TWI683142B - Single-sided protective polarizing film, polarizing film with adhesive layer, image display device and continuous manufacturing method thereof - Google Patents

Abstract

The object of the present invention is to provide a single-sided protective polarizing film having a protective film only on one side of a thin polarizer, which can still suppress penetration cracks and nano-slits even if the thin polarizer has predetermined optical characteristics The occurrence of defects and curl.

In terms of solution, the single-sided protective polarizing film of the present invention is one having a protective film on only one side of the polarizer, characterized in that the polarizer contains a polyvinyl alcohol-based resin and is constructed such that it penetrates with a monomer The optical characteristics represented by the ratio T and the polarization degree P satisfy the condition of the following formula: P>-(10 ^0.929T-42.4 -1)×100 (only T<42.3), or, P≧99.9 (only T≧42.3); and When the thickness of the polarizer is X (μm) and the thickness of the transparent resin layer is Y (μm), X≦12, Y≦15, and 0.15≦(Y/X)≦3 are satisfied.

Description

Single-sided protective polarizing film, polarizing film with adhesive layer, image display device and continuous manufacturing method thereof Field of invention

The invention relates to a single-sided protective polarizing film provided with a protective film on only one side of a polarizer, and a polarizing film having an adhesive layer with the single-sided protective polarizing film and an adhesive layer. The single-sided protective polarizing film and the polarizing film with an adhesive layer can be used as an optical film alone or laminated as an optical film to form an image display device such as a liquid crystal display device (LCD) or an organic EL display device.

Background of the invention

In the liquid crystal display device, it is necessary and necessary to dispose polarizing films on both sides of the glass substrate forming the surface of the liquid crystal panel due to its image forming method. The polarizing film is generally used by bonding a protective film with a polyvinyl alcohol-based adhesive or the like on one or both sides of a polarizer composed of a dichroic material such as polyvinyl alcohol-based film and iodine.

When attaching the polarizing film to a liquid crystal cell or the like, an adhesive is usually used. In addition, due to the advantages of instant fixation of the polarizing film and fixation of the polarizing film without a drying step, the adhesive is provided as an adhesive layer on one side of the polarizing film in advance. That is, in the polarizing film For adhesion, a polarizing film with an adhesive layer is usually used.

In addition, the polarizing film or the polarizing film with an adhesive layer, etc. have the following problems: severe thermal shock (for example, repeating the thermal shock test under the temperature conditions of -30°C and 80°C or the test at a high temperature of 100°C) Under the environment, it is easy to cause cracks (through-through cracks) in the absorption axis direction of the polarizer due to changes in the shrinkage stress of the polarizer. That is, the polarizing film with an adhesive layer is not sufficiently durable against thermal shock under the aforementioned severe environment. In particular, from the viewpoint of thinning, the use of a polarizing film with an adhesive layer provided with a single-sided protective polarizing film provided with a protective film on only one side of the polarizer is not sufficient for the durability of the aforementioned thermal shock. In addition, the aforementioned through cracks due to thermal shock are likely to appear when the size of the polarizing film becomes larger.

In order to suppress the occurrence of the aforementioned through cracks, it has been proposed, for example, to provide a protective layer with a tensile elastic modulus of 100 MPa or more on a single-sided protective polarizing film, and an adhesive layer polarizing film with an adhesive layer on the protective layer ( Patent Literature 1). It has also been proposed to have a protective layer made of a hardened resin composition on one side of a polarizer with a thickness of 25 μm or less, a protective film on the other side of the polarizer, and an adhesive layer on the outer side of the protective layer Such a polarizing film with an adhesive layer (Patent Document 2). The polarizing film with an adhesive layer described in the aforementioned Patent Documents 1 and 2 is effective from the viewpoint of suppressing the occurrence of penetration cracks. In addition, thinning has also been carried out in terms of polarizers. For example, there have been proposed thin polarizers that control the optical characteristics of the single transmittance and the degree of polarization and exhibit high alignment (Patent Document 3).

Advanced technical literature Patent Literature

Patent Document 1: Japanese Patent Publication No. 2010-009027

Patent Document 2: Japanese Patent Publication No. 2013-160775

Patent Document 3: Japanese Patent No. 4551481

Summary of the invention

Patent Documents 1 and 2 seek to reduce the thickness by using a single-sided protective polarizing film having a protective film on only one side of the polarizer, and on the other hand, by providing a protective layer to suppress the use of the single-sided protective polarizing film The occurrence of through cracks in the direction of the absorption axis of the polarizer.

On the other hand, thinning is also in progress with respect to polarizers. When the polarizer used in the polarizing film or the polarizing film with an adhesive layer is made thin, the change in shrinkage stress of the polarizer becomes smaller. Therefore, it has been understood that the use of a thinned polarizer can suppress the occurrence of the aforementioned through cracks.

However, in the case of the single-sided protective polarizing film whose inhibition of the occurrence of the aforementioned through cracks or the polarizing film with an adhesive layer using the same, when the optical characteristics are controlled as in Patent Document 3 and the polarizer is made thin (for example , When the thickness is 10 μm or less), when the polarizing film with a single-sided protective polarizing film or adhesive layer using the film is impacted by a load (including the load caused by the convex fold on the polarizer side), it is known Very thin slits (hereinafter also referred to as nano slits) will appear partly in the direction of the absorption axis of the piece. It is also known that the generation of the nano slits is independent of the size of the polarizing film. Furthermore, it is also known to use a double-sided protective polarizer with protective films on both sides of the polarizer In the case of a thin film, the aforementioned nano slits did not occur. In addition, it is known that when a through crack occurs in the polarizer, the stress around the through crack is relieved, and the through crack does not occur adjacently, but the nano-slits also occur adjacently except when they are generated separately. It is also known that penetration cracks have a tendency to extend in the direction of the absorption axis of the polarizer that has cracks, but the nano-slits do not have the aforementioned progress. As can be seen from this, the aforementioned nano-slit is a new problem that arises when the polarizer is thinned and the optical characteristics are controlled within a predetermined range with respect to the single-sided protective polarizing film where the occurrence of through cracks has been suppressed, and the past It is known that the aforementioned through crack is a problem caused by different phenomena.

In addition, because the nano slits are extremely thin, they cannot be detected under normal circumstances. Therefore, even if it is assumed that nano-slits have occurred in the polarizing member, it is still difficult to confirm the defects caused by light leakage of the polarizing film on one side and the polarizing film with an adhesive layer using the film at a glance. That is, the single-sided protective polarizing film is usually made into a long film shape and inspected for defects by automatic optical inspection, but it is difficult to detect nano-slits as defects by this defect inspection. The defects caused by the nano slits are also known to be applied to the glass substrate of the image display panel when the polarizing film with a single-sided protective polarizing film or an adhesive layer is attached to the glass substrate of the image display panel, etc. It expands laterally and thus becomes detectable (for example, the presence or absence of the aforementioned light leakage).

Therefore, it is desired that the single-sided protective polarizing film using a thin polarizer or the adhesive layer polarizing film using the film should not only prevent penetration cracks but also suppress defects caused by nano-slits. In addition, for a single-sided polarizing film or a polarizing film with an adhesive layer using the polarizing film, the double-sided protective structure with protective films on both sides is biased The optical film is thinner, so it is easy to bend or crack the polarizing film during operation. Therefore, it is expected that the polarizing film or the polarizing film with an adhesive layer using the polarizing film will not curl during operation. In addition, with respect to the single-sided protective polarizing film with a protective layer provided with a protective layer on the single-sided protective polarizing film by curing or hardening, when the protective layer is formed, the shrinkage of the material forming the protective layer is induced. Stress is likely to remain between the protective layers, and curling is likely to occur. Therefore, in terms of protecting the polarizing film on one side or the polarizing film with an adhesive layer using the polarizing film, it is expected that no curling occurs from the viewpoint of operability.

An object of the present invention is to provide a single-sided protective polarizing film having a protective film on only one side of a thin polarizer, which can suppress the occurrence of defects and curling caused by through cracks and nano-slits, and the polarizer has a predetermined optical characteristic. In addition, an object of the present invention is to provide an adhesive layer polarizing film having the single-sided protective polarizing film and the adhesive layer.

In addition, an object of the present invention is to provide an image display device having the single-sided protective polarizing film or the adhesive layer-attached polarizing film, and further to provide a continuous manufacturing method thereof.

The inventors of the present invention have found that the above-mentioned problems can be solved by the following single-sided protection polarizing film, polarizing film with adhesive layer, etc. through the investigation and review, and completed the present invention.

That is, the present invention relates to a single-sided protective polarizing film having a protective film on only one side of the polarizer, characterized in that the polarizer contains a polyvinyl alcohol-based resin and is structured such that it has a single-piece penetration rate The optical characteristics represented by T and the degree of polarization P satisfy the conditions of the following formula: P>-(10 ^0.929T-42.4 -1)×100 (only T<42.3), or P≧99.9 (only T≧42.3); and, in When the thickness of the polarizer is X (μm) and the thickness of the transparent resin layer is Y (μm), X≦12, Y≦15, and 0.15≦(Y/X)≦3 are satisfied.

In the single-sided protective polarizing film, the transparent resin layer preferably has a compressive elastic modulus of 0.1 GPa or more at 80°C.

Among the single-sided protective polarizing films, the transparent resin layer is preferably formed of ultraviolet-curable acrylic resin, ultraviolet-curable epoxy resin, urethane resin or polyvinyl alcohol resin.

The single-sided protective polarizing film preferably has an adhesive layer between the polarizer and the protective film. The thickness of the adhesive layer is preferably 0.1 μm or more and 5 μm or less. In addition, the adhesive layer preferably has a compression elastic modulus at 80° C. of 0.1 GPa or more and 10 GPa or less. In addition, the adhesive layer is preferably formed of an ultraviolet curing acrylic resin, an ultraviolet curing epoxy resin, a urethane resin, or a polyvinyl alcohol resin.

In the single-sided protective polarizing film, when the protective film is one piece, the thickness of the protective film is preferably 10 μm or more and 100 μm or less.

In the above single-sided protective polarizing film, when the protective film is two, the thickness of each protective film is preferably 10 μm or more, the total thickness of the protective film is 100 μm or less, and there is an adhesive between each protective film Layer or adhesive layer.

In the single-sided protective polarizing film, the polarizer preferably contains boric acid at 25% by weight or less based on the total amount of polarizers.

The present invention also relates to a polarizing film having an adhesive layer with the single-sided protective polarizing film and the adhesive layer.

In the polarizing film with an adhesive layer, the thickness of the adhesive layer is preferably 1 μm or more and 40 μm or less. The adhesive layer preferably has a storage elastic modulus at 23° C. of 1.0×10 ⁴ Pa or more.

The polarizing film with an adhesive layer can be used in a state where the adhesive layer is provided on the transparent resin layer that protects the polarizing film on one side. In addition, the polarizing film with an adhesive layer can be used in a state where the adhesive layer is provided on the protective film that protects the polarizing film on one side. In addition, the adhesive layer of the polarizing film with an adhesive layer may be provided with a separating member. The polarizing film with an adhesive layer provided with a separator can be used as a winding.

The present invention also relates to an image display device having the single-sided protective polarizing film or the polarizing film with an adhesive layer.

The present invention also relates to a continuous manufacturing method for an image display device, which includes the steps of: outputting the adhesive layer polarizing film from the winding of the adhesive layer polarizing film and transporting it using the separator, and The polarizing film with the adhesive layer is continuously bonded to the surface of the image display panel through the adhesive layer.

The single-sided protective polarizing film of the present invention and the bias with an adhesive layer The optical film is thinned by using a polarizer with a thickness of 12 μm or less. In addition, the thin polarizer having a thickness of 12 μm or less has a smaller change in shrinkage stress applied to the polarizer due to thermal shock than when the polarizer is thicker, so that the occurrence of through cracks can be suppressed.

On the other hand, thin polarizers with specified optical characteristics will easily have nano slits in the polarizers. Nano slits are considered to be the manufacturing steps of the single-sided protective polarizing film, the manufacturing process of the polarizing film with an adhesive layer provided with an adhesive layer on the single-sided protective polarizing film, and the manufacturing of the polarizing film with an adhesive layer Among the various steps, it is generated when the single-sided protective polarizing film or the polarizing film with an adhesive layer using the polarizing film is subjected to mechanical shock, and it is presumed that the mechanism is different from the through crack caused by thermal shock Produced. In addition, when the defects caused by the nano slits are placed on the glass substrate of the image display panel or the like when the polarizing film with a single-sided protective polarizing film or adhesive layer is attached to the heating environment, the nano fine The slit expands laterally and becomes detectable (for example, whether there is light leakage as described above).

The single-sided protective polarizing film and the polarizing film with an adhesive layer of the present invention are provided with a transparent resin layer on the other side of the polarizer (the side without the protective film), even if the polarizing film is protected on the single side before the transparent resin layer is provided In the state of the polarizer with the aforementioned nano slits, the occurrence of defects due to the expansion of the nano slits in the width direction can still be suppressed. In particular, a transparent resin layer having a compressive elastic modulus at 80°C of 0.1 GPa or more is particularly effective.

As described above, the single-sided protective polarizing film of the present invention and the polarizing film with an adhesive layer using the same have a transparent resin layer, thereby enabling It is enough to reduce the thickness and at the same time, suppress the penetrating cracks generated by the polarizer and defects caused by nano-slits.

In addition, the single-sided protective polarizing film and the polarizing film with an adhesive layer of the present invention are designed to meet the requirements of X≦12, Y≦15 and the thickness X (μm) of the thin polarizer and the thickness Y (μm) of the transparent resin layer. 0.15≦(Y/X)≦3, regardless of whether or not a transparent resin layer capable of suppressing penetrating cracks generated by the polarizer and defects caused by nano-slits can suppress curling.

1‧‧‧ Polarizer

2, 2 ' ‧‧‧ protective film

2a‧‧‧adhesive layer

3‧‧‧Transparent resin layer

4‧‧‧Adhesive layer

5, 5a, 5b ‧‧‧ Separate parts

6, 6a, 6b ‧‧‧ surface protection film

10‧‧‧Single-sided protective polarizing film

11.11’‧‧‧Single-sided protective polarizing film (with transparent resin layer)

12‧‧‧Polarized film with adhesive layer

20‧‧‧Glass plate

20a, 20b‧‧‧ Polarized thin with adhesive layer Film winding (coiled material)

21a, 21b ‧‧‧ Polarizing film with adhesive layer (with surface protective film)

100‧‧‧Continuous manufacturing system of image display device

101a, 101b‧‧‧ Polarized film supply section

151a, 151b ‧‧‧ output section

152a, 152b‧‧‧Cutting Department

153a, 153b

154a, 154b ‧‧‧ take-up department

201a, 201b ‧‧‧ Laminating Department

300‧‧‧Configuration exchange department

a‧‧‧Nano slit

b‧‧‧Through crack

P‧‧‧Image display panel

X‧‧‧ Conveying section of image display panel

FIG. 1 is an example of a schematic cross-sectional view of a single-sided protective polarizing film of the present invention.

2 is an example of a schematic cross-sectional view of a polarizing film with an adhesive layer of the present invention.

FIG. 3 is an example of a conceptual diagram comparing nano slits and through cracks generated in a polarizer.

FIG. 4 is an example of a cross-sectional photograph of a single-sided protective polarizing film, showing whether or not a nano-slit has occurred, and when the nano-slit has been generated, the expansion of the nano-slit due to heating varies depending on the presence or absence of a transparent resin layer.

FIG. 5 is a schematic diagram illustrating nano-slit-related evaluation items of Examples and Comparative Examples.

6 is an example of photographs showing cracks caused by nano-slits in the evaluation of Examples and Comparative Examples.

7 is an example of photographs showing the progress of through cracks evaluated in Examples and Comparative Examples.

8 is an example of a schematic cross-sectional view of a continuous manufacturing system of an image display device.

Forms for carrying out the invention

Hereinafter, the single-sided protective polarizing film 11 and the polarizing film 12 with an adhesive layer of the present invention will be described with reference to FIGS. 1 and 2. The single-sided protective polarizing film 10 (when there is no transparent resin layer 3) is, for example, as shown in FIG. 1(A), and the protective film 2 is provided only on one side of the polarizer 1. The polarizer 1 and the protective film 2 are laminated through an adhesive layer 2a (other intermediary layers such as an adhesive layer, an undercoat layer (primer layer), etc.). Although not shown, the single-sided protective polarizing film 10 may be provided with an easy adhesion layer or activation treatment on the protective film 2 to laminate the easy adhesion layer and the adhesive. The single-sided protective polarizing film 11 (with the transparent resin layer 3) of the present invention is shown in FIG. 1, on the single-sided protective polarizing film 10, on the other side of the polarizer 1 (the side without the protective film 2) ( Directly) the transparent resin layer 3 is provided. Furthermore, as shown in FIG. 1(B), a plurality of protective films 2 may be provided. FIG 1 (B) is a protective film 2 is provided with 2, 2 'one side of the polarizing film protection (with a transparent resin layer) 11'. 2 protective film and the protective film 2 'may agent layer 2a (such as other adhesive layer, an undercoat layer (primer layer) interposer, etc.) via the then be laminated.

As mentioned above, the thickness X (μm) of the polarizer and the thickness Y (μm) of the transparent resin layer are designed to satisfy X≦12, Y≦15, 0.15≦(Y/X)≦3. From the viewpoint of suppressing defects caused by nano slits generated in the polarizer, the aforementioned value (Y/X) is preferably 0.24 or more. On the other hand, from the viewpoint of suppressing curl, the aforementioned value (Y/X) is preferably 0.8 or less, and more preferably 0.5 or less. The aforementioned value (Y/X) is preferably 0.24≦(Y/X)≦0.8, more preferably 0.24≦(Y/X)≦0.5.

Moreover, the polarizing film 12 with an adhesive layer of the present invention, as shown in FIG. 2, has a single-sided protective polarizing film (with a transparent resin layer) 11 and an adhesive layer 4. The adhesive layer 4 is provided on the side of the transparent resin layer 3 in FIG. 2(A), and is provided on the side of the protective film 2 in FIG. 2(B). In addition, a separation member 5 may be provided on the adhesive layer 4 of the polarizing film 12 with an adhesive layer of the present invention, and a surface protection film 6 may be provided on the opposite side. The polarizing film 12 with an adhesive layer in FIG. 2 shows the case where both the separating member 5 and the surface protective film 6 are provided. The polarizing film 12 with at least the adhesive layer of the separating member 5 (further having the surface protective film 6) can be used as a winding, and it is advantageous to be applied to, for example, outputting the adhesion from the winding as described later The polarizing film 12 of the agent layer is transported by the separating member 5 and is pasted on the surface of the image display panel through the adhesive layer 4 (hereinafter, also referred to as "roll-to-panel method"). (Representatively, as described in Japanese Patent No. 4404043). From the viewpoint of suppressing warpage of the display panel after bonding and suppressing the occurrence of nano-slits, the polarizing film with an adhesive layer is preferably as described in FIG. 2(A). The surface protective film 6 may be provided on the single-sided protective polarizing film 10 and the single-sided protective polarizing film (with a transparent resin layer) 11. 2 illustrates the case where the single-sided protective polarizing film (with transparent resin layer) 11 of FIG. 1(A) is used, but the single-sided protective polarizing film (with transparent resin layer) of FIG. 1(B) may also be used )11 ' .

FIG. 3 is a conceptual diagram comparing the nano slit a and the through crack b generated in the polarizer. FIG. 3(A) shows the nano slit a generated in the polarizer 1; and FIG. 3(B) shows the through crack b generated in the polarizer 1. FIG. The nano-slit a is caused by mechanical impact and partially occurs in the direction of the absorption axis of the polarizer 1. Although the nano-slit a cannot be confirmed when it has occurred, it can be in a hot environment (For example, 90%RH at 80°C or 60°C), confirm by expanding in the lateral direction. On the other hand, the nano-slit a is considered not to have progress in the direction of the absorption axis of the polarizer. In addition, the aforementioned nano slit a is considered to be generated regardless of the size of the polarizing film. In addition to the formation of nano slits a, there are also neighbors. On the other hand, the through crack b is caused by thermal shock (for example, thermal shock test). The penetrating crack has a progressive extension in the direction of the absorption axis of the polarizer that has generated the crack. When the penetrating crack b has occurred, the surrounding stress will be relieved, so the penetrating crack will not be generated adjacently.

FIG. 4 is an example of a cross-sectional photograph of a single-sided protective polarizing film 10 or a single-sided protective polarizing film 11 with a transparent resin layer, which relates to the occurrence, expansion, and repair of nano-slits a generated in the polarizer. FIG. 4(A) shows an example of a single-sided protective polarizing film 10 provided with a protective film 2 only on one side of the polarizer 1 through the adhesive layer 2a, when no nano-slits have occurred. FIG. 4(B) is an example of the case where the nano slit a occurs in the single-sided protective polarizing film 10. Figure 4 (A) and (B) are before heating. In addition, FIG. 4(C) is an example of a photograph of a cross-sectional view of a single-sided protective polarizing film 10 in which nano slits a appear after heating. As can be seen from FIG. 4(C), the nano slit a of the polarizer 1 is expanding due to heating. On the other hand, FIG. 4(D) is an example of a photograph of a cross-sectional view of a single-sided protective polarizing film 11 with a transparent resin layer 3 and a transparent resin layer 3 formed on the single-sided protective polarizing film 10 where the nano slit a has occurred. As can be seen from FIG. 4(D), the nano slit a generated in the polarizer 1 is repaired via the transparent resin layer 3 (a ′ ). 4(E) is an example of a photograph of a cross-sectional view of the transparent resin layer-attached single-sided protective polarizing film 11 on which the transparent resin layer 3 has been formed after heating. As can be seen from Fig. 4(E), after heating, the repaired (a ' ) nanoslits did not expand. FIG. 4 is a cross-sectional cutting with a profile grinder or microtome perpendicular to the direction of the absorption axis of the sample, and observation with a scanning electron microscope.

<polarizer>

In the present invention, a polarizer having a thickness of 12 μm or less is used. The thickness of the polarizer is preferably 10 μm or less, preferably 8 μm or less, preferably 7 μm or less, or 6 μm or less from the viewpoint of thinning and suppressing the occurrence of through cracks. On the other hand, the thickness of the polarizer is preferably 2 μm or more, and more preferably 3 μm or more. Such a thin polarizer has less thickness variation, excellent visibility and low dimensional change, so it has excellent durability against thermal shock.

The polarizer is made of polyvinyl alcohol resin. Examples of polarizers include hydrophilic polymer films such as polyvinyl alcohol-based films, partially formalized polyvinyl alcohol-based films, and ethylene-vinyl acetate copolymer-based partially saponified films that absorb iodine or dichroic dyes. The dichromatic materials are uniaxially stretched, and polyolefin-based alignment films such as polyvinyl alcohol dehydration treatment products or polyvinyl chloride dehydrochlorination treatment products. Among these, a polarizer composed of a polyvinyl alcohol-based film and a dichroic substance such as iodine is suitable.

A polarizer made by dyeing a polyvinyl alcohol-based film with iodine and uniaxially extending it can be produced, for example, by immersing polyvinyl alcohol in an aqueous solution of iodine to dye and extend it to 3 to 7 times its original length. It can also be immersed in an aqueous solution of boric acid or potassium iodide, which may also contain zinc sulfate or zinc chloride, as required. In addition, the polyvinyl alcohol-based film can be immersed in water and washed before being dyed according to requirements. By washing the polyvinyl alcohol-based film with water, the dirt and anti-caking agent on the surface of the polyvinyl alcohol-based film can be washed away. Film swelling also has the effect of preventing uneven dyeing. The extension can be carried out after dyeing with iodine, or it can be dyed while being stretched, or it can be dyed with iodine after being stretched. It can also be extended in aqueous solutions such as boric acid or potassium iodide or in a water bath.

The polarizer is preferably one containing boric acid in terms of extension stability or optical durability. In addition, the content of boric acid contained in the polarizer is preferably 25% by weight or less, more preferably 20% by weight or less relative to the total amount of polarizers from the viewpoint of suppressing the occurrence of through cracks and nano-slits and suppressing expansion. It is preferably 18% by weight or less, more preferably 16% by weight or less. When the content of boric acid contained in the polarizer exceeds 20% by weight, even if the thickness of the polarizer is controlled to 10 μm or less, the shrinkage stress of the polarizer is still high and penetrating cracks easily occur, which is not suitable. On the other hand, from the viewpoint of the extension stability and optical durability of the polarizer, the boric acid content relative to the total amount of the polarizer is preferably 10% by weight or more, and more preferably 12% by weight or more.

Examples of the thin polarizers include Japanese Patent No. 4751486, Japanese Patent No. 4751481, Japanese Patent No. 4815544, Japanese Patent No. 5048120, Japanese Patent No. 5587517, and International Publication No. 2014 The thin polarizer described in the specification of /077599, International Publication No. 2014/077636 and the like, or the thin polarizer obtained by the manufacturing method described in the specification.

The aforementioned polarizer is constructed such that its optical characteristics expressed by the single transmittance T and the polarization degree P satisfy the conditions of the following formula: P>-(10 ^0.929T-42.4 -1)×100 (only T<42.3); Or P≧99.9 (but T≧42.3). The polarizer structured to satisfy the aforementioned conditions undoubtedly has the performance required for a liquid crystal television display using a large display element. Specifically, the contrast ratio is 1000:1 or more and the maximum brightness is 500 cd/m ² or more. For other uses, for example, it is attached to the visible side of the organic EL display device.

On the other hand, a polarizer structured to satisfy the aforementioned conditions, since the constituent polymer (for example, polyvinyl alcohol-based molecule) exhibits high alignment, is complementary to the point where the thickness is 10 μm or less, and the polarizer absorbs the direction perpendicular to the axis direction The tensile stress at break becomes significantly smaller. As a result, for example, when subjected to a mechanical impact that exceeds the tensile cracking stress during the manufacturing process of the polarizing film, the possibility that the nano slits are generated in the direction of the absorption axis of the polarizer is extremely high. Therefore, the present invention is particularly suitable for the single-sided protective polarizing film (or the polarizing film with an adhesive layer) using the polarizer.

As the aforementioned thin polarizer, in a manufacturing method including a step of extending in a layered state and a dyeing step, in view of the fact that it can be extended at a high magnification and that the polarizing performance can be improved, for example, Japanese Patent No. 4751486, Japanese Patent Those obtained by the manufacturing method described in Japanese Patent No. 4751481 and Japanese Patent No. 4815544, which are generally included in an aqueous solution of boric acid and subjected to an extension step, are particularly preferably contained in boric acid as described in Japanese Patent No. 4751481 and Japanese Patent No. 4815544. Obtained by a method of performing an auxiliary aerial extension step before extension in an aqueous solution. These thin polarizing films can be produced by a manufacturing method containing the following steps: a step of extending and dyeing a layer of a polyvinyl alcohol-based resin (hereinafter also referred to as a PVA-based resin) and a resin substrate for extension in the state of a laminate A step of. If it is this manufacturing method, the thinner PVA-based resin layer can still be extended without defects such as breakage due to extension by being supported by the extension resin base material.

<protective film>

As the material constituting the protective film, those having excellent transparency, mechanical strength, thermal stability, moisture blocking property, isotropy, etc. are suitable. Examples include polyester-based polymers such as polyethylene terephthalate and polyethylene naphthalate; cellulose-based polymers such as diethyl cellulose and triethyl cellulose; polymethacrylate Acrylic polymers such as esters; styrene polymers such as polystyrene and acrylonitrile-styrene copolymers (AS resins); and polycarbonate polymers. In addition, the following polymers can be cited as examples of the polymer forming the above protective film: polyethylene, polypropylene, polyolefin having a cyclic or even camphene structure, and polyolefin polymerization such as ethylene-propylene copolymer Substances, chlorinated vinyl polymers, nylon and aromatic polyamides, and other amide-based polymers, imine-based polymers, lanyard-based polymers, polyether lanyard-based polymers, polyetheretherketone-based polymers, poly Phenylene sulfide-based polymer, vinyl alcohol-based polymer, chlorinated vinylidene-based polymer, vinyl butyral-based polymer, aryl ester-based polymer, polyoxymethylene-based polymer, epoxy-based polymer or the above-mentioned polymer Of blends, etc.

In addition, the protective film may contain at least one kind of any appropriate additives. Additives include, for example, ultraviolet absorbers, antioxidants, slip agents, plasticizers, release agents, coloring inhibitors, flame retardants, nuclear agents, antistatic agents, pigments, colorants, and the like. In the protective film, the content of the thermoplastic resin is preferably 50 to 100% by weight, preferably 50 to 99% by weight, more preferably 60 to 98% by weight, and particularly preferably 70 to 97% by weight. When the content of the thermoplastic resin in the protective film is 50% by weight or less, there is a possibility that the thermoplastic resin cannot sufficiently express the high transparency originally possessed.

As the protective film, a phase difference film, Bright film, diffused film, etc. Examples of the retardation film include those having a frontal phase difference of 40 nm or more and/or a thickness direction phase difference of 80 nm or more. The frontal phase difference is usually controlled in the range of 40 to 200 nm, while the thickness direction phase difference is usually controlled in the range of 80 to 300 nm. When a retardation film is used as a protective film, since the retardation film also functions as a polarizer protective film, it can be made thinner.

Examples of the retardation film include a birefringent film obtained by uniaxially or biaxially stretching a thermoplastic resin film. The stretching temperature, stretching magnification, etc. can be appropriately set according to the phase difference value, film material and thickness.

The thickness of the protective film can be appropriately determined, but it is generally about 1 to 500 μm from the viewpoints of workability, thinness, etc. such as strength and operability. It is particularly preferably 1 to 300 μm, and preferably 5 to 200 μm. In particular, in the case of one protective film, the thickness is preferably 100 μm or less, preferably 80 μm or less, or 60 μm or less from the viewpoint of thinning. In addition, from the viewpoint of protecting the polarizing film from bending or cracking, it is preferably 10 μm or more, and more preferably 20 μm or more. When the thickness of the protective film is V (μm), the relationship between the thickness of the polarizer X (μm) and the thickness of the transparent resin layer Y (μm) reduces the polarizer when mechanical stress is applied to the polarizer film From the viewpoint of bending, it is preferable to satisfy 4X≦(Y+V), and further preferably satisfy 5X≦(Y+V).

In addition, two protective films can be used. From the viewpoint of protecting the polarizing film from bending or cracking, the total thickness of the protective films of the two protective films is preferably 10 μm or more, more preferably 20 μm or more, and from the viewpoint of thinning the polarizing film on one side See, the total of each protective film can be controlled It is preferably 100 μm or less.

A functional layer such as a hard layer, an anti-reflection layer, an anti-adhesive layer, a diffusion layer, and even an anti-glare layer may be provided on the surface of the protective film that is not attached to the polarizer (especially in the aspect of FIG. 1). In addition, the above-mentioned functional layers such as the hard layer, the anti-reflection layer, the anti-adhesive layer, the diffusion layer, and the anti-glare layer may be provided separately from the protective film in addition to the protective film itself.

<intermediate layer>

The protective film and the polarizer are laminated through intermediary layers such as an adhesive layer, an adhesive layer, and an undercoat layer (primer layer). In this case, it is desirable to stack the two without an air gap via the interposer. The aforementioned protective film and polarizer are preferably laminated with an adhesive layer.

The adhesive layer is formed of an adhesive. The type of adhesive is not particularly limited, and various types can be used. The adhesive layer is not particularly limited as long as it is optically transparent, and various forms such as water-based, solvent-based, hot-melt adhesive-based, and active energy ray-curable types can be used as the adhesive, but the water-based adhesive or active The energy ray hardening type adhesive is ideal.

Examples of the water-based adhesive include isocyanate-based adhesives, polyvinyl alcohol-based adhesives, gelatin-based adhesives, vinyl-based latex-based adhesives, and water-based polyesters. The water-based adhesive is generally used as an adhesive composed of an aqueous solution, and usually contains 0.5 to 60% by weight of a solid component. Among them, isocyanate adhesives and polyvinyl alcohol adhesives are suitable. An urethane-based resin layer is formed as an adhesive layer from an isocyanate-based adhesive.

Active energy ray-curable adhesives are cured with active energy rays such as electron beams, ultraviolet rays (radical curing type, cation curing type), etc. For the adhesive, for example, electron beam curing type and ultraviolet curing type can be used. For the active energy ray hardening type adhesive, for example, a photo radical hardening type adhesive can be used. When a photoradical hardening type active energy ray hardening type adhesive is used as the ultraviolet curing type, the adhesive contains a radical polymerizable compound and a photopolymerization initiator. For example, as the radical curing type ultraviolet curing adhesive, it is preferable to be ultraviolet curing acrylic resin, and as the cation curing type ultraviolet curing adhesive, it is preferably ultraviolet curing epoxy resin.

The coating method of the adhesive is appropriately selected according to the viscosity and the target thickness of the adhesive. Examples of the coating method include, for example, a reverse coater, a gravure coater (direct, reverse or lithography), a bar reverse coater, a roll coater, a mold coater, a bar coater, and a doctor blade Bar coater, etc. In other respects, methods such as dip coating can be used as appropriate for coating.

In addition, the thickness of the adhesive layer is preferably 0.1 μm or more and 5 μm or less, and an ideal range can be set according to the type of the water-based adhesive or the active energy ray-curable adhesive. The thickness is preferably 0.1 μm or more in terms of maintaining the adhesive force, and 5 μm or less in terms of ensuring optical reliability. The application of the aforementioned adhesive is preferably performed in such a manner that the thickness of the adhesive layer finally formed is 100 to 300 nm when using an aqueous adhesive or the like. The thickness of the aforementioned adhesive layer is more preferably 100 to 250 nm. On the other hand, in the case of using an active energy ray-curable adhesive, it is preferable to carry out such that the thickness of the adhesive layer is 0.2 to 5 μm. It is preferably 0.2 to 2 μm, and more preferably 0.5 to 1.5 μm.

Also, the aforementioned adhesive layer relaxes the force applied to the polarizer at the same time The suppression of the through cracks is preferably a compression elastic modulus at 80°C of 0.1 GPa or more and 10 GPa or less. In order to absorb impact and ensure crack resistance (suppression of nano-slits and suppression of penetration cracks), it is preferable to set the compressive elastic modulus to 0.1 GPa or more; from the viewpoint of not suppressing polarizers but suppressing penetration cracks , It is better to set it below 10GPa. In particular, when the active energy ray-curable adhesive is used to form the adhesive layer, the compression elastic modulus is preferably 1 GPa or more, and more preferably 3 GPa or more. On the other hand, the aforementioned compression elastic modulus is preferably 8 GPa or less.

In addition, when laminating the polarizer and the protective film, an easy adhesive layer may be provided between the protective film and the adhesive layer. The easy-adhesion layer may be formed of various resins having, for example, the following skeletons: polyester skeleton, polyether skeleton, polycarbonate skeleton, polyurethane skeleton, polysiloxane system, polyamide skeleton, polyimide skeleton , Polyvinyl alcohol skeleton, etc. These polymer resins can be used alone or in combination of two or more. In addition, other additives may be added to the formation of the easy-adhesion layer. Specifically, stabilizers such as adhesion-imparting agents, ultraviolet absorbers, antioxidants, heat-resistant stabilizers, and the like can be further used.

The easy adhesion layer is usually provided in advance on the protective film, and the easy adhesion layer side of the protective film and the polarizer are laminated by an adhesive layer. The formation of the easy-adhesion layer is carried out by applying the formation material of the easy-adhesion layer to the protective film by a conventional technique and drying it. The forming material of the easy-adhesion layer is usually adjusted and diluted into a solution of appropriate concentration in consideration of the thickness after drying, the smoothness of the coating, and the like. The thickness of the easy adhesion layer after drying is preferably 0.01 to 5 μm, more preferably 0.02 to 2 μm, and even more preferably 0.05 to 1 μm. Moreover, although the easy adhesion layer can Multiple layers are provided, but at this time it is still desirable to make the total thickness of the easy-adhesion layer within the above range.

The adhesive layer is formed by the adhesive. As the adhesive, various adhesives can be used, and examples include rubber-based adhesives, acrylic adhesives, polysiloxane adhesives, urethane-based adhesives, vinyl alkyl ether-based adhesives, and polyethylene. Pyrrolidone-based adhesives, polyacrylamide-based adhesives, cellulose-based adhesives, etc. The adhesive base polymer is selected according to the type of the aforementioned adhesive. Among the above-mentioned adhesives, the use of acrylic adhesives is preferable in terms of excellent optical transparency, adhesive properties exhibiting proper wettability, cohesiveness, and adhesiveness, and excellent weather resistance and heat resistance.

The undercoat layer (primer layer) is formed to improve the adhesion between the polarizer and the protective film. The material constituting the primer layer is not particularly limited as long as it exerts a certain degree of strong adhesion to both the base film and the polyvinyl alcohol-based resin layer. For example, a thermoplastic resin excellent in transparency, thermal stability, extensibility, etc. can be used. Examples of the thermoplastic resin include acrylic resins, polyolefin resins, polyester resins, polyvinyl alcohol resins, and mixtures thereof.

In the case where at least two protective films are used, the lamination of each protective film should preferably pass through the adhesive layer or the adhesive layer. The thickness of the adhesive layer is preferably 0.1 μm or more, and more preferably 0.2 μm or more from the viewpoint of adhesion. On the other hand, from the viewpoint of thinning, the thickness of the adhesive layer is preferably 5 μm or less, and more preferably 2 μm or less. In addition, when an adhesive is used for the lamination of each protective film, the thickness is preferably 2 μm or more from the viewpoint of adhesion. On the other hand, from the viewpoint of thinning, the aforementioned adhesive The thickness of the layer is preferably 20 μm or less.

<transparent resin layer>

In a single-sided protective polarizing film provided with a protective film on only one side of the polarizer, the transparent resin layer is provided on the other side of the polarizer (the side where the protective film is not laminated). In the present invention, it is preferable that the transparent resin layer has a compressive elastic modulus at 80° C. of 0.1 GPa or more. Even if nano-slits are generated in the polarizer due to mechanical impact, and the nano-slits expand in the width direction under a hot environment, the elastic modulus of compression is controlled to 0.1 GPa or more by compressing the transparent resin layer at 80°C, even in the heat Under the environment, the mechanical retention of the transparent resin layer can be maintained and the expansion of the nano slits in the width direction can be suppressed. The compressive elastic modulus of the transparent resin layer is preferably 0.5 GPa or more, more preferably 2 GPa or more, more preferably 3 GPa or more, more preferably 5 GPa or more, more preferably 6 GPa or more, and more preferably 10 GPa or more. The compression elastic modulus of the transparent resin layer can be adjusted by the selection of materials. In addition, the compressive elastic modulus of 80° C. of the transparent resin layer is a value measured based on the description in the examples.

The thickness of the transparent resin layer is 15 μm or less from the viewpoint of thinning and optical reliability. In addition, once the transparent resin layer becomes thick, it becomes easy to protect the polarizing film from curling on one side after storage. The thickness (Y) of the transparent resin layer is more preferably 12 μm or less, more preferably 5 μm or less, and more preferably 1.5 μm or less. On the other hand, the thickness (Y) of the transparent resin layer is preferably 0.2 μm or more, more preferably 0.5 μm or more, even more preferably 0.6 μm or more, and more preferably from the viewpoint of the effect of suppressing the expansion of the nano slits. Above 0.8μm. The thickness (Y) of the transparent resin layer is controlled to satisfy 0.15≦(Y/X)≦3 in relation to the thickness X (μm) of the polarizer.

The transparent resin layer may be formed of a curable type forming material containing curable components. Curable components can be roughly divided into active energy ray curing type and thermosetting type such as electron beam curing type, ultraviolet curing type and visible light curing type. In addition, ultraviolet curing type and visible light curing type can be divided into radical polymerization curing type and cationic polymerization type. In the present invention, the active energy rays with a wavelength range of 10 nm to less than 380 nm are marked as ultraviolet rays, and the active energy rays with a wavelength range of 380 nm to 800 nm are marked as visible rays. The aforementioned radical polymerization hardening type curable component can be used as a thermosetting type curable component.

"Free Radical Polymerization Hardening Forming Materials"

Examples of the curable component include radical polymerizable compounds. The radically polymerizable compound may be exemplified by a compound having a radically polymerizable functional group having a carbon-carbon double bond such as (meth)acryloyl group and vinyl group. As these hardening components, any of a monofunctional radical polymerizable compound or a bifunctional or higher polyfunctional radical polymerizable compound can be used. Moreover, these radically polymerizable compounds can be used individually by 1 type or in combination of 2 or more types. For example, these radically polymerizable compounds are suitably compounds having a (meth)acryloyl group. In the present invention, the term "(meth)acryloyl" means propenyl and/or methacryl, and "(meth)" has the same meaning as below.

"Monofunctional Radical Polymerizable Compound"

For example, the monofunctional radical polymerizable compound can be exemplified by (meth)acrylamide derivatives having a (meth)acrylamide group. In addition to ensuring the adhesion to the polarizer, the (meth)acrylamide derivative is more desirable because of its high polymerization speed and excellent productivity. (Meth)acrylamide Specific examples of derivatives include, for example, N-methyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide N-alkyl-containing (meth)acrylamides such as amines, N-isopropyl(meth)acrylamide, N-butyl(meth)acrylamide, N-hexyl(meth)acrylamide, etc. Amine derivatives; N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-hydroxymethyl-N-propane (meth) acrylamide, etc. contain N- (Meth)acrylamide derivatives of hydroxyalkyl; aminemethyl(meth)acrylamide, amine ethyl(meth)acrylamide, etc. (meth)acrylamide containing N-aminoalkyl Derivatives; (Meth)acrylamide derivatives containing N-alkoxy such as N-methoxymethacrylamide, N-ethoxymethacrylamide; mercaptomethyl (meth)propene N-mercaptoalkyl-containing (meth)acrylamide derivatives such as amide and mercaptoethyl (meth)acrylamide. In addition, the heterocyclic ring-containing (meth)acrylamide derivative in which the nitrogen atom of the (meth)acrylamide group forms a heterocycle can be exemplified by N-propenyl morpholine, N-propenyl acetyl piperidine , N-methacryloyl piperidine, N-propenyl pyrrolidine and so on.

Among the aforementioned (meth)acrylamide derivatives, in view of the adhesion to the polarizer, it is also preferably a (meth)acrylamide derivative containing N-hydroxyalkyl, especially It is preferably N-hydroxyethyl (meth) acrylamide.

In addition, the monofunctional radical polymerizable compound may, for example, be various (meth)acrylic acid derivatives having (meth)acryloyloxy groups. Specifically, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, 2-methyl-2- Nitropropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, third butyl (meth)acrylate, ( N-amyl meth)acrylate, tert-amyl (meth)acrylate, 3-pentyl (methyl) Acrylate, 2,2-dimethylbutyl (meth)acrylate, n-hexyl (meth)acrylate, cetyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethyl (Meth)acrylic acid (carbon number 1-20) alkyl such as hexyl (meth)acrylate, 4-methyl-2-propylpentyl (meth)acrylate, n-octadecyl (meth)acrylate Base esters.

In addition, the (meth)acrylic acid derivatives include, for example, cycloalkyl (meth)acrylates such as cyclohexyl (meth)acrylate and cyclopentyl (meth)acrylate; benzyl (meth) Aralkyl (meth)acrylates such as acrylates; 2-isobornyl (meth)acrylates, 2-norbornylmethyl (meth)acrylates, 5-norcamen-2-yl-methyl (Meth)acrylate, 3-methyl-2-norbornyl methyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (methyl Group) acrylate, dicyclopentyl (meth)acrylate and other polycyclic (meth)acrylate; 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth Group) acrylate, 2-methoxymethoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, ethyl carbitol (meth)acrylate, phenoxy (Meth)acrylates containing alkoxy or phenoxy groups such as ethyl ethyl (meth)acrylate, alkylphenoxy polyethylene glycol (meth)acrylate, etc.

In addition, the (meth)acrylic acid derivative may be exemplified by 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxyl Decyl (meth)acrylate, 12-hydroxylauryl (meth)acrylic Esters such as hydroxyalkyl (meth)acrylate or [4-(hydroxymethyl)cyclohexyl]methacrylate, cyclohexanedimethanol mono(meth)acrylate, 2-hydroxy-3-phenoxy Hydroxy-containing (meth)acrylates such as propylpropyl (meth)acrylate; epoxypropyl (meth)acrylates, 4-hydroxybutyl (meth)acrylate epoxypropyl ethers, etc. Oxygenated (meth)acrylate; 2,2,2-trifluoroethyl (meth)acrylate, 2,2,2-trifluoroethylethyl (meth)acrylate, tetrafluoropropyl (Meth)acrylate, hexafluoropropyl (meth)acrylate, octafluoropentyl (meth)acrylate, heptafluorodecyl (meth)acrylate, 3-chloro-2-hydroxypropyl (Meth)acrylates and other halogen-containing (meth)acrylates; dimethylaminoethyl (meth)acrylates and other alkylaminoalkyl (meth)acrylates; 3-oxetane Alkyl methyl (meth) acrylate, 3-methyl-oxetanyl methyl (meth) acrylate, 3-ethyl-oxetanyl methyl (meth) acrylate , 3-butyl-oxetanyl methyl (meth) acrylate, 3-hexyl-oxetanyl methyl (meth) acrylate, etc. Group) acrylate; tetrahydrofurfuryl (meth) acrylate, butyrolactone (meth) acrylate and other heterocyclic (meth) acrylate or hydroxytrimethyl acetate neopentyl glycol (methyl) Acrylic adducts, p-phenylphenol (meth)acrylate, etc.

Examples of the monofunctional radical polymerizable compound include (meth)acrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid. Of monomers.

The monofunctional radical polymerizable compound may be exemplified by N-vinylpyrrolidone, N-vinyl-ε-caprolactam, and methylvinyl. Pyrrolidone and other amide-based vinyl monomers; vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine, vinylpyrazine, vinylpyrrole, vinylimidazole, vinyloxazole, Vinyl morpholine and other vinyl monomers having a nitrogen-containing heterocycle.

As the monofunctional radical polymerizable compound, a radical polymerizable compound having an active methylene group can be used. A radical polymerizable compound having an active methylene group is a compound having an active double bond group such as a (meth)acryloyl group at the terminal or molecule and having an active methylene group. For example, the active methylene group may be exemplified by acetylacetoyl, alkoxypropanedioxy, cyanoacetoxy, or the like. The aforesaid active methylene group is preferably acetyl acetyl group. For example, specific examples of the radically polymerizable compound having an active methylene group can be listed as follows: 2-acetoxyethyloxyethyl (meth)acrylate, 2-acetoxyethyloxypropyl ( Methacrylic acid ester, 2-acetoxyethyloxy-1-methylethyl (meth)acrylate, etc. Acetylacetoxyalkyl (meth)acrylate; 2-ethoxypropanedi Acetyloxyethyl (meth)acrylate, 2-cyanoacetoxyethyl (meth)acrylate, N-(2-cyanoacetoxyethyl)acrylamide, N- (2-Propionylacetoxybutyl)acrylamide, N-(4-acetylacetoxymethylbenzyl)acrylamide, N-(2-acetylacetoacetamide) Radicals) acrylamide etc. The free-radical polymerizable compound having an active methylene group is preferably acetyl acetyl oxyalkyl (meth) acrylate.

"Multifunctional Radical Polymerizable Compound"

In addition, for example, the bifunctional or higher polyfunctional radical polymerizable compound may be exemplified by tripropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,6-hexanediol Di(meth)acrylate, 1,9-nonanediol di (Meth)acrylate, 1,10-decanediol diacrylate, 2-ethyl-2-butylpropanediol di(meth)acrylate, bisphenol A di(meth)acrylate, bisphenol A Ethylene oxide adduct di(meth)acrylate, bisphenol A propylene oxide adduct di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, new Pentanediol di(meth)acrylate, Tricyclodecane dimethanol di(meth)acrylate, Cyclic trimethylolpropane formal (meth)acrylate, Dioxanediol di(meth) Base) acrylate, trimethylolpropane tri(meth)acrylate, neopentaerythritol tri(meth)acrylate, neopentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth) )) acrylate, dipentaerythritol hexa (meth) acrylate, EO modified diglycerol tetra (meth) acrylate and other esters of (meth) acrylic acid and polyol, 9,9-bis [4- (2-(meth)acryloyloxyethoxy)phenyl] stilbene. Specific examples include: ARONIX M-220, M-306 (manufactured by East Asia Synthetic Corporation), LIGHT ACRYLATE1, 9ND-A (manufactured by Kyoeisha Chemical Company), LIGHT ACRYLATE DGE-4A (manufactured by Kyoeisha Chemical Company), LIGHT ACRYLATE DCP-A (manufactured by Kyoeisha Chemical Co., Ltd.), SR-531 (manufactured by Sadoomer), CD-536 (manufactured by Sadoomer), etc. In addition, various epoxy (meth)acrylates, urethane (meth)acrylates, polyester (meth)acrylates, various (meth)acrylate monomers, etc. can be cited as necessary. .

From the viewpoint of taking into consideration both the adhesion to the polarizer and the optical durability, it is preferable to use a monofunctional radical polymerizable compound and a polyfunctional radical polymerizable compound in combination with the radical polymerizable compound. Generally speaking, the monofunctional radically polymerizable compound is 3 to 80% by weight and the polyfunctional radically polymerizable compound is 20 to 97% based on 100% by weight of the radically polymerizable compound. It is more ideal to use the ratio of volume% in combination.

"The appearance of free radical polymerization hardening type forming material"

Radical polymerization hardening type forming materials can be used as active energy ray hardening type or thermosetting type forming materials. When an electron beam or the like is used as the active energy ray, the active energy ray-curable forming material does not need to contain a photopolymerization initiator; however, when the active energy ray uses ultraviolet light or visible light, it is preferable to contain a photopolymerization initiator. On the other hand, when the curable component is used as a thermosetting component, the forming material preferably contains a thermal polymerization initiator.

"Photopolymerization Initiator"

(thioxanthone)、2-氯9-氧硫

、2-甲基9-氧硫

、2,4-二甲基9-氧硫

、異丙基9-氧硫

、2,4-二氯9-氧硫

、2,4-二乙基9-氧硫

、2,4-二異丙基9-氧硫

、十二基9-氧硫

等9-氧硫

系化合物；樟腦醌；鹵化酮；醯基氧化膦；醯基膦酸酯等。 When a radically polymerizable compound is used, the photopolymerization initiator can be appropriately selected according to the active energy ray. When curing by ultraviolet rays or visible rays, a photopolymerization initiator that splits ultraviolet rays or visible rays is used. For example, the aforementioned photopolymerization initiator can be exemplified by diphenyl ethyl ketone, diphenyl ketone, benzoyl benzoic acid, 3,3'-dimethyl-4-methoxydiphenyl ketone, etc. Phenyl ketone compounds; 4-(2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, α -hydroxy- α , α' -dimethylacetophenone, 2-methyl Aromatic ketone compounds such as -2-hydroxyphenylacetone and α -hydroxycyclohexyl phenyl ketone; methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-bis Acetophenone compounds such as ethoxyacetophenone, 2-methyl-1-[4-(methylthio)-phenyl]-2-morpholinepropane-1; benzoin methyl ether, benzoin Benzoin ether compounds such as diethyl ether, benzoin isopropyl ether, benzoin butyl ether, anisein methyl ether, etc.; aromatic ketal compounds such as diphenyl ethyl ketone dimethyl ketal; 2-naphthalene Aromatic sulfonyl chloride compounds such as sulfonyl chloride; photoactive oxime compounds such as 1-benzophenone-1,1-propanedione-2-(o-ethoxycarbonyl)oxime; 9-oxosulfur

(thioxanthone), 2-chloro 9-oxysulfur

, 2-methyl 9-oxysulfur

, 2,4-Dimethyl 9-oxysulfur

, Isopropyl 9-oxysulfur

, 2,4-Dichloro 9-oxysulfur

, 2,4-Diethyl 9-oxysulfur

, 2,4-Diisopropyl 9-oxysulfur

, Dodecyl 9-oxysulfur

9-oxygen sulfur

Compounds; camphorquinone; halogenated ketones; acylphosphine oxide; acylphosphonate, etc.

For the total amount of 100 parts by weight of the hardenable component (radical polymerizable compound), the blending amount of the aforementioned photopolymerization initiator is 20 parts by weight or less. The blending amount of the photopolymerization initiator is preferably 0.01 to 20 parts by weight, and more preferably 0.05 to 10 parts by weight, and further 0.1 to 5 parts by weight.

In addition, when the hardening type forming material for polarizing film of the present invention is used as the visible light hardening type "containing a radically polymerizable compound as a hardening component", it is particularly preferable to use light with high sensitivity to light of 380 nm or more Polymerization initiator. The photopolymerization initiator having high sensitivity to light of 380 nm or more is described later.

It is preferable to use the compound represented by the following general formula (1) alone or to use the compound represented by the general formula (1) and a photopolymerization initiator having high sensitivity to light with a wavelength of 380 nm or more as described below as the photopolymerization initiator:

。相對於100重量份之硬化性成分的總量，該形成材中一般式(1)所示化合物之組成比率以0.1~5重量份為佳，0.5~4重量份較佳，而0.9~3重量份更佳。 (In the formula, 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). The compound represented by the general formula (1) is superior in adhesion when the photopolymerization initiator with high sensitivity to light of 380 nm or more is used alone. In the compound represented by the general formula (1), it is particularly preferred that R ¹ and R ² are -CH ₂ CH ₃ diethyl 9-oxysulfur

. The composition ratio of the compound represented by general formula (1) in the forming material is preferably 0.1 to 5 parts by weight, preferably 0.5 to 4 parts by weight, and 0.9 to 3 parts by weight relative to 100 parts by weight of the total amount of the hardenable components. Served better.

Moreover, if necessary, it is preferable to add a polymerization initiation aid. The polymerization initiation aid can be exemplified by triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid Ethyl ester, isoamyl 4-dimethylaminobenzoate, etc., particularly preferably ethyl 4-dimethylaminobenzoate. When using a polymerization initiation aid, the addition amount is usually 0 to 5 parts by weight, preferably 0 to 4 parts by weight, and most preferably 0 to 3 parts by weight, relative to 100 parts by weight of the total amount of hardenable components.

In addition, if necessary, a known photopolymerization initiator may be used in combination. Since the protective film with UV absorption capability does not transmit light below 380 nm, it is preferable to use a photopolymerization initiator that is highly sensitive to light above 380 nm. Specific examples include 2-methyl-1-(4-methylthiophenyl)-2-morpholinepropane-1-one and 2-benzyl-2-dimethylamino-1-( 4-morpholinylphenyl)-butanone-1, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)benzene Group]-1-butanone, 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzyl)-phenylphosphine Oxides, bis(η 5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl) titanium, etc.

In particular, in addition to the photopolymerization initiator of the general formula (1), it is preferable to further use the compound represented by the following general formula (2):

(In the formula, 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). For the compound represented by general formula (2), 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-one (trade name: IRGACURE907, which is also commercially available) can be used as appropriate. Manufacturer: BASF). In addition, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1 (trade name: IRGACURE369, manufacturer: BASF), 2-(dimethylamine Yl)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: IRGACURE379, manufacturer: BASF) The sensitivity is high, so it is ideal.

<Free radical polymerizable compound with active methylene group and free radical polymerization initiator with hydrogen abstraction function>

In the aforementioned active energy ray-curable forming material, when a radical 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 abstraction effect.

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

系自由基聚合引發劑。舉例言之，9-氧硫

系自由基聚合引發劑可列舉為：藉由前述一般式(1)所示化合物。舉例言之，藉由一般式(1)所示化合物之具體例可列舉為：9-氧硫

、二甲 基9-氧硫

、二乙基9-氧硫

、異丙基9-氧硫

、氯9-氧硫

等。於藉由一般式(1)所示化合物中，亦特別宜為R¹及R²為-CH₂CH₃之二乙基9-氧硫

。 Examples of free radical polymerization initiators with hydrogen abstraction include: 9-oxysulfur

Radical polymerization initiators, diphenyl ketone radical polymerization initiators, etc. The aforementioned free radical polymerization initiator is preferably 9-oxosulfur

It is a radical polymerization initiator. For example, 9-oxosulfur

The radical polymerization initiator can be exemplified by the compound represented by the general formula (1). For example, specific examples of the compound represented by the general formula (1) can be listed as: 9-oxysulfur

Dimethyl 9-oxysulfur

, Diethyl 9-oxysulfur

, Isopropyl 9-oxysulfur

, Chlorine 9-oxygen sulfur

Wait. Among the compounds represented by the general formula (1), diethyl 9-oxysulfur wherein R ¹ and R ² are -CH ₂ CH ₃ is also particularly preferred

.

In the case where the active energy ray-curable forming material contains a radically polymerizable compound having an active methylene group and a radical polymerization initiator having a hydrogen abstraction function, the total amount of curable components is 100% by weight In view of this, it is preferable to contain 1 to 50% by weight of the radical polymerizable compound having an active methylene group described above, and it is preferable to contain 0.1 to 10 parts by weight of the radical polymerization initiator with respect to 100 parts by weight of the total amount of the hardening component.

"Thermal Polymerization Initiator"

The thermal polymerization initiator is preferably one that does not start polymerization through thermal cracking when the adhesive layer is formed. For example, the thermal polymerization initiator is preferably a 10-hour half-life temperature of 65 ℃ or more, and further 75 to 90 ℃. In addition, the half-life is an index indicating the decomposition rate of the polymerization initiator, and means the time until the remaining amount of the polymerization initiator becomes half. The decomposition temperature that reaches half-life at any time, or the half-life time at any temperature, is described in the manufacturer’s catalog, etc., such as the “Organic Peroxide Catalogue 9th Edition (2003) May)" etc.

Examples of thermal polymerization initiators include lauryl peroxide (10-hour half-life temperature: 64°C), benzyl peroxide (10-hour half-life temperature: 73°C), and 1,1-bis (third butyl) Peroxy)-3,3,5-trimethylcyclohexane (10-hour half-life temperature: 90°C), bis(2-ethylhexyl) peroxydicarbonate (10-hour half-life temperature: 49°C), di (4-tert-butylcyclohexyl) peroxydicarbonate, di-second butylperoxydicarbonate (10-hour half-life temperature: 51 ℃), tert-butyl peroxyneodecanoate (10-hour half-life temperature: 48℃), tertiary hexyl peroxytrimethyl acetate, tertiary butyl peroxytrimethyl acetate, dilaurel Acetyl peroxide (10-hour half-life temperature: 64°C), di-n-octyl peroxide, 1,1,3,3-tetramethylbutoxyperoxy-2-ethylhexanoate (10-hour half-life temperature) : 66℃), bis(4-methylbenzyl) peroxide, dibenzoyl peroxide (10 hour half-life temperature: 73℃), third butyl peroxyisobutyrate (10 Hourly half-life temperature: 81°C), 1,1-bis (third hexyl peroxy) cyclohexane and other organic peroxides.

In addition, the thermal polymerization initiator system can be exemplified by 2,2'-azobisisobutyronitrile (10 hour half-life temperature: 67°C), 2,2'-azobis(2-methylbutyronitrile) ( Azo compounds such as 10-hour half-life temperature: 67°C), 1,1-azobis-cyclohex-1-carbonitrile (10-hour half-life temperature: 87°C).

The blending amount of the thermal polymerization initiator is 0.01 to 20 parts by weight relative to 100 parts by weight of the total amount of the hardenable component (radical polymerizable compound). The blending amount of the thermal polymerization initiator is more preferably 0.05 to 10 parts by weight, and further 0.1 to 3 parts by weight.

"Cationic Polymer Hardening Forming Materials"

The curable component of the cationic polymerization hardening type forming material can be exemplified by compounds having epoxy groups or oxetanyl groups. The compound having an epoxy group is not particularly limited as long as it has at least two epoxy groups in the molecule, and various generally known hardenable epoxy compounds can be used. Examples of ideal epoxy compounds include compounds having at least 2 epoxy groups and at least one aromatic ring in the molecule (aromatic epoxy compounds), or at least 2 epoxy groups in the molecule. And at least one of them is adjacent to the two adjacent alicyclic rings Compounds formed between carbon atoms (alicyclic epoxy compounds), etc.

<other ingredients>

The hardening type forming material according to the present invention preferably contains the following components.

<Acrylic oligomer>

The active energy ray-curable forming material of the present invention may contain an acrylic oligomer obtained by polymerizing a (meth)acrylic monomer in addition to the curable component in the radical polymerizable compound. By containing the propylene amide oligomer in the energy-curing type forming material, the curing shrinkage when the active energy ray is irradiated and the transparent resin layer is cured can be reduced, and the transparent resin layer and the polarizer can be coated The interfacial stress of the object is reduced. As a result, it is possible to suppress a decrease in the adhesion between the adhesive layer and the coating object. In order to sufficiently suppress the curing shrinkage, the content of the propylene oligomer is preferably 20 parts by weight or less, and preferably 15 parts by weight or less with respect to 100 parts by weight of the total amount of curable components. If the content of the propylene amide oligomer in the forming material is too large, the reaction rate when the active energy ray is irradiated to the forming material may rapidly decrease, resulting in poor curing. On the other hand, it is preferable to contain 3 parts by weight or more of acrylic oligomer (A) with respect to 100 parts by weight of the total amount of hardenable components, preferably 5 parts by weight or more.

If the workability or uniformity during coating is considered, the active energy ray-curable forming material should have a low viscosity, so the acrylic oligomer polymerized by (meth)acrylic monomers should also have a low viscosity. The acrylic oligomer having a low viscosity and preventing hardening and shrinkage of the transparent resin layer preferably has a weight average molecular weight (Mw) of 15,000 or less, and preferably 10,000 or less, and particularly preferably 5,000 or less. On the other hand, in order to sufficiently suppress the hardening shrinkage of the transparent resin layer, acrylic The weight average molecular weight (Mw) of the amide oligomer is preferably 500 or more, preferably 1000 or more, and particularly preferably 1500 or more. Specifically, examples of the (meth)acrylic acid monosystem constituting the acrylic oligomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, Isopropyl (meth)acrylate, 2-methyl-2-nitropropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, (meth)acrylic acid Second butyl ester, third butyl (meth) acrylate, n-pentyl (meth) acrylate, third pentyl (meth) acrylate, 3-pentyl (meth) acrylate, 2,2-di Methylbutyl (meth)acrylate, n-hexyl (meth)acrylate, cetyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (Meth)acrylic acid (carbon number 1-20) alkyl esters such as 4-methyl-2-propylpentyl (meth)acrylate, n-octadecyl (meth)acrylate, etc. (Meth)acrylate (e.g. cyclohexyl (meth)acrylate, cyclopentyl (meth)acrylate, etc.), aralkyl (meth)acrylate (e.g. benzyl (meth)acrylate, etc.) , Polycyclic (meth)acrylate (such as 2-isobornyl (meth)acrylate, 2-norbornylmethyl (meth)acrylate, 5-norbornen-2-yl-methyl (Meth)acrylate, 3-methyl-2-norbornyl methyl (meth)acrylate, etc.), (meth)acrylates containing hydroxyl groups (such as hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2,3-dihydroxypropylmethyl-butyl (meth)methacrylate, etc.), (meth)acrylic acid containing alkoxy or phenoxy Esters (2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-methoxymethoxyethyl (meth)acrylate, 3- Methoxybutyl (meth)acrylate, ethyl carbitol (meth)acrylate, phenoxyethyl (meth)acrylate, etc.), (meth)acrylates containing epoxy groups (E.g. epoxypropyl (Meth)acrylate, etc.), halogen-containing (meth)acrylates (e.g. 2,2,2-trifluoroethyl (meth)acrylate, 2,2,2-trifluoroethyl ethyl (Meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptafluorodecyl (meth) acrylate Esters, etc.), alkylaminoalkyl (meth)acrylates (eg, dimethylaminoethyl (meth)acrylates, etc.), and the like. These (meth)acrylates can be used alone or in combination of two or more. Specific examples of acrylic oligomers include "ARUFON" manufactured by East Asia Synthetic Co., "ACTFLOW" manufactured by Kenshin Chemical Co., Ltd., and "JONCRYL" manufactured by BASF Japan.

<Photoacid generator>

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

General formula (3) [Chem 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 -, disulfide Carbamate anions, relative anions in the group consisting of SCN-.)

Specific examples of the onium salt constitutes over photoacid generating agent is selected from _{^{PF 6 -, SbF 6 -,}} AsF 6 -, SbCl 6 -, BiCl 5 -, SnCl 6 -, ClO 4 -, an amine disulfide carboxylate anion, SCN ^- anion formed onium salt.

Specifically, the ideal specific examples that can be cited as the photoacid generator are: "CYRACURE UVI-6992", "CYRACURE UVI-6974" (the above is manufactured by Japan Dow Chemical Co., Ltd.), "ADEKA OPTOMER SP150'', ``ADEKA OPTOMER SP152'', ``ADEKA OPTOMER SP170'', ``ADEKA OPTOMER SP172'' (above manufactured by ADEKA Co., Ltd.), ``IRGACURE250'' (Ciba Specialty Chemicals) System), ``CI-5102'', ``CI-2855'' (the above is made by Soda Corporation), ``SAN-AID SI-60L'', ``SAN-AID SI-80L'', ``SAN-AID SI-100L'', ``SAN-AID SI-110L'', ``SAN-AID SI-180L'' (above manufactured by Sanxin Chemical Co., Ltd.), ``CPI-100P'', ``CPI-100A'' (above are Sanya Apro) Company-made), ``WPI-069'', ``WPI-113'', ``WPI-116'', ``WPI-041'', ``WPI-044'', ``WPI-054'', ``WPI-055'', ``WPAG-281 ", "WPAG-567", "WPAG-596" (above manufactured by Wako Pure Chemical Industries, Ltd.).

The content of the photoacid generator is not more than 10 parts by weight relative to 100 parts by weight of the total amount of the hardening component, and is preferably 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, and particularly preferably 0.1 to 3 parts by weight.

"Photo-cationic polymerization initiator"

The cationic polymerization hardening type forming material contains the epoxy compound and the oxetane compound described above as hardening components, and all of them are hardened by cationic polymerization, so a photo-cationic polymerization initiator is used. The Gwangyangli The sub-polymerization initiator generates a cationic species or a Lewis acid by irradiation of active energy rays such as visible rays, ultraviolet rays, X-rays, and electron rays to initiate the polymerization reaction of epoxy groups or oxetanyl groups.

The formation of the transparent resin layer using the aforementioned hardening type forming material is performed by applying the hardening type forming material on the surface of the polarizer and then hardening it.

The polarizer can also be surface-modified before being coated with the above-mentioned hardened forming material. Specific treatments include treatment by corona treatment, plasma treatment, and saponification treatment.

The coating method of the hardening type forming material is appropriately selected according to the viscosity and the target thickness of the hardening type forming material. Examples of the coating method include, for example, a reverse coater, a gravure coater (direct, reverse or lithography), a bar reverse coater, a roll coater, a mold coater, and a bar coater. Scraper bar coater, etc. For coating, other methods such as dip coating can be used as appropriate.

<hardening of forming material>

The aforementioned hardening type forming material can be used as an active energy ray hardening type forming material or a thermosetting type forming material. Among the active energy ray-curable forming materials, it can be used in the form of electron beam curing type, ultraviolet curing type, and visible light curing type. From the viewpoint of productivity, the form of the aforementioned hardening type forming material is that the active energy ray hardening type forming material is superior to the thermosetting type forming material; further, from the viewpoint of productivity, it is preferable to use visible light The linear hardening type forming material is an active energy linear hardening type forming material.

"Active Energy Ray Hardening Type"

In the active energy ray-curable forming material, after the active energy ray-curable forming material is applied to the polarizer, the active energy ray (electron rays, ultraviolet rays, visible light, etc.) is irradiated to make the active energy ray-curing forming material Harden to form a transparent resin layer. The irradiation direction of active energy rays (electron rays, ultraviolet rays, visible rays, etc.) can be irradiated from any appropriate direction. It is desirable to irradiate from the transparent resin layer side.

"Electronic beam hardening type"

In the electron beam curing type, the irradiation condition of the electron beam may be any condition as long as it can cure the aforementioned active energy ray curing type forming material, and any suitable conditions can be adopted. For example, for electron beam irradiation, the acceleration voltage is preferably 5 kV to 300 kV, and more preferably 10 kV to 250 kV. When the acceleration voltage is less than 5kV, there will be a risk that the electron beam cannot reach the deepest part of the transparent resin layer and become insufficient hardening; and if the acceleration voltage is greater than 300kV, the penetration force of the sample will be too strong to protect the film or polarizer Risk of damage. The irradiation dose is 5~100kGy, and more preferably 10~75kGy. When the irradiation dose is less than 5kGy, the adhesive will be insufficiently hardened. If it is greater than 100kGy, the protective film or polarizer will be damaged, and the mechanical strength will be reduced or yellowed, and the predetermined optical characteristics cannot be obtained.

Electron beam irradiation is usually carried out in an inert gas. However, if necessary, it may be carried out in the atmosphere or under a condition in which a small amount of oxygen is introduced.

"Ultraviolet curing type, visible light curing type"

In the manufacturing method of the polarizing film of the present invention, the active energy ray preferably uses visible light with a wavelength range of 380 nm to 450 nm, especially the wave Active energy ray with the longest visible light exposure of 380nm~450nm. The active energy line in the present invention is preferably a metal halogen lamp enclosed with gallium and an LED light source with a light emitting wavelength range of 380-440 nm. Or, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, incandescent lamps, xenon lamps, halogen lamps, carbon arc lamps, metal halogen lamps, fluorescent lamps, tungsten filament lamps, gallium lamps, excimer lasers or Sunlight and other light sources including ultraviolet rays and visible rays can also be used with a band-pass filter to block ultraviolet rays with a wavelength shorter than 380nm.

≪Thermosetting type≫

On the other hand, in the thermosetting type forming material, after the polarizer and the protective film are bonded, polymerization is initiated by heating with a thermal polymerization initiator to form a hardened layer. The heating temperature can be set according to the thermal polymerization initiator, but it is about 60~200℃, preferably 80~150℃.

As the material for forming the transparent resin layer, for example, a cyanoacrylate-based forming material, an epoxy-based forming material, or an isocyanate-based forming material can be used.

Examples of the cyanoacrylate-based forming material include methyl-α-cyanoacrylate, ethyl-α-cyanoacrylate, butyl-α-cyanoacrylate, and octyl-α-cyano Alkyl-α-cyanoacrylate such as acrylate, cyclohexyl-α-cyanoacrylate, methoxy-α-cyanoacrylate, etc. The cyanoacrylate-based forming material can be used, for example, as a cyanoacrylate-based adhesive.

The epoxy-based forming material may be used as an epoxy resin monomer, or may contain an epoxy hardener. When using epoxy resin in the form of monomer, The photopolymerization initiator is added and irradiated to harden it. When an epoxy hardener is added as an epoxy-based forming material, it can be used as an epoxy-based adhesive, for example. The use form of the epoxy-based forming material can be used as a one-component type containing an epoxy resin and its hardener, or as a two-component type in which a hardener is mixed with an epoxy resin. Epoxy-based forming materials are usually used as solutions. The solution may be a solvent system, or an aqueous system such as latex, colloidal dispersion liquid, or aqueous solution.

Epoxy resins can be exemplified by various compounds containing two or more epoxy groups in the molecule, such as bisphenol epoxy resin, aliphatic epoxy resin, aromatic epoxy resin, halogenated bisphenol epoxy Resin, biphenyl epoxy resin, etc. Also, the epoxy resin can be appropriately determined according to the epoxy equivalent and the number of functional groups, but from the viewpoint of durability, it is desirable to use an epoxy equivalent of 500 or less.

The curing agent of the epoxy resin is not particularly limited, and various substances such as phenol resin-based, acid anhydride-based, carboxylic acid-based, and polyamine-based materials can be used. For the phenol resin-based hardener, for example, phenol novolak resin, bisphenol novolak resin, xylylene phenol resin, cresol novolak resin, and the like can be used. Anhydride-based hardeners; for example, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, etc., and carboxylic acid-based hardeners, for example, pyromellitic acid, 1,2,4 -Carboxylic acids such as trimellitic acid and block carboxylic acids added with vinyl ether. In addition, as the epoxy-based two-component forming material, for example, those composed of two components of epoxy resin and polythiol, and those composed of two components of epoxy resin and polyamide can be used.

The blending amount of the hardener varies according to the equivalent weight of the epoxy resin, but it is preferably 30 to 70 parts by weight relative to 100 parts by weight of the epoxy resin. More preferably, it is made into 40 to 60 parts by weight.

In addition, in the epoxy-based forming material, various curing accelerators can be used in addition to the epoxy resin and its curing agent. Examples of hardening accelerators include various imidazole compounds and their derivatives, dicyandiamide and the like.

Examples of the isocyanate-based forming material include those used as crosslinking agents in the formation of adhesive layers. As the isocyanate-based crosslinking agent, a compound having at least 2 isocyanate groups can be used. For example, the aforementioned polyisocyanate compound can be used as an isocyanate-based forming material. More specifically, it can be exemplified by 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, xylylene diisocyanate, 1,3-diisocyanatomethylcyclohexane, and hexamethylene diisocyanate. Isocyanate, tetramethyl xylylene diisocyanate, m-isopropenyl-α,α-dimethylbenzyl isocyanate, methylene bis 4-phenyl isocyanate, p-phenylene diisocyanate or dimerization of these Substances or terpolymers such as triisocyanurate tris(6-isocyanatohexyl), as well as those obtained by reaction with polyhydric alcohols or polyamines such as biuret or trimethylolpropane. In addition, as the isocyanate-based crosslinking agent, those having three or more isocyanate groups such as tris(6-isocyanatohexyl) isocyanurate are preferred. As the isocyanate-based forming material, for example, those used as isocyanate-based adhesives may be used.

Among the isocyanate-based forming agents, for the present invention, it is preferable to use a hard structure with a large proportion of the cyclic structure (benzene ring, cyanurate ring, isocyanurate ring, etc.) in the molecular structure in the structure Constructor. As the isocyanate-based forming agent, for example, trimethylolpropane-tri-toluene isocyanate, tris(hexamethylene isocyanate group) isocyanurate, and the like are suitably used.

The aforementioned isocyanate-based cross-linking agent can also use The cyanate ester group imparts a protective group. As the protective group, there are oxime or lactam. If the isocyanate group has been protected, the protective group can be dissociated from the isocyanate group by heating to allow the isocyanate group to react.

Furthermore, in order to increase the reactivity of the isocyanate group, a reaction catalyst may be used. The reaction catalyst is not particularly limited, but the ideal is a tin catalyst or an amine catalyst. One kind or two or more kinds of reaction catalysts can be used. The amount of the reaction catalyst used is usually 5 parts by weight or less relative to 100 parts by weight of the isocyanate-based crosslinking agent system. Once the amount of reaction catalyst is high, the cross-linking reaction speed will become faster and cause foaming of the forming agent. The use of the foamed forming agent may fail to obtain sufficient adhesion. Generally, when using a reaction catalyst, it is preferably 0.01 to 5 parts by weight, and more preferably 0.05 to 4 parts by weight.

As the tin-based catalyst, either an inorganic system or an organic system can be used, but the organic system is suitable. Examples of the inorganic tin-based catalyst include stannous chloride and tin chloride. The organic tin-based catalyst preferably contains at least one of the following organic groups: that is, an aliphatic group having a skeleton such as a methyl group, an ethyl group, an ether group, an ester group, and an organic group such as an alicyclic group. Examples thereof include tetra-n-butyl tin, tri-n-butyl tin acetate, n-butyl tin trichloride, trimethyl tin hydroxide, dimethyl tin dichloride, and dibutyl tin dilaurate.

In addition, the amine catalyst is not particularly limited. For example, those having at least one organic group such as an alicyclic group such as quinuclidine, amidines, diazabicycloundecene and the like are preferable. In addition, the amine catalyst includes triethylamine and the like. In addition, reaction catalysts other than the above can be exemplified by cobalt naphthenate, benzyltrimethylammonium hydroxide, and the like.

The isocyanate-based forming material is usually used as a solution. The solution can be The solvent system may be an aqueous system such as an emulsion, colloidal dispersion liquid, or aqueous solution. The organic solvent is not particularly limited as long as the components constituting the forming material can be uniformly dissolved. Examples of organic solvents include toluene, methyl ethyl ketone, and ethyl acetate. In the case of making an aqueous solution, alcohols such as n-butanol and isopropanol, and ketones such as acetone can still be blended. In the case of preparing an aqueous solution, it can be carried out by using a dispersant, or by introducing a functional group having a low reactivity with an isocyanate group, such as a carboxylate, sulfonate, or quaternary ammonium salt, into the isocyanate-based crosslinking agent. , Or water-dispersible components such as polyethylene glycol.

The formation of a transparent resin layer using a cyanoacrylate-based forming material, an epoxy-based forming material, or an isocyanate-based forming material can be appropriately selected according to the type of the aforementioned forming material, but usually by drying at about 30 to 100°C It takes about 0.5 to 15 minutes, and it should be 50 to 80℃. In the case of a cyanoacrylate-based forming material, since the hardening is rapid, the transparent resin layer can be formed in a shorter time than the aforementioned time.

The transparent resin layer may be formed of a forming material that does not contain a curable component. For example, it may be formed of a forming material containing the aforementioned polyvinyl alcohol-based resin as a main component. The polyvinyl alcohol resin forming the transparent resin layer may be the same as or different from the polyvinyl alcohol resin contained in the polarizer as long as it is a "polyvinyl alcohol resin".

Examples of the polyvinyl alcohol-based resin include polyvinyl alcohol. Polyvinyl alcohol is obtained by saponifying polyvinyl acetate. Examples of the polyvinyl alcohol-based resin include saponified products of copolymers of vinyl acetate and copolymerizable monomers. When the aforementioned copolymerizable monomer is ethylene, an ethylene-vinyl alcohol copolymer is obtained. In addition, the aforementioned copolymerizable monomers include (anhydrous) maleic acid, fumaric acid, Unsaturated carboxylic acids such as crotonic acid, itaconic acid, (meth)acrylic acid and their esters; α-olefins such as ethylene and propylene, (meth)allylsulfonic acid (sodium), sodium sulfonate (monoalkyl Malate), sodium disulfonate alkyl malate, N-methylol acrylamide, base salt of acrylamide alkyl sulfonate, N-vinylpyrrolidone, N-vinylpyrrolidone derivatives, etc. . These polyvinyl alcohol-based resins may be used alone or in combination of two or more. From the viewpoint of controlling the heat of crystal fusion of the transparent resin layer to 30 mj/mg or more and satisfying the heat and moisture resistance and water resistance, polyvinyl alcohol obtained by saponification of vinyl acetate is preferred.

The saponification degree of the polyvinyl alcohol-based resin can be, for example, 95% or more, but from the viewpoint of controlling the heat of crystal fusion of the transparent resin layer to 30 mj/mg or more to satisfy the moisture and heat resistance and water resistance, The degree of saponification should be above 99.0%, preferably above 99.7%. The degree of saponification means the ratio of units that can actually be converted into vinyl alcohol units by saponification, and the residues are vinyl ester units. The degree of saponification is determined based on JIS K 6726-1994.

For the average degree of polymerization of the polyvinyl alcohol-based resin, for example, 500 or more can be used. However, from the viewpoint of controlling the heat of crystal fusion of the transparent resin layer to 30 mj/mg or more to satisfy the hygrothermal resistance and water resistance, the average The degree of polymerization is preferably 1000 or more, more preferably 1500 or more, and even more preferably 2000 or more. The average degree of polymerization of the polyvinyl alcohol-based resin is measured in accordance with JIS-K6726.

As the polyvinyl alcohol-based resin, a modified polyvinyl alcohol-based resin having a hydrophilic functional group in the side chain of the polyvinyl alcohol or its copolymer can also be used. Examples of the hydrophilic functional group include acetyl acetyl, carbonyl Base etc. In other respects, modified polyvinyl alcohol obtained by subjecting a polyvinyl alcohol-based resin to acetalization, urethaneization, etherification, grafting, phosphorylation, or the like can be used.

The aforementioned forming material containing the polyvinyl alcohol-based resin as a main component may contain a curable component (crosslinking agent) and the like. The ratio of the polyvinyl alcohol-based resin in the transparent resin layer or the forming material (solid content) is preferably 80% by weight or more, more preferably 90% by weight or more, and even more preferably 95% by weight or more. However, from the viewpoint of easily controlling the heat of crystal fusion of the transparent resin layer to 30 mj/mg or more, the aforementioned forming material preferably does not contain a curable component (crosslinking agent).

As the cross-linking agent, a compound having at least two reactive functional groups (reactive to the polyvinyl alcohol-based resin) can be used. Examples include alkylene diamines such as ethylenediamine, triethylenediamine, and hexamethylenediamine having alkylene groups and two amine groups; toluene diisocyanate, hydrogenated toluene diisocyanate, and trimethylolpropane toluene diamine Isocyanate adducts, triphenylmethane triisocyanate, methylene bis(4-phenylmethane triisocyanate, isophorone diisocyanate, and other isocyanates such as ketoxime block or phenol block; ethylene glycol Diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol di or triglycidyl ether, 1,6-hexane glycol diglycidyl ether, trimethylol Epoxides such as propane triglycidyl ether, diglycidyl aniline, diglycidyl amine; monoaldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde; glyoxal, malondialdehyde, Dialdehydes such as succinaldehyde, glutaraldehyde, maleic dialdehyde, and phthalaldehyde; methylol urea, methylol melamine, alkylated methylol urea, alkylated methylol melamine, ethyl Amido-formaldehyde resins such as condensates of guanidine amine, benzoguanamine and formaldehyde; dihydrazine adipic acid, dihydrazine oxalate, dihydrazide malonate, dihydrazide succinate, Dicarboxylic acid dihydrazine such as glutaric acid dihydrazide, isophthalic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, fumaric acid fumarate, itaconic acid dihydrazide; ethylene- 1,2-Dihydrazine, propylene-1,3-dihydrazine, butene-1,4-dihydrazine and other water-soluble dihydrazine. Among them, amino-formaldehyde resin and water-soluble dihydrazine are preferred. The amino-formaldehyde resin is preferably a compound having a methylol group. Among them, methylolmelamine, which is a compound having methylol groups, is particularly preferable.

The aforementioned curable component (crosslinking agent) can be used from the viewpoint of improving water resistance, but the ratio is preferably 20 parts by weight or less, 10 parts by weight or less, and 5 parts by weight or less with respect to 100 parts by weight of the polyvinyl alcohol-based resin.

The forming material is adjusted to a solution in which the polyvinyl alcohol-based resin is dissolved in a solvent. Examples of the solvent include polyvalent alcohols such as water, dimethylsulfoxide, dimethylformamide, dimethylacetamide-N-methylpyrrolidone, various diols, and alcohols, and ethylenedioxide. Amine, diethylene triamine and other amines. These can be used alone or in combination of two or more. Among these, an aqueous solution using water as a solvent is preferably used. Although the concentration of the polyvinyl alcohol-based resin in the aforementioned forming material (for example, aqueous solution) is not particularly limited, it is 0.1 to 15% by weight, preferably 0.5 to 10% by weight in consideration of coatability and placement stability. %.

In addition, in the aforementioned forming material (for example, aqueous solution), examples of the additive include plasticizers and surfactants. Examples of plasticizers include polyhydric alcohols such as ethylene glycol and glycerin. The surfactant may, for example, be a nonionic surfactant. In addition, it can also be used with silane coupling agent, titanium coupling agent and other coupling agents, various adhesive granting agents, ultraviolet absorbers, antioxidants, heat-resistant stabilizers, hydrolysis-resistant stabilizers and other stabilizers.

The transparent resin layer can be formed by applying the aforementioned forming material on the other surface of the polarizer (the surface where the protective film is not laminated) and drying. The coating operation is not particularly limited, and any appropriate method can be adopted. For example, a roll coating method, a spin coating method, a wire bar coating method, a dip coating method, a die coating method, a curtain coating method, a spray coating method, a blade coating method (comma blade coating method, etc.) ) And other means.

The transparent resin layer is preferably formed of an ultraviolet curing acrylic resin, an ultraviolet curing epoxy resin, a urethane resin, or a polyvinyl alcohol resin. The urethane-based resin layer system is formed of the aforementioned isocyanate-based forming material.

<adhesive layer>

For the formation of the adhesive layer, an appropriate adhesive can be used, and there is no particular limitation on the type. Examples of the adhesive include rubber adhesives, acrylic adhesives, polysiloxane adhesives, urethane adhesives, vinyl alkyl ether adhesives, polyvinyl alcohol adhesives, and polyadhesives. Vinylpyrrolidone-based adhesives, polyacrylamide-based adhesives, cellulose-based adhesives, etc.

Among these adhesives, those having good optical transparency, exhibiting appropriate wettability, cohesiveness and adhesiveness, and excellent weather resistance and heat resistance are suitable for use. For those who show such characteristics, it is better to use acrylic adhesives.

As for the method of forming the adhesive layer, for example, it can be produced by applying the aforementioned adhesive to a separator subjected to peeling treatment, etc., and drying and removing the polymerization solvent etc. to form the adhesive layer. The aspect of 2(A) is transferred to the polarizer (or the aspect of FIG. 2(B) is transferred to the protective film) Method; or apply the adhesive to the polarizer in the aspect of FIG. 2(A) (the protective film in the aspect of FIG. 2(B)), dry and remove the polymerization solvent, etc. to form an adhesive on the polarizer Agent method and so on. In addition, when applying the adhesive, one or more solvents other than the polymerization solvent may be newly added as appropriate.

The separation piece after peeling treatment should use polysiloxane release liner. In the step of coating and drying the adhesive of the present invention on such a liner to form an adhesive layer, as a method of drying the adhesive, a suitable and appropriate method can be adopted according to the purpose. It is desirable to use a method of heating and drying the coating film. The heating and drying temperature is preferably 40°C to 200°C, more preferably 50°C to 180°C, and particularly preferably 70°C to 170°C. By setting the heating temperature to the above range, an adhesive having excellent adhesive properties can be obtained.

The drying time can be a suitable and appropriate time. The above drying time is preferably 5 seconds to 20 minutes, more preferably 5 seconds to 10 minutes, and particularly preferably 10 seconds to 5 minutes.

Various methods can be used to form the adhesive layer. Specifically, for example, a roll coating method, a contact gum coating method, a gravure coating method, a reverse coating method, a roll brush method, a spray coating method, a dip roll coating method, a bar coating method, a knife coating method, a gas coating method The knife coating method, the curtain coating method, the lip die coating method, the extrusion coating method using a die coater, etc. are methods.

From the viewpoint of suppressing peeling, the thickness of the adhesive layer is preferably 1 μm or more, and more preferably 5 μm or more. On the other hand, if the thickness of the adhesive is too thick, the mechanical impact caused by the polarizing film attached to the liquid crystal cell will easily bend the polarizer and cause nano-slits, so it is preferably 40 μm, more preferably 35 μm Below, it is more preferably 25 μm or less. Also, even from the viewpoint of suppressing shrinkage of the polarizer due to thermal shock, the thickness of the adhesive layer is also It is preferably 35 μm or less.

The above-mentioned adhesive layer allows the polarizing film with the adhesive layer to be loaded at 23° C. on the polarizer side without load caused by buckling and ensuring crack resistance (suppression of nano-slits). The number is preferably 1.0×10 ⁴ Pa or more. The storage elastic modulus of the adhesive layer is preferably 5.0×10 ⁴ Pa or more. On the other hand, once the storage elastic modulus of the adhesive layer becomes large, it becomes too hard and tends to deteriorate reworkability, so the storage elastic modulus of the adhesive layer is preferably 1×10 ⁸ Pa or less , More preferably 1×10 ⁷ Pa or less.

When the aforementioned adhesive layer is exposed, the sheet (separator) after peeling treatment may be used to protect the adhesive layer before being supplied for practical use.

Examples of constituent materials of the separator include plastic films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films; porous materials such as paper, cloth, and non-woven fabric; meshes, and foamed sheets , Metal foil, and other appropriate laminates, etc., but from the point of surface smoothness, plastic film is suitable.

The plastic film is not particularly limited as long as it can protect the adhesive layer. Examples include polyethylene film, polypropylene film, polybutene film, polybutadiene film, and polymethylpentene film. Polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, ethylene-vinyl acetate copolymer film, etc.

The thickness of the aforementioned separator is generally 5 to 200 μm, preferably about 5 to 100 μm. For the aforementioned separator, polysilicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based release agents, silicon oxide can also be used as needed. Powder release and anti-fouling treatment, as well as antistatic treatment such as coating type, kneading type, evaporation type, etc. In particular, by appropriately performing peeling treatments such as silicone treatment, long-chain alkyl treatment, and fluorine treatment on the surface of the separator, the peelability from the adhesive layer can be further improved.

<surface protective film>

A surface protective film can be provided on one side to protect the polarizing film and the polarizing film with an adhesive layer. The surface protection film usually has a base material film and an adhesive layer, and protects the polarizer through the adhesive layer.

The base film of the surface protective film is selected from the viewpoints of inspection and management, etc., and has an isotropic or nearly isotropic film material. Examples of the film material include polyester-based resins such as polyethylene terephthalate films, cellulose-based resins, acetate-based resins, polyether-based resins, polycarbonate-based resins, and polyamide-based resins. Polyimide-based resin, polyolefin-based resin, and acrylic-based resin-like transparent polymer. Among these, polyester resins are suitable. As the substrate film, a laminate of one kind or two or more kinds of film materials may be used, and an extension of the aforementioned film may also be used. The thickness of the substrate film is usually 500 μm or less, preferably 10 to 200 μm.

As for the adhesive forming the adhesive layer of the surface protection film, (meth)acrylic polymer, polysiloxane polymer, polyester, polyurethane, polyamide, poly Ether, fluorine-based and rubber-based polymers are used as adhesives for the base polymer. From the viewpoints of transparency, weather resistance, heat resistance, etc., it is preferably an acrylic adhesive based on an acrylic polymer as a base polymer. The thickness of the adhesive layer (dry film thickness) is determined according to the required adhesive force. Usually it is about 1~100μm, preferably 5~50μm.

In addition, in the surface protection film, a peeling treatment layer may be provided on the surface opposite to the surface of the base film provided with the adhesive layer using a low-adhesion material such as polysiloxane treatment, long-chain alkyl treatment, or fluorine treatment.

<other optical layer>

The single-sided protective polarizing film and the polarizing film with an adhesive layer of the present invention can use optical films that have been laminated with other optical layers in actual use. The optical layer is not particularly limited, and one or more layers such as a reflective plate and a semi-transmissive plate, a retardation plate (including 1/2 and 1/4 wavelength plates), a viewing angle compensation film, etc. can be used An optical layer such as a liquid crystal display device is formed. It is particularly desirable that the single-sided protective polarizing film of the present invention is a reflective polarizing film or semi-transmissive polarizing film formed by re-stacking a reflective plate or a semi-transmissive reflective plate, and the polarizing film is further laminated by a polarizing film. A polarizing film or a circular polarizing film, a polarizing film and a polarizing film formed by laminating a viewing angle compensation film, a wide viewing angle polarizing film, or a polarizing film and a brightening film.

The optical film with the above-mentioned optical layer laminated on the single-sided protective polarizing film and the polarizing film with an adhesive layer can also be formed by sequentially layering in the manufacturing process of liquid crystal display devices, etc., but the optical film is laminated in advance In addition, it has the advantages of excellent quality stability and assembly work, etc., which can improve the manufacturing process of the liquid crystal display device and the like. For lamination, an appropriate adhesion means such as an adhesive layer can be used. When the polarizing film with an adhesive layer and the other optical layers are attached, the optical axes of the polarizing films and other optical layers can be arranged at an appropriate angle in accordance with the purpose of phase difference characteristics.

The single-sided protective polarizing film, polarizing film with adhesive layer or optical film of the present invention can be suitably used in liquid crystal display devices and organic EL displays The formation of various image display devices such as devices. The formation of the liquid crystal display device can be implemented according to conventional knowledge. That is, the liquid crystal display device is generally formed by appropriately assembling the liquid crystal cell and the polarizing film or optical film with an adhesive layer, and the lighting system as required, and installing the driving circuit, etc. In the present invention, except for use The single-sided protective polarizing film, the polarizing film with an adhesive layer, or the optical film of the present invention are not particularly limited except this point, and may be based on conventional knowledge. As for the liquid crystal cell, any type such as IPS type, VA type, etc. can also be used, but the IPS type is particularly ideal.

The following liquid crystal display devices can be formed: a liquid crystal display device in which a single-sided protective polarizing film, a polarizing film with an adhesive layer or an optical film is arranged on one or both sides of the liquid crystal cell; or a backlight or reflective plate is used in the lighting system Suitable liquid crystal display device. In this case, the polarizing film or optical film with adhesive layer of the present invention may be disposed on one side or both sides of the liquid crystal cell. When a single-sided protective polarizing film, an adhesive layer polarizing film or an optical film are provided on both sides, these may be the same or different. In addition, when forming a liquid crystal display device, appropriate components such as a diffusion plate, an anti-glare layer, an anti-reflection film, a protective plate, a prism array, a lens array sheet, a light diffusion plate, a backlight, etc. Layer or more than 2 layers.

<Continuous manufacturing method of image display device>

The above image display device is preferably manufactured by a continuous manufacturing method (coil-to-panel method) including the following steps: the adhesive layer-attached polarized light is output from the roll (coil) of the adhesive layer-attached polarizing film of the present invention The film is transported by the separating member, and the polarizing film with the adhesive layer is continuously attached to the surface of the image display panel through the adhesive layer. Attachment of the invention The polarizing film of the adhesive layer is a very thin film, so once it is cut into sheets (sheet cutting) and then each piece is attached to the image display panel (also known as the "sheet-to-panel method"), The operation when the sheet is conveyed and attached to the display panel is very difficult, and the polarizing film (sheet) with an adhesive layer is subjected to a large mechanical impact (such as deflection caused by adsorption, etc.) during these processes The risk will become higher. In order to reduce this risk, countermeasures such as the use of a surface protective film with a thickness of the base film of 50 μm or more are required separately. On the other hand, if the roll-to-panel method is adopted, the polarizing film with an adhesive layer does not need to be cut into a sheet shape (sheet cutting), and is continuously conveyed from the roll material to the image display panel by a continuous separation member, and thus bonded On the image display panel, there is no need to use a thick surface protection film, which can greatly reduce the above risks. As a result, an image display panel can be continuously produced at high speed, which can use a transparent resin layer to ease mechanical impact and complement it to effectively suppress the occurrence of nano-slits.

FIG. 8 is a schematic diagram showing an example of a continuous manufacturing system of a liquid crystal display device using a web-to-panel method.

The continuous manufacturing system 100 of a liquid crystal display device, as shown in FIG. 8, includes a series of conveying parts X conveying the liquid crystal display panel P, a first polarizing film supply part 101a, a first bonding part 201a, and a second polarizing film supply part 101b, and the 2nd bonding part 201b.

In addition, an object having an absorption axis in the longitudinal direction and the aspect described in FIG. 2(A) is used as the first adhesive layer polarizing film roll (first coil) 20a and the second adhesive layer polarizing film Winding material (second coil) 20b.

(Conveying Department)

The conveying section X conveys the liquid crystal display panel P. The conveying unit X includes a plurality of conveying rollers, suction plates, and the like. The transport unit X includes a configuration switching unit 300 between the first bonding unit 201a and the second bonding unit 201b, which adjusts the long and short sides of the liquid crystal display panel P relative to the transport direction of the liquid crystal display panel P The configuration relationship of (for example, 90° horizontal rotation of the liquid crystal display panel P). With this, the first adhesive layer polarizing film 21 a and the second adhesive layer polarizing film 21 b can be bonded to the liquid crystal display panel P in a cross nicol relationship.

(1st polarizing film supply unit)

The first polarizing film supply unit 101a continuously supplies the first adhesive layer polarizing film (with surface protection film) 21a that is output from the first roll 20a and transported by the separator 5a to the first bonding unit 201a. The first polarizing film supply unit 101a has a first output unit 151a, a first cutting unit 152a, a first peeling unit 153a, a first winding unit 154a, and a plurality of accumulation rollers, such as transport rollers and floating rollers.

The first output unit 151a has an output shaft provided with a first roll 20a, and outputs the tape-shaped adhesive layer polarizing film 21a provided with a separator 5a from the first roll 20a.

The first cutting section 152a has cutting means such as a cutter and a laser device and suction means. The first cutting portion 152a is to continuously cut the strip-shaped first adhesive layer-attached polarizing film 21a laterally with a predetermined length while continuing to leave the separator 5a. However, when the strip-shaped adhesive layer polarizing film 21a in which a plurality of cut lines are formed laterally with a predetermined length is stacked on the separator 5a (optical film roll with slits) as the first roll 20a In this case, the first cutting section 152a is unnecessary (the same applies to the second cutting section 152b described later).

The first peeling portion 153a peels the first adhesive layer-attached polarizing film 21a from the separator 5a by folding back the separator 5a inside. Examples of the first peeling portion 153a include a wedge-shaped member and a roller.

The first winding part 154a winds the separator 5a from which the polarizing film 21a of the first adhesive layer has been peeled off. The first winding unit 154a has a winding shaft, and a roller for winding the separator 5a is provided.

(1st bonding part)

The first bonding portion 201a is to continuously bond the first adhesive-layer polarizing film 21a peeled by the first peeling portion 153a through the adhesive layer of the first adhesive-layer polarizing film 21a, and then to the conveying unit X is conveyed on the liquid crystal display panel P (first bonding step). The first bonding portion 81 includes a pair of bonding rollers, and at least one of the bonding rollers is configured by a driving roller.

(Second Polarizing Film Supply Section)

The second polarizing film supply unit 101b continuously supplies the second adhesive layer polarizing film (with surface protection film) 21b that is output from the second web 20b and transported by the separator 5b to the second bonding unit 201b. The second polarizing film supply unit 101b includes a second output unit 151b, a second cutting unit 152b, a second peeling unit 153b, a second take-up unit 154b, and a plurality of accumulation rollers such as transport rollers and floating rollers. In addition, the second output portion 151b, the second cutting portion 152b, the second peeling portion 153b, and the second winding portion 154b respectively have a first output portion 151a, a first cutting portion 152a, a first peeling portion 153a, The first winding unit 154a has the same structure and function.

(Second bonding section)

The second bonding portion 201b passes the second adhesive layer polarizing film 21b peeled by the second peeling portion 153b, and passes through the second adhesive layer polarizing film 21b The adhesive layer is continuously bonded to the liquid crystal display panel P transported by the transport unit X (second bonding step). The second bonding portion 201b includes a pair of bonding rollers, and at least one of the bonding rollers is configured by a driving roller.

Examples

Hereinafter, the present invention will be described with examples, but the present invention is not limited to the examples shown below. In addition, the parts and% in each example are based on weight. The room temperature storage conditions not specified below are 23°C 65%RH.

<Production of polarizers>

(Production of polarizer A0)

Apply corona to one side of the substrate of amorphous isophthalic acid-co-polyethylene terephthalate (IPA-co-PET) film (thickness: 100μm) with a water absorption of 0.75% and Tg75℃ Treatment, coated with polyvinyl alcohol (degree of polymerization 4200, degree of saponification 99.2 mol%) and modified PVA (degree of polymerization 1200) with a ratio of 9:1 on the corona treated surface at 25°C , Acetyl Acetyl Modification Degree 4.6%, Saponification Degree 99.0 mol% or more, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., under the trade name "Gohsefimer Z200") and dried to form a PVA resin layer with a thickness of 11 μm, making a laminate body.

The resulting laminate was subjected to free-end uniaxial stretching (air assisted stretching treatment) in a longitudinal direction (longitudinal direction) 2.0 times in the longitudinal direction (longitudinal direction) between rollers having different peripheral speeds in a 120°C oven.

Next, the laminate was immersed in an insolubilization bath (a boric acid aqueous solution obtained by blending 4 parts by weight of boric acid with respect to 100 parts by weight of water) at a liquid temperature of 30°C for 30 seconds (insolubilization treatment).

Next, in a dye bath at a liquid temperature of 30° C., the iodine concentration and the immersion time were adjusted while immersing so that the polarizing plate reached a predetermined transmittance. In this example, it was immersed in an aqueous iodine solution obtained by blending 0.2 parts by weight of iodine and 1.0 parts by weight of potassium iodide with respect to 100 parts by weight of water for 60 seconds (dyeing treatment).

Next, it was immersed in a crosslinking bath (a boric acid aqueous solution obtained by mixing 3 parts by weight of potassium iodide and 3 parts by weight of boric acid with respect to 100 parts by weight of water) at a liquid temperature of 30°C (crosslinking treatment).

Then, while immersing the laminate in a boric acid aqueous solution at a liquid temperature of 70°C (an aqueous solution obtained by blending 4 parts by weight of boric acid and 5 parts by weight of potassium iodide with respect to 100 parts by weight of water), the rollers differ in the peripheral speed Uniaxial stretching is carried out between the cylinders so that the total stretching ratio in the longitudinal direction (longitudinal direction) is 5.5 times (underwater stretching treatment).

Then, the laminate was immersed in a washing bath (aqueous solution obtained by mixing 4 parts by weight of potassium iodide with respect to 100 parts by weight of water) at a liquid temperature of 30° C. (washing treatment).

Through the above, an optical film laminate containing a polarizer having a thickness of 5 μm was obtained.

(Production of polarizers A0~A3)

Regarding the production of the polarizer A0 described above, the manufacturing conditions were changed to those shown in Table 1, except that the polarizers A1 to A3 were produced in the same manner as the production of the polarizer A0. Table 1 shows the thickness, optical characteristics (single transmittance, polarization degree) and boric acid concentration of polarizers A1 to A3.

Table 1

(Manufacture of polarizer B (polarizer with a thickness of 12 μm))

A polyvinyl alcohol film with a thickness of 30 μm and an average polymerization degree of 2400 and a saponification degree of 99.9 mol% was immersed in warm water at 30° C. for 60 seconds to swell. Next, the film was dyed while being immersed in an aqueous solution having a concentration of 0.3% of iodine/potassium iodide (weight ratio=0.5/8), and extended to 3.5 times. Then, stretching was carried out in an aqueous solution of boric acid ester at 65°C so that the total stretching ratio was 6 times. After stretching, drying was carried out in a 40° C. oven for 3 minutes to obtain a PVA-based polarizer. The thickness of the obtained polarizer was 12 μm.

(Production of polarizer C)

Apply corona to one side of the substrate of amorphous isophthalic acid-co-polyethylene terephthalate (IPA-co-PET) film (thickness: 130μm) with a water absorption of 0.75% and Tg75℃ Treatment, coated with polyvinyl alcohol (degree of polymerization 4200, degree of saponification 99.2 mol%) and modified PVA (degree of polymerization 1200) with a ratio of 9:1 on the corona treated surface at 25°C , Acetyl Acetyl Modification Degree 4.6%, Saponification Degree 99.0 mol% or more, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., under the trade name "Gohsefimer Z200") and dried to form a PVA resin layer with a thickness of 11 μm, making a laminate body.

Using a simultaneous biaxial stretching machine, the resulting laminate was shrunk by 30% in the first direction (MD) at 110°C, and at the same time, 5.0 times in-air stretching (stretching treatment) was performed in the second direction (TD).

Next, the laminate was immersed in a 25°C iodine aqueous solution (iodine concentration: 0.2% by weight, potassium iodide concentration: 1.4% by weight) for 40 seconds (dyeing treatment).

The layered body after dyeing was immersed in a 60°C boric acid aqueous solution (boric acid concentration: 5 wt%, potassium iodide concentration: 5 wt%) for 80 seconds (crosslinking treatment).

After the cross-linking treatment, the laminate was immersed in a 25°C potassium iodide aqueous solution (potassium iodide concentration: 5 wt%) for 20 seconds (washing treatment).

Through the above, an optical film laminate including a polarizer having a thickness of 3 μm was obtained.

<protective film>

Acrylic film 1: Use a corona treatment on the easy-to-adhere surface of a (meth)acrylic resin film with a lactone ring structure with a thickness of 40 μm.

Acrylic film 2: The (meth)acrylic resin film having a lactone ring structure with a thickness of 60 μm is applied to the easy-to-treat surface of the film.

Acrylonitrile film 3: The (meth)acrylic resin film having a lactone ring structure with a thickness of 20 μm is applied to the easy-adhesive surface for treatment.

TAC1: Use triacetyl cellulose film with a thickness of 60 μm.

TAC2: Use cellulose acetate film with a thickness of 40 μm.

<Preparation of adhesive suitable for protective film>

(Acrylic Adhesive 1)

The composition of the acryl-based forming material (acrylonitrile 1) is the same as that of the aforementioned transparent resin layer forming material.

(Acrylic Adhesive 2)

12.5 servings of N-hydroxyethylacrylamide (manufactured by Kyoto Co., Ltd., trade name "HEAA")

Acrylic Acrylic Acid Folin (produced by Xingren Company, trade name "ACMO (registered trademark)") 25 copies

Dimethylol-tricyclodecane diacrylate (manufactured by Kyoeisha Chemical Co., Ltd. Product name "LIGHT ACRYLATE DCP-A") 62.5 copies

Photoradical polymerization initiator (2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropan-1-one, manufactured by BASF, trade name "IRGACURE907") 2 parts

，日本化藥公司製，商品名「KAYACURE DETX-S」) 2份 Light sensitizer (diethyl 9-oxysulfur

, Manufactured by Nippon Kayaku Co., Ltd., trade name "KAYACURE DETX-S") 2 copies

(Acrylic Adhesive 3)

12.5 servings of N-hydroxyethylacrylamide (manufactured by Kyoto Co., Ltd., trade name "HEAA")

2-hydroxy-3-phenoxypropyl acrylate (manufactured by East Asia Synthetic Co., Ltd., trade name "ARONIX (registered trademark) M-5700" 25 copies

1,9-nonanediol diacrylate (produced by Kyoeisha Chemical Co., Ltd., trade name "LIGHT ACRYLATE 1.9ND-A") 40 parts

Dimethylol-tricyclodecane diacrylate (made by Kyoeisha Chemical Co., Ltd., trade name "LIGHT ACRYLATE DCP-A") 22.5 servings

Photoradical polymerization initiator (2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropan-1-one, manufactured by BASF, trade name "IRGACURE907") 3 parts

，日本化藥公司製，商品名「KAYACURE DETX-S」) 2份 Light sensitizer (diethyl 9-oxysulfur

, Manufactured by Nippon Kayaku Co., Ltd., trade name "KAYACURE DETX-S") 2 copies

(Epoxy Adhesive 3)

It has the same composition as the epoxy-based forming material (epoxy 1) of the aforementioned transparent resin layer forming material.

(PVA adhesive)

With respect to 100 parts of a polyvinyl alcohol-based resin containing acetylacetoyl groups (average degree of polymerization: 1200, degree of saponification: 98.5 mol%, degree of acetoacetylation: 5 mol%), 50 parts of Hydroxymethyl melamine is dissolved in pure water at a temperature of 30°C and adjusted to an aqueous solution with a solid concentration of 3.7%. To 100 parts of the aforementioned aqueous solution, 18 minutes of an alumina colloidal aqueous solution (average particle diameter 15 nm, solid concentration 10%, positive charge) was added to prepare a PVA adhesive.

<Transparent resin layer forming material>

(Polyvinyl alcohol-based forming material: PVA1)

A polyvinyl alcohol resin with a polymerization degree of 2500 and a saponification degree of 99.7 mol% was dissolved in pure water to prepare an aqueous solution having a solid content concentration of 4% by weight.

(Composition of propylene-based forming materials: propylene-based 1)

N-hydroxyethyl acrylamide (manufactured by Kyoto Co., Ltd., trade name "HEAA") 20 servings

Urethane acrylate (manufactured by Nippon Synthetic Chemical Co., Ltd., trade name "UV-1700B") 80 parts

Photoradical polymerization initiator (2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropan-1-one, manufactured by BASF, trade name "IRGACURE907") 3 parts

，日本化藥公司製，商品名「KAYACURE DETX-S」) 2份 Light sensitizer (diethyl 9-oxysulfur

, Manufactured by Nippon Kayaku Co., Ltd., trade name "KAYACURE DETX-S") 2 copies

(Composition of epoxy-based forming material: Epoxy 1)

3’,4’-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate (Daicel Chemical Industry Co., Ltd., trade name "CelloXide 2021P") 100 parts

Photo cationic polymerization initiator (4-(phenylsulfide) phenyl diphenyl alkane hexafluorophosphate, manufactured by SAN-APRO, trade name "CPI-100P") 1 part

(Modulation of active energy ray hardening type forming material)

Among the above-mentioned adhesives and transparent resin forming materials, acryl-based and epoxy-based materials were blended and stirred at 50° C. for 1 hour to prepare various active energy ray-curable forming materials.

<Formation of adhesive layer>

(Acrylic Adhesive 1)

≪Preparation of acrylic polymer≫

In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen introduction tube, and a cooler, a monomer mixture containing 99 parts of butyl acrylate and 1 part of 4-hydroxybutyl acrylate was put. With respect to the monomer mixture (solid content) 100 parts, as a polymerization initiator of 2,2 '- azobisisobutyronitrile 0.1 parts by inputs with ethyl acetate, while stirring slowly for introducing nitrogen gas After nitrogen substitution, the temperature of the liquid in the flask was maintained at about 60°C to carry out the polymerization reaction for 7 hours. After that, ethyl acetate was added to the resulting reaction liquid to prepare a propylene amide-based polymer solution having a solid content concentration adjusted to 30% and a weight average molecular weight of 1.4 million.

≪Preparation of adhesive composition≫

Relative to 100 parts of the solid content of the above-mentioned acrylic polymer solution, 0.2 parts of ethylmethylpyrrolidinium-bis(trifluoromethanesulfonyl) amide imide (manufactured by Tokyo Chemical Industry) and lithium bis(trifluoro Methanesulfonyl) amide imine (manufactured by Mitsubishi Materials Electronics Co., Ltd.) 1 part, and then further mixed with 0.1 part of trimethylolpropane xylyl diisocyanate (made by Mitsui Chemicals Co., Ltd.: TAKENATE D110N), dibenzoyl amide 0.3 parts of oxide, and γ-glycidoxypropyl methoxysilane (Shin-Etsu Chemical Industry Co., Ltd.: KBM-403) 0.075 parts, to prepare a propylene-based adhesive solution.

(Acrylic Adhesive 2)

In the preparation of the acryl-based polymer of the acryl-based adhesive 1, the one containing 65 parts of butyl acrylate, 34 parts of methmethacrylate, and 1 part of 4-hydroxybutyl acrylate was used as the monomer mixture , And use toluene instead of ethyl acetate as a solvent to prepare an acrylic polymer solution with a weight average molecular weight of 1.1 million. In addition, in the preparation of the adhesive composition, 1 part of a crosslinking agent (made by Japan Polyurethanes Co., Ltd., trade name "CORONATE L") using a compound having an isocyanate group as a main component is used instead of trimethylolpropane Except for 0.1 parts of xylylene diisocyanate (manufactured by Mitsui Chemicals Co., Ltd.: TAKENATE D110N), except that acrylic propylene-based adhesive solution 1 was prepared in the same manner as acrylic propylene-based adhesive 1.

(Acrylic Adhesive 3)

In the preparation of the acryl-based polymer of the acryl-based adhesive 1, the one containing 95 parts of butyl acrylate, 4 parts of acrylic acid, and 1 part of 4-hydroxybutyl acrylate was used as a monomer mixture, and toluene was used. Instead of ethyl acetate as a solvent, an acrylic polymer solution having a weight average molecular weight of 2.2 million was prepared. In addition, in the preparation of the adhesive composition, 0.6 parts of a cross-linking agent (product made from Japanese polyurethane (share), trade name "CORONATE L") containing a compound having an isocyanate group as the main component was used instead of the third Except for 0.1 part of hydroxymethylpropane xylyl diisocyanate (manufactured by Mitsui Chemicals Corporation: TAKENATE D110N), the acrylic propylene-based adhesive solution was prepared in the same manner as the acrylic adhesive-based adhesive 1.

Examples 1 to 28, Comparative Examples 1 to 5

(Manufacture of polarized film with single-sided protection)

The polarizer, adhesive, and protective film shown in Table 1 were used to produce a single-sided protective polarizing film. Table 2 shows the optical characteristics (single transmittance and polarization degree) of the obtained single-sided protective polarizing film. In addition, in Example 9, two protective films were used, but the lamination of the two protective films used the adhesive layer described in Table 1.

In the above, when the polarizers A0 to A3 and C are used, the protective film is bonded to the surface of the polarizer of the optical film laminate through the adhesive layer of the thickness shown in Table 1. Next, the amorphous PET substrate was peeled off to prepare a single-sided protective polarizing film using a thin polarizer. When the polarizer B is used, the protective film is pasted on the side of the PVA polarizer through the adhesive layer of the thickness shown in Table 1.

In addition, in the above, when the adhesives are acrylic adhesives 1 to 3 and epoxy adhesive 1 (in the case of ultraviolet curing adhesives), the thickness of the adhesive layer after curing shown in Table 1 is Method, while applying the adhesive on the surface of the polarizer, the protective film is attached, and then ultraviolet rays as active energy rays are irradiated to harden the adhesive. Ultraviolet irradiation uses a metal halogen lamp sealed with gallium, irradiation device: Fusion UV Systems, Inc. Light HAMMER10, bulb: V bulb, peak illuminance: 1600mW/cm ² , cumulative exposure 1000/mJ/cm ² (wavelength 380~ 440nm), and the illuminance of ultraviolet ray is measured using Sola-Check system made by Solatell. In the case where the adhesive is a PVA-based adhesive, the protective film is applied while applying the adhesive to the surface of the polarizer in such a manner as to be the thickness of the adhesive layer after drying shown in Table 1. Dry at 60°C for 1 minute.

<Making single-sided protective polarizing film with transparent resin layer>

On the polarizer surface of the above single-sided protective polarizing film (the polarizer surface not provided with a transparent protective film), the transparent resin layer forming material shown in Table 2 was used to produce a transparent resin layer so as to have the thickness shown in Table 2 One side protects the polarizing film.

Among the above, when the forming material of acryl 1 and epoxy 1 is used as the transparent resin layer forming material, it is applied to the surface of the polarizer using a wire bar coater and then irradiated with activity under a nitrogen atmosphere Energy rays, thereby forming a transparent resin layer. In addition, the irradiation of active energy rays is performed in the same manner as used in the production of the single-sided protective polarizing film.

In addition, in the above, when PVA1 is used as the transparent resin layer forming material, the forming material adjusted to 25° C. is coated with a wire bar in such a manner that the thickness after drying becomes as described in Table 2, at 60 Hot air drying was performed at ℃ for 1 minute to produce a single-sided protective polarizing film with a transparent resin layer.

<Preparation of polarizing film with adhesive layer>

The solution of the above acrylic adhesives 1 to 3 was uniformly coated on the polyparaphenylene treated with the polysiloxane-based release agent with a spray coating machine so that the thickness after drying became 5 μm, 15 μm, 20 μm or 40 μm. On the surface of the ethylene dicarboxylate film (release film), it was dried in an air circulation constant temperature oven at 155°C for 2 minutes to form an adhesive layer on the surface of the release film.

Next, on the transparent resin layer that has been formed on the single-sided protective polarizing film, it is bonded and formed so as to be of the type and thickness shown in Table 2. The adhesive layer on the peeling surface of the release sheet (separator) is described to produce a polarizing film with an adhesive layer.

The adhesive film-attached polarizing films obtained in the above examples and comparative examples were evaluated as follows. The results are shown in Table 2.

<Single Transmissivity T and Polarization P of Polarizer>

Using a spectroscopic transmittance measuring instrument with an integrating sphere (Dot-3c from Murakami Color Technology Research Institute), the single transmittance T and polarization degree P of the obtained single-sided protective polarizing film were measured.

In addition, the degree of polarization P is the transmittance (parallel transmittance: Tp) when two identical polarizing films are overlapped in parallel with the transmission axes of the two and the transmission axes of the two are orthogonal The transmittance (orthogonal transmittance: Tc) in the case of overlap is applied to the one obtained by the following formula. Polarization P(%)={(Tp-Tc)/(Tp+Tc)} ^1/2 ×100

Each transmittance is shown by setting the fully polarized light obtained through the Glan-Taylor 稜鏡 polarizer to 100%, and using the Y value for visual acuity compensation with a 2 degree viewing angle (C light source) of JIS Z8701.

<Determination of boric acid content in polarizers>

For the polarizers obtained in Examples and Comparative Examples, a Fourier transform infrared spectrophotometer (FTIR) (manufactured by Perkin Elmer, trade name "SPECTRUM 2000") was used, and the total reflection attenuation spectroscopy (ATR) using polarized light as measurement light The measuring method measures the intensity of the boric acid peak (665 cm ^-1 ) and the intensity of the reference peak (2941 cm ^-1 ). From the obtained boric acid peak intensity and the reference peak intensity, a boric acid amount index is calculated by the following formula, and then the boric acid content (weight %) is determined by the calculated boric acid amount index through the following formula.

(Boric acid amount index) = (intensity of boric acid peak 665 cm ^-1 ) / (reference intensity of peak 2941 cm ^-1 )

(Boric acid content (% by weight)) = (boric acid content index) × 5.54 + 4.1

<Determination of Compression Elastic Modulus at 80℃>

The compression elastic modulus was measured using TI900 TriboIndenter (manufactured by Hysitron). The obtained single-sided protective polarizing film 11 with a transparent resin layer was cut into a size of 10 mm×10 mm, fixed to a support equipped with a TriboIndenter, and the compression elastic modulus was measured by nanoindentation. At this time, the position of the indenter is adjusted so as to be pressed into the vicinity of the center of the transparent resin layer. The measurement conditions are shown below.

Use indenter: Berkovich (triangular cone type)

Measurement method: single press-in measurement

Measuring temperature: 80℃

Press depth setting: 100nm

<Measurement of storage elastic modulus>

The storage elastic modulus at 23°C was measured using a viscoelasticity analyzer (trade name: RSA-II) manufactured by Rheometric Corporation. The measurement conditions are measured values at 23°C in the range of -50°C to 200°C at a frequency of 1 Hz, a sample thickness of 2 mm, a compression weight of 100 g, and a heating rate of 5°C/min.

<Suppression effect of nano-slits: guitar shrapnel test>

The obtained polarizing film with an adhesive layer was cut into a size of 50 mm×150 mm (the absorption axis direction was 50 mm) as Sample 11. The sample 11 was used by bonding the surface protective film 6 produced by the following method to the transparent protective film 2 side.

(Surface protective film for testing)

The substrate molding material composed of low-density polyethylene with a density of 0.924 g/cm3 and a melt flow rate of 2.0 g/10 min at 190° C. was supplied to a blown film molding machine for co-extrusion.

At the same time, the adhesive molding material composed of a propylene-butene copolymer with a melt flow rate of 10.0g/10min and a density of 0.86g/cm3 at 230°C (with a mass ratio of propylene:butene=85:15, miscellaneous row structure) was supplied to the mold A film blowing machine with a temperature of 220°C is used for co-extrusion molding.

By this, a surface protective film composed of a base material layer with a thickness of 33 μm and an adhesive layer with a thickness of 5 μm was manufactured.

Next, as shown in the conceptual diagram of FIG. 5(A) and the cross-sectional view of FIG. 5(B), the release sheet (separator) is peeled from the sample, and is attached to the exposed adhesive layer 4 through On the glass plate 20. Next, the center of the sample 11 (surface protection film 6 side) was loaded with a load of 200 g through a guitar shrapnel (manufactured by HISTORY, model "HP2H (HARD)"), and the absorption axis of the polarizer 1 in the sample 11 The orthogonal direction repeats a load of 50 times back and forth at a distance of 100mm. The aforementioned load is carried out at one place.

Next, after the sample 11 was left in an environment of 80° C. for 1 hour, it was confirmed whether or not the sample 11 had light leakage cracks according to the following criteria.

◎: No occurrence.

○: 1 to 5.

△: 6-20.

×: 21 or more.

Figure 6, it becomes a single-sided protective polarizing film 10 or with transparent resin The following indicators of the confirmation of light leakage cracks (nano slits) in the guitar shrapnel test of the single-sided protective polarizing film 11 of the layer are an example of a microscope photograph of the surface of the polarizing film. In FIG. 6(A), no light leakage cracks caused by the nano slits a were confirmed. The state as shown in FIG. 6(A) corresponds to the heating of the guitar shrapnel test of the comparative example, and the heating of the guitar shrapnel test of the embodiment (due to the expansion suppressing effect, the nano slit does not cause light leakage). On the other hand, FIG. 6(B) shows a case where three light leakage cracks caused by the nano slit a due to heating occur in the direction of the absorption axis of the polarizer. The state shown in Fig. 6(B) is after heating in accordance with the guitar shrapnel test of the comparative example. Fig. 6 is a differential dry microscope observation of a sample with nano slits. When photographing the sample, the sample with no nano-slits is placed under the sample with the nano-slits (through the light source side) to make it orthogonally polarized Observe.

<Confirmation of through cracks: thermal shock test>

Cut the obtained polarizing film with adhesive layer into 50mm×150mm (absorption axis direction is 50mm) and 150mm×50mm (absorption axis direction is 150mm), and stick it on both sides of 0.5mm thick alkali-free glass with orthogonal polarization direction Close and make a sample. After putting this sample in an environment of -40 to 85°C thermal shock for 30 minutes × 300 times each, take it out and visually confirm whether there is a through crack (number) in the polarizing film with adhesive layer. Perform 5 trials. The evaluation is based on the following number of cracks that have occurred.

◎: 0 items.

○: One.

△: 2 bars.

×: 3 or more.

FIG. 7 is an example of a microscope photograph of the surface of the polarizing film, which is a single-sided protective polarizing film 10 or a single-sided protective polarizing film 11 with a transparent resin layer, which is an indicator of the penetration crack b confirmation. Fig. 7 uses a differential interference microscope to observe a sample where a through crack has occurred.

<amount of curl>

After peeling off the release film from the obtained polarizing film with an adhesive layer, the adhesive layer was faced up at 23°C and 55% RH for 30 days and the curl height (mm) was measured according to the following criteria Evaluation.

◎: 0~5mm.

○: More than 5mm~10mm.

△: More than 10mm~30mm.

×: More than 30mm.

Table 2

In addition, as in Comparative Examples 4 and 5, when the optical characteristics expressed by the monomer transmittance T and the degree of polarization P do not satisfy the conditions of the following formula, P>-(10 ^0.929T-42.4 -1)×100(However, T<42.3), or P≧99.9 (but T≧42.3), the subject of this case (the occurrence of through cracks and nano-slits) did not appear.

Example 29

Use a long body as a single-sided protective polarizing film, use a micro gravure coater to coat the forming material, and use a long body as the release sheet (separator) and the following surface protection film Same as Example 1. By this, the wound product of the polarizing film (the aspect described in FIG. 2(A)) with a transparent resin layer on one side and the transparent resin layer side with the separator deposited and the transparent protective film side with the surface protective film deposited thereon. In addition, the winding of the single-sided protective polarizing film with a transparent resin layer is prepared by thin slit processing with a width corresponding to the short and long sides of 32-inch alkali-free glass as a set. It is cut by continuously conveying the polarized film with a transparent resin layer on one side to protect it.

(Surface protection film for coil to panel)

The anti-static treatment surface of the polyethylene terephthalate film (trade name: Diafoil T100G38, manufactured by Mitsubishi Resin Co., Ltd., thickness 38 μm) with the anti-static treatment layer is the opposite surface, and the acrylic adhesive is applied to form The thickness of the agent is 15 μm to obtain a surface protective film.

Next, as shown in FIG. 8, a continuous manufacturing system using a roll-to-panel method is used to continuously supply the single-sided protection with a transparent resin layer that is supplied from the set of single-sided protective polarized film-coated windings with a transparent resin layer. Polarizing film, continuously laminated on both sides of 100 pieces of 0.5mm thick 32-inch alkali-free glass to make it The relationship is orthogonal polarized light.

Examples 30, 31

The single-sided protective polarizing film with a transparent resin layer was produced in the same manner as in Examples 2 and 3, respectively, except that it was the same as Example 29.

<Confirm the occurrence of nano-slits: heating test>

Place 100 pieces of non-alkali glass with a single-sided protective polarizing film with a transparent resin layer attached to both sides in an 80°C oven for 24 hours, and then visually confirm whether there are nano slits. In any of Examples 28 to 30, no defects (light leakage) due to nano-slits were observed.

1‧‧‧ Polarizer

2, 2 ' ‧‧‧ protective film

2a‧‧‧adhesive layer

3‧‧‧Transparent resin layer

10‧‧‧Single-sided protective polarizing film

11.11’‧‧‧Single-sided protective polarizing film (with transparent resin layer)

Claims (18)

A single-sided protective polarizing film, which only has a protective film on one side of the polarizer, characterized in that: the other side of the polarizer is provided with a transparent resin layer; the compression elastic modulus of the transparent resin layer at 80°C is 0.1 GPa Above; the aforementioned polarizer contains a polyvinyl alcohol-based resin and is constructed so that its optical characteristics expressed by the monomer transmittance T and the degree of polarization P satisfy the conditions of the following formula: P>-(10 ^0.929T-42.4 -1)× 100 (only T<42.3), or, P≧99.9 (only T≧42.3); and, when the thickness of the polarizer is set to X (μm) and the thickness of the transparent resin layer is set to Y (μm), satisfy X≦ 12. Y≦15, and 0.15≦(Y/X)≦3. The single-sided protective polarizing film according to claim 1, wherein the transparent resin layer is formed of ultraviolet-curing acrylic resin, ultraviolet-curing epoxy resin, urethane resin or polyvinyl alcohol resin . The single-sided protective polarizing film according to claim 1, which has an adhesive layer between the polarizer and the protective film. The single-sided protective polarizing film according to claim 3, wherein the thickness of the adhesive layer is 0.1 μm or more and 5 μm or less. The single-sided protective polarizing film according to claim 3, wherein the compressive elastic modulus of the adhesive layer at 80°C is 0.1 GPa or more and 10 GPa or less. The single-sided protective polarizing film according to claim 3, wherein the adhesive layer is formed of ultraviolet-curable acrylic resin, ultraviolet-curable epoxy resin, urethane resin or polyvinyl alcohol resin. The single-sided protective polarizing film according to claim 1, wherein the protective film is one piece, and the thickness of the protective film is 10 μm or more and 100 μm or less. The single-sided protective polarizing film according to claim 1, wherein the protective film is 2 pieces, each protective film has a thickness of 10 μm or more, and the total thickness of the protective film is 100 μm or less, and there is an adhesive layer or adhesion between each protective film剂层。 Agent layer. The single-sided protective polarizing film according to any one of claims 1 to 8, wherein the polarizer contains boric acid at 25% by weight or less relative to the total amount of polarizers. A polarizing film with an adhesive layer is characterized by having a single-sided protective polarizing film according to any one of claims 1 to 9, and an adhesive layer. The polarizing film with an adhesive layer according to claim 10, wherein the adhesive layer is provided on the transparent resin layer of the single-sided protective polarizing film. The polarizing film with an adhesive layer according to claim 10, wherein the adhesive layer is provided on the protective film that protects the polarizing film on one side. The polarizing film with an adhesive layer according to claim 10, wherein the thickness of the adhesive layer is 1 μm or more and 40 μm or less. The polarizing film with an adhesive layer according to claim 10, wherein the storage elastic modulus of the adhesive layer at 23° C. is 1.0×10 ⁴ Pa or more. The polarizing film with an adhesive layer according to any one of claims 10 to 14, wherein the adhesive layer is provided with a separating member. The polarizing film with an adhesive layer as claimed in claim 15 is a winding. An image display device having a single-sided protective polarizing film according to any one of claims 1 to 9, or an adhesive layer-attached polarizing film according to any one of claims 10 to 14. A continuous manufacturing method of an image display device, comprising the steps of: outputting the polarizing film with an adhesive layer from the winding of the polarizing film with an adhesive layer as claimed in claim 16 and transporting the polarizing film with an adhesive layer, and transferring the The transported polarizing film with an adhesive layer is continuously attached to the surface of the image display panel through the adhesive layer.

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