder plate method) of JIS Z0208. A sample cut into a diameter of 60 mm was placed in a moisture-permeable cylindrical plate containing about 15 g of calcium chloride, and placed in a thermostat at a temperature of 40 ° C and a humidity of 90% RH, and the chlorination was measured for about 24 hours. The weight of calcium was increased, and the moisture permeability (g/m ² /24h) was determined.

<active energy line>

Active energy ray, using visible light (a metal halide lamp containing gallium) irradiation device: Light HAMMER10 valve manufactured by Fusion UV Systems, Inc.: V valve peak illuminance: 1600 mW/cm ² , integrated irradiation amount 1000/mJ/cm ² ( Wavelength 380~440nm). Further, the illuminance of visible light was measured using a Sola-Check system manufactured by Solatell.

Examples 1 to 5 and Comparative Examples 1 to 2

(Modulation of active energy ray-curable adhesive composition)

Each component was mixed according to the blending table described in Table 1, and stirred at 50 ° C for 1 hour to obtain active energy ray-curable adhesive compositions of Examples 1 to 5 and Comparative Examples 1 and 2.

(production of polarizing film)

On the transparent protective film A, B or C, an MCD coater (manufactured by Fuji Machinery Co., Ltd.) was used (lattice shape: honeycomb shape, number of concave plate rolls: 1000 pieces/inch, rotation speed 140% / pair line speed) The active energy ray-curable adhesive composition of Examples 1 to 5 or Comparative Examples 1 and 2 was applied to have the thickness of the adhesive layer described in Table 1, and when the polarizer X was used, the roller was attached to both surfaces thereof. Transparent protective film. On the other hand, when the thin polarizer Y is used, the transparent protective film is bonded to the reverse side of the PVA layer by a roll machine. Thereafter, the transparent protective film side after self-bonding (both sides when the polarizer X is used) was heated to 50 ° C using an IR heater, and the visible light rays were irradiated on both sides to make Examples 1 to 5 and Comparative Example 1 After the active energy ray-curable adhesive composition of ~2 was hardened, it was dried by hot air at 70 ° C for 3 minutes to obtain a polarizing film having a transparent protective film on both sides of the polarizing member. The bonding was carried out at a line speed of 25 m/min.

The polarizing films obtained in the foregoing Examples and Comparative Examples were evaluated as follows. The evaluation results are shown in Table 1.

<Confirmation of the composition gradient structure of the adhesive layer>

The transparent protective film was mechanically cut, and after exposing the adhesive layer, the thickness direction analysis of the adhesive layer was carried out by repeating the etching using the cluster ions and the TOF-SIMS measurement. TOF-SIMS uses ULVAC. PHI company "TRIFTV". The secondary ions specific to each component are selected, and the components which are located in the thickness direction portion are specified by comparing the intensity ratio of the secondary ions in the thickness direction. The evaluation was performed by calculating the ratio of the A component of the adhesive layer to the polarizer side interface when the ratio of the A component having a log Pow of -1 to 1 in the center portion in the thickness direction of the adhesive layer was 1. When the ratio of the component A of the adhesive layer to the polarizer side interface is more than 1, it means that the concentration of the component A on the polarizer side is high. The evaluation results are shown in Table 1.

<Measurement of temperature of active energy ray-curable adhesive composition>

The surface of the transparent protective film coated with the adhesive composition was measured with a temperature detector "FLIR-E49001" manufactured by FLIR. Furthermore, because of the coating The agent layer is a very thin film with respect to the transparent protective film, so it is presumed that the temperature of the adhesive composition is the same as that of the transparent protective film immediately after coating.

<Continue force>

The polarizing film obtained in each example was cut into a size parallel to the extending direction of the polarizing member by 200 mm and a vertical direction of 20 mm, and a cutting blade was cut between the transparent protective film and the polarizing member to bond the polarizing film to the glass plate. The peeling strength was measured by peeling off the transparent protective film and the polarizing member at a peeling speed of 500 mm/min in a direction of 90 degrees by Tensilon. Further, the infrared absorption spectrum of the peeled surface after peeling was measured by the ATR method, and the peeling interface was evaluated in accordance with the following criteria.

A: Cohesive failure of transparent protective film

B: Interfacial peeling between the transparent protective film/adhesive layer

C: interface peeling between the adhesive layer/polarizer

D: cohesive failure of the polarizer

In the above-mentioned standard, A and D are more than the cohesive force of the film because of the adhesion force, and the adhesion force is extremely excellent. On the other hand, B and C are meanings of insufficient adhesion (and subsequent force difference) at the interface of the transparent protective film/adhesive layer (adhesive layer/polarizer). Consider these, and set the force of A or D to ○, A. B (At the same time, "cohesive failure of the transparent protective film" and "interfacial peeling between the transparent protective film/adhesive layer") or A. C (the simultaneous generation of "cohesive failure of the transparent protective film" and "interfacial layer/polarizer interface peeling") is set to Δ, B or C.

<Continue durability (warm water immersion test)>

Cutting the polarizing film obtained in each case into the extending direction of the polarizing member 50mm, 25mm rectangle in the vertical direction. After the polarizing film was immersed in warm water of 60 ° C for 6 hours, the length of the peeling was visually measured by a magnifying glass. The vertical distance from the partial section from which peeling occurred was measured as the maximum value (mm).

<Continue durability (water peeling resistance)>

The polarizing film obtained in each example was cut into a size parallel to the extending direction of the polarizing member of 200 mm and a vertical direction of 20 mm. After the polarizing film was immersed in pure water at 23 ° C for 24 hours, it was taken out from pure water, and dried with a dry cloth. Then, a cutting blade was cut between the transparent protective film and the polarizing member, and the polarizing film was bonded to the glass plate. It was taken out from pure water and evaluated within 1 minute until the evaluation. In the future, the same evaluation as the above <adjacent force> is performed.

The compound used in Table 1 is: 4HBA; butyl 4-hydroxyacrylate, logPow = 0.68, manufactured by Osaka Organic Chemical Industry Co., Ltd., HEAA: hydroxyethyl acrylamide, logPow = -0.56, manufactured by Xingren Co., Ltd., ACMO: propylene Base Porphyrin, logPow=0.20, manufactured by Xingren Co., Ltd., FANCRYL FA511AS: dicyclopentenyl acrylate, logPow=2.26, manufactured by Hitachi Chemical Co., Ltd., Light Acrylate DCP-A: tricyclodecane dimethanol diacrylate, logPow=3.05 ,Accord Chemical Co., Ltd., Light Acrylate 1,9ND-A: 1,9-decanediol diacrylate, logPow=3.68, manufactured by Kyoeisha Chemical Co., Ltd., FANCRYL FA-P324A: Bisphenol A PO4 Mo Modified diacrylate, logPow=6.43, manufactured by Hitachi Chemical Co., Ltd., ARONIX M-220: tripropylene glycol diacrylate, logPow=1.68, manufactured by Toagosei Co., Ltd., ARONIX M-5700: 2-hydroxy-3-phenoxypropane Acrylate, logPow=1.17, manufactured by Toagosei Co., Ltd., ARUFON UG-4010: an acrylic oligomer obtained by polymerizing a (meth)acrylic acid monomer, manufactured by Toagosei Co., Ltd., NIKANOL Y-1000: xylene resin, Manufactured by FUDOW, IRGACURE907: 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropan-1-one, manufactured by BASF Corporation, KAYACURE DETX-S: diethyl 9-oxosulfur , manufactured by Nippon Kayaku Co., Ltd., IRGACURE 184: 1-hydroxycyclohexyl phenyl ketone, manufactured by BASF Corporation.

Example 6

The active energy ray-curable adhesive composition containing the following compounds was adjusted.

The first active energy ray-curable adhesive composition (liquid viscosity: 10 mPa·s / 25 ° C); HEAA 94% by weight, IRGACURE 907 3% by weight, and KAYACURE DETX-S 3% by weight.

The second active energy ray-curable adhesive composition (liquid viscosity: 350 mPa·s / 25 ° C); Light Acrylate 1, 9 ND-A 94% by weight, IRGACURE 907 3% by weight, KAYACURE DETX-S 3% by weight.

(production of polarizing film)

The first active energy ray-curable adhesive composition (adhesive layer thickness: 0.3 μm) was applied to the PVA layer of the thin polarizer Y. Further, a second active energy ray-curable adhesive composition (adhesive layer thickness: 0.7 μm) was applied to the bonding surface of the transparent protective film A, and these were bonded together by a roll mill. The ratio of the first active energy ray-curable adhesive composition to the second active energy ray-curable adhesive composition was 30:70. Thereafter, the transparent protective film side after bonding is heated to 50° C. using an IR heater, and the visible light rays are irradiated on both surfaces to cure the first and second active energy ray-curable adhesive composition at 70° C. The film was dried by hot air for 3 minutes to obtain a polarizing film having a transparent protective film on both sides of the polarizing member. The line speed of the bonding was carried out at 25 m/min.

With respect to the polarizing film obtained in the above Example 6, the adhesion of the thin polarizing member Y and the transparent protective film A was evaluated. Further, the contact of the first active energy ray-curable adhesive composition with the thin polarizer Y is performed. Evaluation of the contact angle of the transparent protective film Y by the angle and the second active energy ray-curable adhesive composition. In addition, the evaluation of the contact angle was performed in accordance with JIS-K 6768. The evaluation results are shown in Table 2.

<Storage Elasticity Coefficient>

The storage elastic modulus can be measured using the TA Instrument dynamic viscoelasticity measuring device RSAIII under the following measurement conditions.

Sample size: width 10 mm, length 30 mm, clamping distance 20 mm, measurement mode: stretching, frequency: 1 Hz, heating rate: 5 ° C / min.

The measurement of dynamic viscoelasticity was carried out as a measurement at a storage elastic modulus of 25 °C.

Examples 7 to 15 and Comparative Example 3

(Modulation of active energy ray-curable adhesive composition)

According to the blending table described in Table 3, the components were mixed and stirred at 50 ° C for 1 hour to obtain active energy ray-curable adhesive compositions of Examples 7 to 15 and Comparative Example 3.

The compound used in Table 3 represents: TPGDA: tripropylene glycol diacrylate, manufactured by Toagosei Co., Ltd. (ARONIX M-220), metal alkoxide, and metal chelate compound: TC-750: ethyl acetate ethyl acetate chelate (Carbon number 6 of organic group), manufactured by Matsumoto Fine Chemical Co., Ltd.; TC-100: titanium acetonitrile acetone (carbon number of organic group 5), manufactured by Matsumoto Fine Chemical Co., Ltd.; TA-30: titanium octoxide (organic carbon) (8), manufactured by Matsumoto Fine Chemical Co., Ltd.; D20: titanium butyl oxidized (organic group carbon number 4), manufactured by Shin-Etsu Chemical Co., Ltd.; ZA65: zirconium butadiene oxidation (organic group carbon number 4), manufactured by Matsumoto Fine Chemical Co., Ltd.; Aluminum chelate M: alkyl acetoacetate diisopropyl alcohol (organic group carbon number 4 or more), manufactured by Kawasaki Fine Chemical Co., Ltd.; vinyl ether compound: VEEA: 2-(2-vinyloxy) acrylate Ethoxy)ethyl, manufactured by Japan Catalyst Co., Ltd.; photoacid generator: CPI-100P, manufactured by SAN-APRO.

Examples 16 to 19 and Comparative Examples 4 to 7

(Modulation of active energy ray-curable adhesive composition)

According to the blending table described in Table 4, the components were mixed and stirred at 50 ° C for 1 hour to obtain active energy ray hardening of Examples 16 to 19 and Comparative Examples 4 to 7. Type of adhesive composition.

The alkoxyalkylene group-containing compound in Table 4 represents: TA polymer SA100S: main chain (meth)acrylic polymer type, manufactured by Kaneka Co., Ltd., X-MAP SA110S: main chain (meth)acrylic polymer type, Manufactured by Kaneka Co., Ltd., X-40-9225: oligo-type alkoxy fluorenyl compound, KR-213: oligo-type alkoxy fluorenyl compound, manufactured by Shin-Etsu Chemical Co., Ltd. KC-89S: a low molecular weight alkoxyalkyl group-containing compound, manufactured by Shin-Etsu Chemical Co., Ltd., KBM403: a low molecular weight alkoxyalkyl group-containing compound, manufactured by Shin-Etsuketone.

1‧‧‧ polarizer

2‧‧‧Transparent protective film

3‧‧‧ adhesive layer

Claims (26)

A polarizing film is characterized in that at least one of the polarizing members is laminated with a transparent protective film through an adhesive layer, wherein the adhesive layer is irradiated with an active energy ray by an active energy ray-curable adhesive composition. The formed active energy ray-curable adhesive composition contains an A component having a logPow of -1 to 1 representing an octanol/water distribution coefficient, and a B component having a log Pow of 2 to 7, and the foregoing Then, the concentration of the aforementioned A component on the side of the polarizer on the side of the polarizer is high. The polarizing film of claim 1, wherein the active energy ray-curable adhesive composition contains a (meth) acrylamide derivative as the component A. The polarizing film according to claim 1 or 2, wherein the active energy ray-curable adhesive composition contains a polyfunctional (meth) acrylate as the component B. The polarizing film according to any one of claims 1 to 3, wherein the active energy ray-curable adhesive composition contains an acrylic oligomer obtained by polymerizing a (meth)acrylic monomer. The polarizing film according to any one of claims 1 to 4, wherein the active energy ray-curable adhesive composition contains a hydroxyl group-containing photopolymerization initiator. The polarizing film according to any one of claims 1 to 5, wherein the active energy ray-curable adhesive composition contains at least one organic metal selected from the group consisting of metal alkoxides and metal chelates. Compound. The polarizing film of claim 6, wherein the metal of the organometallic compound contained in the active energy ray-curable adhesive composition is titanium. The polarizing film of claim 6 or 7, wherein the active energy ray-curable adhesive composition contains the metal alkoxide as the organometallic compound, and the metal alkoxide has an organic group having a carbon number of 6 or more . The polarizing film of claim 6 or 7, wherein the active energy ray-curable adhesive composition contains the metal chelate compound as the organometallic compound, and the metal chelate has an organic group having a carbon number of 4 or more . The polarizing film according to any one of claims 1 to 9, which has a viscosity of 15 mPa. An alkoxyalkylene group-containing compound above s. The polarizing film of claim 10, wherein the main chain of the alkoxyalkyl group-containing compound is an acrylic polymer structure. The polarizing film according to any one of claims 1 to 11, wherein the adhesive layer obtained by curing the active energy ray-curable adhesive composition has a storage elastic modulus at 25 ° C of 1.0 × 10 ⁷ Pa or more. A method of producing a polarizing film according to any one of claims 1 to 12, characterized by comprising the step of coating a coating on at least one side of the polarizing member and the transparent protective film The active energy ray-curable adhesive composition; a bonding step of bonding the polarizing member and the transparent protective film; and a subsequent step of transmitting the polarizing member and the foregoing through the adhesive layer a transparent protective film, wherein the adhesive layer is obtained by irradiating an active energy ray from the surface side of the polarizer or the surface of the transparent protective film to harden the active energy ray-curable adhesive composition; The temperature of the active energy ray-curable adhesive composition is adjusted to 15 to 40 ° C between the steps and the subsequent steps. A method for producing a polarizing film, wherein the polarizing film is formed by laminating at least one of the polarizing members through a layer of a transparent protective film, and the method for producing the polarizing film is characterized in that the adhesive layer is cured by a pair of active energy rays. a method of forming a cured layer by irradiating an active energy ray with a composition of the active material; and the manufacturing method includes the step of: applying a first active component containing the component A to the bonding surface of the polarizer; An energy ray-curable adhesive composition, wherein the log component of the component A represents an octanol/water distribution coefficient of -1 to 1; and in the second coating step, the coating surface of the transparent protective film is coated with a logPow of 2~ a second active energy ray-curable adhesive composition of the B component of 7; a bonding step of bonding the polarizing member and the transparent protective film; and a subsequent step of transmitting the polarizing member and the transparent protective film through the adhesive layer Next, the adhesive layer is formed by irradiating an active energy ray from the surface side of the polarizer or the surface of the transparent protective film to harden the active energy ray-curable adhesive composition. Too; Further, the concentration of the component A on the polarizer side of the adhesive layer formed after the subsequent step is high. The method for producing a polarizing film according to claim 14, wherein the active energy ray-curable adhesive composition contains a (meth) acrylamide derivative as the component A. The method for producing a polarizing film according to claim 14 or 15, wherein the active energy ray-curable adhesive composition contains a polyfunctional (meth) acrylate as the component B. The method for producing a polarizing film according to any one of claims 14 to 16, wherein the active energy ray-curable adhesive composition contains an acrylic oligomer obtained by polymerizing a (meth)acrylic monomer. The method for producing a polarizing film according to any one of claims 14 to 17, wherein the active energy ray-curable adhesive composition contains a hydroxyl group-containing photopolymerization initiator. The method for producing a polarizing film according to any one of claims 14 to 18, wherein the active energy ray-curable adhesive composition contains at least one selected from the group consisting of metal alkoxides and metal chelates. An organometallic compound. The method for producing a polarizing film according to claim 19, wherein the first active energy ray-curable adhesive composition contains the organometallic compound. The method for producing a polarizing film according to claim 19 or 20, wherein the metal of the organometallic compound contained in the active energy ray-curable adhesive composition is titanium. The method for producing a polarizing film according to any one of claims 19 to 21, wherein The active energy ray-curable adhesive composition contains the metal alkoxide as the organometallic compound, and the organic alkoxide of the metal alkoxide has a carbon number of 6 or more. The method for producing a polarizing film according to any one of claims 19 to 22, wherein the active energy ray-curable adhesive composition contains the metal chelate compound as the organometallic compound, and the organic metal chelate has an organic The carbon number of the base is 4 or more. The method for producing a polarizing film according to any one of claims 14 to 23, which has a viscosity of 15 mPa. An alkoxyalkylene group-containing compound above s. The method for producing a polarizing film according to claim 24, wherein the main chain of the alkoxyalkyl group-containing compound is an acrylic polymer structure. The method for producing a polarizing film according to any one of claims 17 to 21, wherein the active energy ray-curable adhesive composition is cured to obtain a storage elastic modulus of 1.0 × 10 ⁷ Pa at 25 ° C. the above.