CN108780181B - Method for producing single-side protective polarizing film with adhesive layer - Google Patents

Method for producing single-side protective polarizing film with adhesive layer Download PDF

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Publication number
CN108780181B
CN108780181B CN201780017068.2A CN201780017068A CN108780181B CN 108780181 B CN108780181 B CN 108780181B CN 201780017068 A CN201780017068 A CN 201780017068A CN 108780181 B CN108780181 B CN 108780181B
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polarizing film
adhesive layer
protective polarizing
polarizer
meth
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CN108780181A (en
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上野友德
三田聪司
岸敦史
池岛健太郎
茂手木佑辅
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Nitto Denko Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/245—Vinyl resins, e.g. polyvinyl chloride [PVC]
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/42—Polarizing, birefringent, filtering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2551/00—Optical elements

Abstract

The present invention relates to a method for producing a one-side protective polarizing film with an adhesive layer, the one-side protective polarizing film with an adhesive layer having a thickness of 10 μm or less and having a transparent resin layer and an adhesive layer in this order from the polarizer side of the one-side protective polarizing film having a protective film only on one side of a polarizer having specific optical characteristics, the method comprising carrying out step (3) after forming a transparent resin layer by carrying out step (1) and step (2), wherein in the step (1), a coating liquid containing a resin component or a curable component capable of constituting a resin layer is applied to the polarizer side of the one-side protective polarizing film while carrying the one-side protective polarizing film, the step (2) is carried out after the coating step (1), the step (2) is performed by curing or hardening the coating liquid, and the step (3) is performed without winding the obtained one-side protective polarizing film with a transparent resin layer in a roll form, and forming an adhesive layer on the transparent resin layer. Even when a thin one-side protective film is used, the transparent resin layer can be stably formed and then the pressure-sensitive adhesive layer can be formed.

Description

Method for producing single-side protective polarizing film with adhesive layer
Technical Field
The present invention relates to a method for manufacturing a single-sided protective polarizing film with an adhesive layer. The pressure-sensitive adhesive layer-attached one-side protective polarizing film obtained by the above-described production method can be used alone to form an image display device such as a Liquid Crystal Display (LCD) or an organic EL display, or can be used as an optical film in which the pressure-sensitive adhesive layer-attached one-side protective polarizing film is laminated to form an image display device such as a Liquid Crystal Display (LCD) or an organic EL display.
Background
The market demand for liquid crystal display devices is rapidly expanding in watches, mobile phones, PDAs, notebook computers, monitors for computers, DVD players, TVs, and the like. A liquid crystal display device is a device for visualizing a polarization state caused by switching (switching) of liquid crystal, and a polarizer is currently used according to a display principle thereof.
As the polarizer, an iodine-containing polarizer having a structure in which, for example, polyvinyl alcohol is adsorbed with iodine and stretched is most widely used in view of high transmittance and high degree of polarization. Such polarizers have disadvantages of extremely low mechanical strength, shrinkage due to heat and moisture, and significant deterioration of polarization function. Therefore, the polarizer obtained was immediately bonded to a protective film coated with an adhesive via the adhesive to prepare a polarizing film.
When the polarizing film is bonded to a liquid crystal cell or the like, an adhesive is generally used. In addition, since there are advantages in that the polarizing film can be instantaneously fixed, a drying process for fixing the polarizing film is not required, and the like, the adhesive may be previously provided on one surface of the polarizing film in the form of an adhesive layer. That is, in the lamination of the polarizing film, a polarizing film with an adhesive layer is generally used.
On the other hand, image display devices such as liquid crystal display devices are becoming thinner, and polarizing films are also required to be thinner. Therefore, the polarizer is also thinned (patent document 1). Further, the thickness reduction can be performed by using a single-sided protective polarizing film in which a protective film is provided only on one side of the polarizer and no protective film is provided on the other side. This single-sided protective polarizing film can be thinned because it has less protective films than a double-sided protective polarizing film in which protective films are provided on both sides of a polarizer.
On the other hand, a polarizing film in which a protective layer (transparent resin layer) is provided on the polarizer side has been proposed because the one-side protective polarizing film has insufficient durability against the thermal shock (patent documents 2 and 3).
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 4751481 Specification
Patent document 2: japanese patent application laid-open No. 2010-009027
Patent document 3: japanese patent laid-open publication No. 2013-160775
Disclosure of Invention
Problems to be solved by the invention
In patent documents 2 and 3, while thinning is achieved by using a one-side protective polarizing film having a protective film only on one side of a polarizer, the protective film is provided to suppress the occurrence of through cracks (cracks occurring in the entire absorption axis direction of the polarizer due to a change in shrinkage stress of the polarizer under a severe environment of thermal shock (for example, a thermal shock test repeating temperature conditions of-30 ℃ and 80 ℃ or a high temperature test of 100 ℃) which occurs in the entire absorption axis direction of the polarizer) caused by using the one-side protective polarizing film. Patent documents 2 and 3 describe that when a protective layer (transparent resin layer) is formed on one-side protective polarizer, the formation of the protective layer can be performed by various coating methods.
On the other hand, as described above, the polarizer is also thinned. In the case of a polarizer used in a polarizing film or a polarizing film with an adhesive layer being thinned (for example, in the case of making the thickness 10 μm or less), the change in the shrinkage stress of the polarizer is small. It is thus understood that the occurrence of the through crack can be suppressed by the thinner polarizer.
However, in the case where the polarizer is thinned (for example, in the case where the thickness is 10 μm or less) while controlling the optical characteristics as in patent document 1 in the case of using the one-side protective polarizing film or the pressure-sensitive adhesive layer-equipped polarizing film using the one-side protective polarizing film in which the occurrence of the through crack is suppressed, it is known that when a mechanical impact is applied to the one-side protective polarizing film or the pressure-sensitive adhesive layer-equipped polarizing film using the one-side protective polarizing film (including the case where a load is applied by bending the polarizer side), an extremely fine slit (hereinafter, also referred to as a nano slit) is locally generated in the absorption axis direction of the polarizer. It is also known that the generation of the nano-slit is not related to the size of the polarizing film. It is also known that the above-described nano-slit does not occur when a double-sided protective polarizing film having protective films on both sides of a polarizer is used. In addition, in the case where the through crack is generated in the polarizer, the stress around the through crack is released, and therefore the through crack is not generated adjacently, but it is known that the nano slit is generated not only singly but also adjacently. It is also known that through cracks have progressiveness that extends in the absorption axis direction of the polarizer in which the cracks have occurred, but the nano slits do not have the progressiveness. Therefore, the nano-slit is a new problem that occurs when the polarizer is thinned and the optical characteristics are controlled to a predetermined range in a single-sided protective polarizing film in which the occurrence of through-cracks is suppressed, and is a problem caused by a phenomenon different from the conventionally known through-cracks.
In addition, the nano-slit is extremely fine and thus cannot be detected in a normal environment. Therefore, even if a nano-slit is formed in the polarizer, it is difficult to confirm defects of the one-side protective polarizing film and the pressure-sensitive adhesive layer-attached polarizing film using the one-side protective polarizing film from light leakage only by simple observation. That is, the defect inspection is usually performed by forming the single-sided protective polarizing film into a long film shape and performing automatic optical inspection, but it is difficult to detect the nano-slit as a defect by the defect inspection. It is also known that the above-described defects caused by the nano-slits can be detected by causing the nano-slits to expand in the width direction (for example, the presence or absence of the above-described light leakage) when a single-side protective polarizing film or a polarizing film with an adhesive layer is bonded to a glass substrate or the like of an image display panel and placed in a heated environment.
Therefore, in a single-side protective polarizing film having a polarizer thickness of 10 μm or less or a polarizing film with an adhesive layer using the single-side protective polarizing film, it is expected to suppress not only through cracks but also the occurrence of nano slits.
However, in the case of using a thin one-side protective polarizing film, after a transparent resin layer is formed from a coating liquid of a protective layer (transparent resin layer), in order to promote curing and obtain a transparent resin layer controlled to a predetermined film thickness, for example, it is desired to once wind the one-side protective polarizing film with a transparent resin layer in a roll shape, continuously draw out the wound one-side protective polarizing film with a transparent resin layer again, and then transfer to a next step of an adhesive layer, that is, a forming step, when the one-side protective polarizing film with a transparent resin layer is continuously drawn out, there is a case where stress is locally applied to a polarizer due to blocking (adhesion between wound films). Therefore, the risk of occurrence of the nano-slit in the roll of the obtained one-side protective polarizing film with a transparent resin layer is increased, and continuous drawing in the next step becomes difficult. On the other hand, when the transparent resin layer is formed, and then the surface protective film is attached to the transparent resin layer and then wound, although blocking due to the transparent resin layer is prevented, when the surface protective film is peeled off, stress is locally applied to the polarizer, and therefore the risk of occurrence of a nano slit is increased.
The present invention provides a method for manufacturing a single-sided protective polarizing film with an adhesive layer, which can stably form a transparent resin layer and then an adhesive layer even when a thin single-sided protective film is used, and can suppress the occurrence of a nano-slit.
Means for solving the problems
As a result of intensive studies, the present inventors have found that the above problems can be solved by the following method for producing a single-sided protective polarizing film with an adhesive layer, and have completed the present invention.
That is, the present invention relates to a method for producing a one-side protective polarizing film with an adhesive layer, the one-side protective polarizing film with an adhesive layer comprising a transparent resin layer and an adhesive layer in this order from the polarizer side of the one-side protective polarizing film having a protective film only on one surface of the polarizer,
the polarizer contains a polyvinyl alcohol resin, has a thickness of 10 [ mu ] m or less, and is configured so that optical properties represented by a monomer transmittance T and a polarization degree P satisfy the following conditions:
P＞－(100.929T-42.4-1) x 100 (wherein T < 42.3), or
P is more than or equal to 99.9 (wherein, T is more than or equal to 42.3),
the formation of the transparent resin layer and the adhesive layer is performed by the following method:
forming a transparent resin layer by performing a step (1) of applying a coating liquid containing a resin component or a coating liquid containing a curable component capable of constituting a resin layer on the polarizer side of the one-side protective polarizing film while conveying the one-side protective polarizing film and a step (2) of curing or hardening the coating liquid and then,
and (3) forming an adhesive layer on the transparent resin layer without winding the obtained single-sided protective polarizing film with the transparent resin layer in a roll shape.
The method for producing the pressure-sensitive adhesive layer-equipped one-side protective polarizing film may further include a step (4) of measuring the thickness of the transparent resin layer in a transport line after the step (2) and before the step (3). The step (4) may be performed by an optical interference method using a polarizing element at the tip of the light source.
In the method for producing the pressure-sensitive adhesive layer-equipped one-side protective polarizing film, the transparent resin layer can be formed by using a coating liquid containing a resin component dissolved or dispersed in water as the coating liquid in the step (1) and curing the coating liquid in the step (2). The coating liquid containing a resin component preferably contains an aqueous solution of a polyvinyl alcohol resin.
In the method for producing the one-side protective polarizing film with an adhesive layer, the coating liquid in the step (1) preferably has a viscosity of 1000mPa · s or less at 25 ℃.
In the method for producing a one-side protective polarizing film with an adhesive layer, the polarizer preferably contains boric acid in an amount of 20 wt% or less with respect to the total amount of polarizers.
In the method for producing the one-side protective polarizing film with an adhesive layer, a separator may be laminated on the adhesive layer. The adhesive layer-carrying single-sided protective polarizing film provided with the separator may be obtained in the form of a roll.
ADVANTAGEOUS EFFECTS OF INVENTION
The pressure-sensitive adhesive layer-attached single-sided protective polarizing film obtained by the production method of the present invention is thinned by using a polarizer having a thickness of 10 μm or less. In addition, in the thin polarizer having a thickness of 10 μm or less, the change in the shrinkage stress applied to the polarizer due to thermal shock is small as compared with the case where the thickness of the polarizer is large, and therefore, the occurrence of through cracks can be suppressed.
On the other hand, a thin polarizer with given optical properties tends to produce nano-slits on the polarizer. It is considered that the nano-slit is generated when a mechanical impact is applied to the one-side protective polarizing film or the polarizing film with an adhesive layer using the one-side protective polarizing film in various steps after the production of the polarizing film with an adhesive layer on the one-side protective polarizing film, and is generated based on a mechanism different from a through crack generated by the thermal impact. In addition, the defects caused by the nano-slits can be detected by the expansion of the nano-slits in the width direction (for example, the presence or absence of the above-described light leakage) when the one-side protective polarizing film with an adhesive layer is bonded to a glass substrate or the like of an image display panel and placed in a heated environment.
In the pressure-sensitive adhesive layer-attached one-side protective polarizing film obtained by the production method of the present invention, the formation of the nano-slit can be suppressed by providing a transparent resin layer on the other surface (the surface not having the protective film) of the polarizer.
According to the manufacturing method of the present invention, after the transparent resin layer is formed on the one-side protective film using the thin polarizer by the steps (1) and (2), the one-side protective polarizing film with the transparent resin layer is transferred to the next step (3) without performing an operation of temporarily winding the obtained one-side protective polarizing film with the transparent resin layer in a roll shape and continuously taking out the wound one-side protective polarizing film with the transparent resin layer again, thereby forming the adhesive layer on the transparent resin layer. As described above, in the manufacturing method of the present invention, since the winding step and the continuous drawing step of the one-side protective polarizing film with a transparent resin layer are not performed, the one-side protective polarizing film with an adhesive layer can be continuously and stably manufactured without increasing the risk of occurrence of nano-slits due to blocking of the one-side protective polarizing film with a transparent resin layer.
In the production method of the present invention, the step (4) of measuring the film thickness of the transparent resin layer of the one-side protective polarizing film with a transparent resin layer may be provided after the step (2) and before the step (3). In the step (4), the film thickness of the transparent resin layer can be stably measured without winding the single-sided protective polarizing film with a transparent resin layer in a roll form, and the transparent resin layer can be controlled to have a predetermined film thickness. As a result, it is not necessary to check the film thickness management off-line, and therefore, productivity is improved.
Drawings
Fig. 1 is a schematic diagram showing an example of an embodiment of the production method of the present invention.
Fig. 2 is a schematic diagram showing one embodiment of step (4) in the manufacturing method of the present invention.
Fig. 3 is an example of a schematic diagram for comparing a nano-slit and a through-crack generated in a polarizer.
Description of the symbols
1 Single-sided protective polarizing film
10 polarizer
20 protective film
2' coating liquid
2 a transparent resin layer
3 adhesive layer
40 light source
41 polarizer
A single-side protective polarizing film with transparent resin layer
B Single-sided protective polarizing films with adhesive layer
Detailed Description
The steps (1) to (3) of the method for producing a pressure-sensitive adhesive layer-equipped one-side protective polarizing film of the present invention will be described below with reference to fig. 1.
In the coating step (1), the coating liquid 2' is applied to the one-side protective polarizing film 1 during transportation. The one-sided protective polarizing film 1 has a protective film 20 only on one side of the polarizer 10, and the structure is represented by polarizer 10/protective film 20. In fig. 1, the coating liquid 2' is shown in a state of being (directly) applied to a polarizer of the one-side protective polarizing film 1. The single-sided protective polarizing film 1 is preferably transported at 5 to 50 m/min, and more preferably transported at 10 to 40 m/min. In the curing or hardening step (2), the transparent resin layer 2 is formed from the coating liquid 2' to obtain the transparent resin layer-attached one-side protective polarizing film a. Next, the step (3) of forming the pressure-sensitive adhesive layer 3 on the transparent resin layer 2 without winding the one-side protective polarizing film a with a transparent resin layer in a roll shape was carried out to produce the one-side protective polarizing film B with a pressure-sensitive adhesive layer.
As shown in fig. 1, the manufacturing method of the present invention may further include a step (4) of measuring the film thickness of the transparent resin layer in the transport line after the step (2) and before the step (3). The step (4) can be performed by an optical interference method using a polarizing element 41 between the light source 40 and the single-side protective polarizing film as shown in fig. 2. The light source 40 is disposed in a manner perpendicular to the transparent resin layer 2 side of the one-side protective polarizing film a with a transparent resin layer. Between the light source 40 and the one-side protective polarizing film a with a transparent resin layer, the light source 40 was disposed using the polarizing element 41 so that the polarizer 10 of the one-side protective polarizing film a with a transparent resin layer was orthogonal to the absorption axis, and the thickness of the transparent resin layer 2 was measured by optical interference.
Further, although not shown, a separator may be provided on the pressure-sensitive adhesive layer of the pressure-sensitive adhesive layer-attached one-side protective polarizing film B of the present invention. In addition, a surface protective film may be provided on the protective film 20 side of the pressure-sensitive adhesive layer-attached one-side protective polarizing film B of the present invention. The one-side protective polarizing film with an adhesive layer having at least a separator (further, a polarizing film with a surface protective film) can be used as a roll, and for example, an image display device can be continuously manufactured by applying the polarizing film with an adhesive layer, which is continuously drawn out from the roll and conveyed by a separator, to a system in which the polarizing film is bonded to the surface of an image display panel via an adhesive layer (also referred to as a "roll-to-panel system", typically, japanese patent No. 4406043 specification).
Fig. 3 is a schematic diagram comparing a nanoslit a and a through crack b generated on a polarizer. Fig. 3(a) shows a nanoslit a produced on the polarizer 10, and fig. 3(B) shows a through crack B produced on the polarizer 10. The nano-slits a are generated by mechanical impact, and the nano-slits a locally generated in the absorption axis direction of the polarizer 10 cannot be confirmed at the time of initial generation, but can be confirmed by expansion in the width direction in a thermal environment (e.g., 80 ℃ or 60 ℃, 90% RH). On the other hand, the nanoslit a is not considered to have a progressivity extending in the absorption axis direction of the polarizer. The generation of the nano-slit a is not considered to be related to the size of the polarizing film. The nano-slits a are not only individually generated but also adjacently generated in some cases. On the other hand, the through crack b is generated by thermal shock (e.g., thermal shock test). The through crack has a progressivity extending in the absorption axis direction of the polarizer in which the crack has occurred. When the through crack b is generated, the stress around the through crack b is released, and thus the through crack is not generated adjacently.
< Process (1) >
Single side protective polarizing film
The single-sided protective polarizing film is a polarizing film having a protective film only on one side of a thin polarizer. The single-sided protective polarizing film preferably has a thickness (total thickness) of 60 μm or less. In the thin one-side protective film, the transparent resin layer having a stable thickness can be formed by the manufacturing method of the present invention. The thickness of the single-sided protective polarizing film may be 55 μm or less. On the other hand, from the viewpoint of transportability, the thickness of the thin one-side protective film is preferably 20 μm or more, and more preferably 25 μm or more.
Polarizer
In the present invention, a polarizer having a thickness of 10 μm or less is used. From the viewpoint of reducing the thickness and suppressing the occurrence of through cracks, the thickness of the polarizer is preferably 8 μm or less, more preferably 7 μm or less, and still more preferably 6 μm or less. On the other hand, the thickness of the polarizer is preferably 2 μm or more, more preferably 3 μm or more. Such a thin polarizer has excellent durability against thermal shock because of small thickness unevenness, excellent visibility, and small dimensional change.
As the polarizer, a polarizer using a polyvinyl alcohol resin can be used. Examples of the polarizer include films obtained by uniaxially stretching hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and ethylene-vinyl acetate copolymer partially saponified films, and polyene oriented films such as polyvinyl alcohol dehydrated products and polyvinyl chloride desalted products, and the like. Among these, a polarizer made of a dichroic material such as a polyvinyl alcohol film and iodine is preferable.
The polarizer obtained by uniaxially stretching a polyvinyl alcohol film dyed with iodine can be produced, for example, by dyeing a polyvinyl alcohol film by immersing the film in an aqueous iodine solution and stretching the film to 3 to 7 times the original length. If necessary, boric acid, zinc sulfate, zinc chloride, or the like may be contained, and the film may be immersed in an aqueous solution of potassium iodide or the like. Further, the polyvinyl alcohol film may be immersed in water and washed with water before dyeing, if necessary. By washing the polyvinyl alcohol film with water, dirt and an anti-blocking agent on the surface of the polyvinyl alcohol film can be washed off, and the polyvinyl alcohol film can be swollen to prevent unevenness such as uneven dyeing. The stretching may be performed after the dyeing with iodine, or may be performed while dyeing, or may be performed after the stretching with iodine. Stretching may be carried out in an aqueous solution or water bath of boric acid, potassium iodide, or the like.
The polarizer preferably contains boric acid from the viewpoint of tensile stability and optical durability. In addition, from the viewpoint of suppressing the occurrence of through cracks and suppressing the elongation, the content of boric acid contained in the polarizer is preferably 20% by weight or less, more preferably 18% by weight or less, and further preferably 16% by weight or less with respect to the total amount of the polarizer. On the other hand, the boric acid content relative to the total amount of the polarizers is preferably 10% by weight or more, more preferably 12% by weight or more, from the viewpoint of the tensile stability and optical durability of the polarizers.
Typical examples of the thin polarizers include thin polarizers described in japanese patent No. 4751486, japanese patent No. 4751481, japanese patent No. 4815544, japanese patent No. 5048120, international publication No. 2014/077599, and international publication No. 2014/077636, and thin polarizers obtained by the production methods described in these documents.
The polarizer is configured such that optical characteristics represented by a single transmittance T and a polarization degree P satisfy the following conditions:
P＞－(100.929T-42.4-1) x 100 (wherein T < 42.3), or
P is more than or equal to 99.9 (wherein, T is more than or equal to 42.3).
A polarizer configured to satisfy the above conditions has performance required for a display for a liquid crystal television using a large-sized display element. Specifically, the contrast ratio is 1000:1 or more and the maximum luminance is 500cd/m2The above. For another application, for example, the adhesive sheet can be bonded to the visible side of an organic EL display device.
As the thin polarizer, among the production methods including the step of stretching in a state of a laminate and the step of dyeing, from the viewpoint of being able to stretch to a high magnification to improve the polarizing performance, a thin polarizer obtained by a production method including the step of stretching in an aqueous boric acid solution as described in japanese patent No. 4751486, japanese patent No. 4751481, and japanese patent No. 4815544 is preferable, and a thin polarizer obtained by a production method including the step of stretching in an auxiliary gas atmosphere before stretching in an aqueous boric acid solution as described in japanese patent No. 4751481 and japanese patent No. 4815544 is particularly preferable. These thin polarizers can be obtained by a production method including a step of stretching a polyvinyl alcohol resin (hereinafter, also referred to as PVA-based resin) layer and a resin base material for stretching in a laminated state, and a step of dyeing. With this method, even if the PVA-based resin layer is thin, it can be stretched without causing troubles such as breakage due to stretching, because it is supported by the resin base material for stretching.
Protective film
The material constituting the protective film is preferably excellent in transparency, mechanical strength, thermal stability, moisture barrier properties, isotropy, and the like. Examples thereof include: polyester polymers such AS polyethylene terephthalate and polyethylene naphthalate, cellulose polymers such AS cellulose diacetate and cellulose triacetate, acrylic polymers such AS polymethyl methacrylate, styrene polymers such AS polystyrene and acrylonitrile-styrene copolymer (AS resin), and polycarbonate polymers. Examples of the polymer forming the protective film include: examples of the polymer include polyolefin polymers such as polyethylene, polypropylene, cyclic polyolefins having a norbornene structure, and ethylene-propylene copolymers, amide polymers such as vinyl chloride polymers, nylon and aromatic polyamides, imide polymers, sulfone polymers, polyethersulfone polymers, polyetheretherketone polymers, polyphenylene sulfide polymers, vinyl alcohol polymers, vinylidene chloride polymers, vinyl butyral polymers, aromatic ester polymers, polyoxymethylene polymers, epoxy polymers, and blends of the above polymers. These protective films are generally bonded to the polarizer via an adhesive layer.
The protective film may contain 1 or more kinds of any appropriate additives. Examples of additives include: ultraviolet absorbers, antioxidants, lubricants, plasticizers, mold release agents, anti-coloring agents, flame retardants, nucleating agents, antistatic agents, pigments, colorants, and the like. The content of the thermoplastic resin in the protective film is preferably 50 to 100 mass%, more preferably 50 to 99 mass%, further preferably 60 to 98 mass%, and particularly preferably 70 to 97 mass%. When the content of the thermoplastic resin in the protective film is 50% by mass or less, there is a possibility that high transparency inherent in the thermoplastic resin cannot be sufficiently exhibited.
As the protective film, a retardation film, a brightness enhancement film, a diffusion film, or the like can be used. Examples of the retardation film include a retardation film having a front retardation of 40nm or more and/or a thickness direction retardation of 80nm or more. The front phase difference is usually controlled within a range of 40 to 200nm, and the thickness direction phase difference is usually controlled within a range of 80 to 300 nm. When the retardation film is used as the protective film, the retardation film also functions as a polarizer protective film, and therefore, the thickness can be reduced.
Examples of the retardation film include a birefringent film obtained by uniaxially stretching or biaxially stretching a thermoplastic resin film. The temperature and stretch ratio of the stretching can be appropriately set depending on the retardation value, the material and thickness of the film.
The thickness of the protective film may be suitably determined, but is preferably 2 to 200 μm, more preferably 3 to 100 μm, from the viewpoints of strength, workability such as workability, and thin layer property. In particular, when the thickness (total thickness) of the single-sided protective polarizing film is adjusted to 60 μm or less, the thickness of the protective film (when a film is formed in advance) is preferably 15 to 60 μm, and more preferably 20 to 55 μm, from the viewpoint of transportability. On the other hand, the thickness of the protective film (in the case of being formed by coating and curing) is preferably 3 to 50 μm, and more preferably 5 to 40 μm, from the viewpoint of transportability. The protective film may be used in a plurality of or a plurality of layers.
A functional layer such as a hard coat layer, an antireflection layer, an adhesion prevention layer, a diffusion layer, or an antiglare layer may be provided on the side of the protective film to which the polarizer is not bonded. The functional layers such as the hard coat layer, the antireflection layer, the adhesion prevention layer, the diffusion layer, and the antiglare layer may be provided as the protective film itself, or may be provided separately from the protective film.
< sandwiching layer >
The protective film and the polarizer may be laminated together with an adhesive layer, an undercoat layer (primer layer), and the like interposed therebetween. In this case, it is preferable to stack both layers without an air gap by using an interlayer. The interlayer between the polarizer 1 and the protective film 2 is not shown in fig. 1.
The adhesive layer may be formed using an adhesive. The type of the adhesive is not particularly limited, and various adhesives can be used. The adhesive layer is not particularly limited as long as it is an optically transparent layer, and various types of adhesives such as aqueous, solvent, hot melt, and active energy ray-curable adhesives can be used as the adhesive, but an aqueous adhesive or an active energy ray-curable adhesive is preferable.
Examples of the aqueous adhesive include isocyanate adhesives, polyvinyl alcohol adhesives, gelatin adhesives, vinyl latexes, and aqueous polyesters. The aqueous adhesive is generally used in the form of an aqueous adhesive, and usually contains 0.5 to 60% by weight of solid content.
The active energy ray-curable adhesive is an adhesive that is cured by an active energy ray such as an electron beam or ultraviolet ray (radical-curable type or cation-curable type), and can be used in the form of, for example, an electron beam-curable type or an ultraviolet-curable type. As the active energy ray-curable adhesive, for example, a radical photo-curable adhesive can be used. When a radical photo-curable active energy ray-curable adhesive is used as the ultraviolet-curable adhesive, the adhesive contains a radical polymerizable compound and a photopolymerization initiator.
The application method of the adhesive can be appropriately selected depending on the viscosity of the adhesive and the target thickness. Examples of the coating method include: reverse coaters, gravure coaters (direct, reverse, or offset), bar reverse coaters, roll coaters, die coaters, wire wound bar coaters, and the like. Further, the coating may be performed by a dipping method or the like.
When an aqueous adhesive or the like is used for the application of the adhesive, the thickness of the adhesive layer to be finally formed is preferably 30 to 300 nm. The thickness of the adhesive layer is more preferably 60 to 150 nm. On the other hand, when the active energy ray-curable adhesive is used, the thickness of the adhesive layer is preferably 0.2 to 20 μm.
In the case of laminating the polarizer and the protective film, an easy adhesion layer may be provided between the protective film and the adhesive layer. The easy-adhesion layer can be formed using various resins having, for example, a polyester skeleton, a polyether skeleton, a polycarbonate skeleton, a polyurethane skeleton, silicones, a polyamide skeleton, a polyimide skeleton, a polyvinyl alcohol skeleton, and the like. These polymer resins may be used alone in 1 kind, or in combination of 2 or more kinds. In addition, other additives may be added to the formation of the easy adhesion layer. Specifically, a thickener, an ultraviolet absorber, an antioxidant, a stabilizer such as a heat stabilizer, and the like can be further exemplified.
Generally, an easy-adhesion layer is provided in advance on a protective film, and the easy-adhesion layer side of the protective film is laminated on the polarizer via an adhesive layer. The easy adhesion layer can be formed by applying a material for forming the easy adhesion layer to the protective film by a known technique and drying the applied material. The material for forming the easy-adhesion layer is usually prepared as a solution diluted to an appropriate concentration in consideration of the thickness after drying, the smoothness of 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 further preferably 0.05 to 1 μm. In this case, the total thickness of the easy adhesion layer is preferably within the above range.
The adhesive layer is formed of an adhesive. As the binder, various binders can be used, and examples thereof include: rubber-based adhesives, acrylic-based adhesives, silicone-based adhesives, urethane-based adhesives, vinyl alkyl ether-based adhesives, polyvinyl pyrrolidone-based adhesives, polyacrylamide-based adhesives, cellulose-based adhesives, and the like. The adhesive base polymer can be selected corresponding to the kind of the above-mentioned adhesive. Among the above-mentioned pressure-sensitive adhesives, acrylic pressure-sensitive adhesives are preferably used because they are excellent in optical transparency, exhibit adhesive properties such as suitable wettability, cohesiveness and adhesiveness, and are excellent in weather resistance, heat resistance and the like.
The undercoat layer (undercoat layer) is formed to improve the adhesion between the polarizer and the protective film. The material constituting the undercoat 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 resin layer. For example, a thermoplastic resin or the like excellent in transparency, thermal stability, stretchability, and the like can be used. Examples of the thermoplastic resin include: acrylic resin, polyolefin resin, polyester resin, polyvinyl alcohol resin, or a mixture thereof.
Coating liquid
The coating liquid contains a resin component or a curable component that can constitute the resin layer. The transparent resin layer is formed by the coating liquid.
The form of the coating liquid is not particularly limited as long as it is liquid, and may be any form of aqueous, aqueous dispersion, solvent system, or solvent-free.
The coating liquid is advantageously low in viscosity because it easily penetrates into a damaged portion of the polarizer. The value of the viscosity measured at 25 ℃ is preferably 2000 mPas or less, more preferably 1000 mPas or less, further preferably 500 mPas or less, further preferably 100 mPas or less.
The coating of the coating liquid on the one-side protective polarizing film (polarizer side) is preferably performed so that the thickness of the transparent resin layer formed after the step (2) becomes 0.2 μm or more. The thickness of the transparent resin layer is preferably 0.5 μm or more, and more preferably 0.7 μm or more. On the other hand, when the transparent resin layer is too thick, the optical reliability and water resistance are lowered, and therefore, the thickness of the transparent resin layer is preferably 3 μm or less, more preferably less than 3 μm, and further preferably 2 μm or less.
Examples of the material for forming the transparent resin layer include: polyester-based resins, polyether-based resins, polycarbonate-based resins, polyurethane-based resins, silicone-based resins, polyamide-based resins, polyimide-based resins, PVA-based resins, acrylic resins, epoxy-based resins, isocyanate-based resins, and the like. These resin materials may be used alone in 1 kind, or in combination in 2 or more kinds, and among these, 1 or more kinds selected from the group consisting of polyurethane-based resins, PVA-based resins, acrylic resins, and epoxy-based resins are preferable, and PVA-based resins and acrylic resins are more preferable.
The coating liquid preferably contains a coating liquid in which a resin component is dissolved or dispersed in water. The resin component dissolved or dispersed in water is a resin dissolved in water at normal temperature (25 ℃) or a resin component obtained by dissolving a water-soluble resin in an aqueous solvent. When the coating liquid is aqueous or water-dispersed, the surface of the polarizer swells, and the coating liquid is thereby impregnated into the damaged portion, which is advantageous. That is, when the coating liquid is aqueous or aqueous dispersion, the orientation of polyvinyl alcohol molecules around the damaged portion constituting the polarizer can be partially relaxed, and the boric acid content around the damaged portion can be reduced, so that even if the thickness of the transparent resin layer is small (for example, less than 3 μm, preferably 2 μm or less), the expansion of the damaged portion can be effectively suppressed.
Typical examples of the resin component that can be dissolved or dispersed in water include: polyvinyl alcohol resin, poly (meth) acrylic acid, polyacrylamide, methylolated melamine resin, methylolated urea resin, phenol-formaldehyde resole resin, polyethylene oxide, carboxymethyl cellulose, and the like. These may be used alone or in combination of two or more. As the resin component, polyvinyl alcohol-based resins, poly (meth) acrylic acid, and methylolated melamine are preferably used. In particular, from the viewpoint of adhesion to a polyvinyl alcohol-based resin constituting the polarizer, a polyvinyl alcohol-based resin is preferable as the resin component. Hereinafter, a case where a polyvinyl alcohol resin is used will be described.
The transparent resin layer is preferably formed of a material containing a polyvinyl alcohol resin. 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 resin include polyvinyl alcohol. Polyvinyl alcohol can be obtained by saponifying polyvinyl acetate. The polyvinyl alcohol resin may be a saponified product of a copolymer of vinyl acetate and a copolymerizable monomer. When the copolymerizable monomer is ethylene, an ethylene-vinyl alcohol copolymer can be obtained. Further, as the copolymerizable monomer, there may be mentioned: unsaturated carboxylic acids such as maleic acid (anhydride), fumaric acid, crotonic acid, itaconic acid, and (meth) acrylic acid, and esters thereof; α -olefins such as ethylene and propylene, (meth) allylsulfonic acid (sodium), sodium monoalkyl maleate sulfonate, sodium monoalkyl maleate disulfonate, N-methylolacrylamide, alkali metal salts of acrylamidoalkylsulfonic acid, N-vinylpyrrolidone derivatives, and the like. These polyvinyl alcohol resins may be used singly or in combination of two or more.
The polyvinyl alcohol resin having a saponification degree of, for example, 95 mol% or more can be used, but from the viewpoint of satisfying the moist heat resistance and the water resistance, the saponification degree is preferably 99 mol% or more, and more preferably 99.7 mol% or more. The saponification degree indicates the proportion of the unit actually saponified to a vinyl alcohol unit among the units convertible to the vinyl alcohol unit by saponification, and the residue is a vinyl ester unit. The degree of saponification can be determined in accordance with JIS K6726-.
The polyvinyl alcohol resin having an average degree of polymerization of, for example, 500 or more can be used, but from the viewpoint of satisfying the moist heat resistance and water resistance, the average degree of polymerization is preferably 1000 or more, more preferably 1500 or more, and still more preferably 2000 or more. The average polymerization degree of the polyvinyl alcohol resin can be measured according to JIS-K6726.
As the polyvinyl alcohol resin, a modified polyvinyl alcohol resin having a hydrophilic functional group in a side chain of the polyvinyl alcohol or a copolymer thereof can be used. Examples of the hydrophilic functional group include an acetoacetyl group and a carbonyl group. Further, a modified polyvinyl alcohol obtained by acetalizing, urethanizing, etherifying, grafting, phosphorylating, or the like, a polyvinyl alcohol resin may be used.
The proportion of the polyvinyl alcohol resin in the transparent resin layer or the forming material (solid content) is preferably 80 wt% or more, more preferably 90 wt% or more, and still more preferably 95 wt% or more.
The coating liquid may be prepared by dissolving the polyvinyl alcohol resin in a solvent. Examples of the solvent include: water, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, various glycols, polyhydric alcohols such as trimethylolpropane, and amines such as ethylenediamine and diethylenetriamine. These solvents may be used alone or in combination of two or more. Among these solvents, an aqueous solution using water as a solvent is preferably prepared and used. The concentration of the polyvinyl alcohol resin in the forming material (e.g., aqueous solution) is not particularly limited, but is 0.1 to 15 wt%, preferably 0.5 to 10 wt%, in consideration of coating properties, storage stability, and the like.
In the coating liquid (e.g., aqueous solution), examples of the additive include polyhydric alcohols such as ethylene glycol and glycerin. Examples of the surfactant include nonionic surfactants. Further, a coupling agent such as a silane coupling agent or a titanium coupling agent, a stabilizer such as various thickeners, an ultraviolet absorber, an antioxidant, a heat stabilizer, a hydrolysis stabilizer, or the like may be added.
The coating liquid is preferably applied so that the thickness after drying becomes 0.2 μm or more. The coating operation is not particularly limited, and any suitable method may be employed. For example, the following may be employed: various methods such as a gravure coating method (direct, reverse, or offset), a roll coating method, a spin coating method, a wire bar coating method, a dip coating method, a die coating method, a shower coating method, a spray coating method, and a blade coating method (a doctor blade coating method, etc.).
Next, a case where a coating liquid containing a curable component capable of constituting a resin is used for forming the transparent resin layer will be described. The curable components are broadly classified into active energy ray-curable types such as electron beam-curable types, ultraviolet-curable types, and visible light-curable types, and heat-curable types. Ultraviolet-curable types and visible-light-curable types are classified into radical polymerization-curable types and cationic polymerization-curable types. In the present invention, the active energy ray having a wavelength range of 10nm to 380nm is described as ultraviolet ray, and the active energy ray having a wavelength range of 380nm to 800nm is described as visible light. The radical polymerization curing type curable component can be used as a thermosetting type curable component.
Free radical polymerization curing type Forming Material
Examples of the curable component include a radical polymerizable compound. Examples of the radical polymerizable compound include compounds having a radical polymerizable functional group having a carbon-carbon double bond such as a (meth) acryloyl group or a vinyl group. Any of monofunctional radical polymerizable compounds and difunctional or higher polyfunctional radical polymerizable compounds can be used as the curable component. These radical polymerizable compounds may be used alone in 1 kind, or in combination with 2 or more kinds. As these radical polymerizable compounds, for example, compounds having a (meth) acryloyl group are preferable. In the present invention, (meth) acryloyl means acryloyl and/or methacryloyl, and "(meth)" means the same as defined below.
Monofunctional radical polymerizable Compound
Examples of the monofunctional radical polymerizable compound include a (meth) acrylamide derivative having a (meth) acrylamide group. The (meth) acrylamide derivative is preferable in that it not only ensures adhesion to a polarizer, but also has a high polymerization rate and excellent productivity. Specific examples of the (meth) acrylamide derivative include N-alkyl-containing (meth) acrylamide derivatives such as N-methyl (meth) acrylamide, N-dimethyl (meth) acrylamide, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, and N-hexyl (meth) acrylamide; n-hydroxyalkyl (meth) acrylamide-containing derivatives such as N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, and N-methylol-N-propyl (meth) acrylamide; n-aminoalkyl-containing (meth) acrylamide derivatives such as aminomethyl (meth) acrylamide and aminoethyl (meth) acrylamide; n-alkoxy group-containing (meth) acrylamide derivatives such as N-methoxymethylacrylamide and N-ethoxymethylacrylamide; n-mercaptoalkyl group-containing (meth) acrylamide derivatives such as mercaptomethyl (meth) acrylamide and mercaptoethyl (meth) acrylamide; and so on. Examples of the heterocycle-containing (meth) acrylamide derivative in which the nitrogen atom of the (meth) acrylamide group forms a heterocycle include N-acryloylmorpholine, N-acryloylpiperidine, N-methacryloylpiperidine, and N-acryloylpyrrolidine.
Among the above (meth) acrylamide derivatives, N-hydroxyalkyl (meth) acrylamide derivatives are preferable from the viewpoint of adhesion to a polarizer, and N-hydroxyethyl (meth) acrylamide is particularly preferable.
Examples of the monofunctional radical polymerizable compound include various (meth) acrylic acid derivatives having a (meth) acryloyloxy group. Specific examples thereof 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, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, (C1-20) alkyl (meth) acrylates such as t-amyl (meth) acrylate, 3-pentyl (meth) acrylate, 2-dimethylbutyl (meth) acrylate, n-hexyl (meth) acrylate, hexadecyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 4-methyl-2-propylpentyl (meth) acrylate, and n-octadecyl (meth) acrylate.
Examples of the (meth) acrylic acid derivative include: cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate and cyclopentyl (meth) acrylate;
aralkyl (meth) acrylates such as benzyl (meth) acrylate;
polycyclic (meth) acrylates such as 2-isobornyl (meth) acrylate, 2-norbornyl methyl (meth) acrylate, 5-norbornen-2-yl methyl (meth) acrylate, 3-methyl-2-norbornyl methyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and dicyclopentanyl (meth) acrylate;
(meth) acrylic acid esters having an alkoxy group or a phenoxy group such as 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-methoxymethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, and alkylphenoxypolyethylene glycol (meth) acrylate; and so on.
Further, examples of the (meth) acrylic acid derivative include: hydroxyalkyl (meth) acrylates such as 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-hydroxydecyl (meth) acrylate, and 12-hydroxylauryl (meth) acrylate, hydroxy-containing (meth) acrylates such as [4- (hydroxymethyl) cyclohexyl ] methyl acrylate, cyclohexanedimethanol mono (meth) acrylate, and 2-hydroxy-3-phenoxypropyl (meth) acrylate;
epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate glycidyl ether;
halogen-containing (meth) acrylates such as 2,2, 2-trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, and 3-chloro-2-hydroxypropyl (meth) acrylate;
alkylaminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate;
oxetanyl (meth) acrylates such as 3-oxetanyl methyl (meth) acrylate, 3-methyloxetanyl methyl (meth) acrylate, 3-ethyloxetanyl methyl (meth) acrylate, 3-butyloxetanyl methyl (meth) acrylate, and 3-hexyloxetanyl methyl (meth) acrylate;
and (meth) acrylates having a heterocyclic ring such as tetrahydrofurfuryl (meth) acrylate and butyrolactone (meth) acrylate, hydroxypivalic acid neopentyl glycol (meth) acrylic acid adducts, and p-phenylphenol (meth) acrylate.
Examples of the monofunctional radical polymerizable compound include: carboxyl group-containing monomers such as (meth) acrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid.
Examples of the monofunctional radical polymerizable compound include: lactam-type vinyl monomers such as N-vinylpyrrolidone, N-vinyl-epsilon-caprolactam and methyl vinyl pyrrolidone; vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine, vinylpyrazine, vinylpyrrole, vinylimidazole, vinylpyridine
Figure BDA0001798411230000171
Vinyl monomers having a nitrogen-containing heterocycle such as oxazole and vinyl morpholine.
As the monofunctional radical polymerizable compound, a radical polymerizable compound having an active methylene group can be used. The radical polymerizable compound having an active methylene group is a compound having an active methylene group and an active double bond group such as a (meth) acryloyl group at a terminal or in a molecule. Examples of the active methylene group include: acetoacetyl, alkoxymalonyl, cyanoacetyl, or the like. The active methylene group is preferably an acetoacetyl group. Specific examples of the radical polymerizable compound having an active methylene group include: acetoacetoxyethyl alkyl (meth) acrylates such as 2-acetoacetoxyethyl (meth) acrylate, 2-acetoacetoxyethyl propyl (meth) acrylate, and 2-acetoacetoxyethyl-1-methylethyl (meth) acrylate; 2-ethoxymalonyloxyethyl (meth) acrylate, 2-cyanoacetoxyethyl (meth) acrylate, N- (2-cyanoacetoxyethyl) acrylamide, N- (2-propionylacetyloxybutyl) acrylamide, N- (4-acetoacetoxyethylmethylbenzyl) acrylamide, N- (2-acetoacetylaminoethyl) acrylamide and the like. The radical polymerizable compound having an active methylene group is preferably acetoacetoxyethyl (meth) acrylate.
Polyfunctional radical polymerizable Compound
Further, examples of the bifunctional or higher polyfunctional radical polymerizable compound include: 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 ethylene oxide adduct di (meth) Acrylate, bisphenol A propylene oxide adduct di (meth) Acrylate, bisphenol A diglycidyl ether di (meth) Acrylate, neopentyl glycol di (meth) Acrylate, tricyclodecane dimethanol di (meth) Acrylate, Cyclic trimethylolpropane formal (meth) Acrylate, diethylene glycol formal (meth) Acrylate, and the like
Figure BDA0001798411230000181
Esters of (meth) acrylic acids and polyhydric alcohols such as alkanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and EO-modified diglycerol tetra (meth) acrylate, and 9, 9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl]Fluorene. Specific examples thereof include ARONIXM-220 (manufactured by Toyo Kabushiki Kaisha), LIGHT ACRYLATE 1,9ND-A (manufactured by Kyoeisha Kaisha), LIGHT ACRYLATE DGE-4A (manufactured by Kyowa Kagaku K.K.), LIGHT ACRYLATE DCP-A (manufactured by Kyowa Kagaku K.K.), SR-531 (manufactured by Sartomer K.K.), CD-536 (manufactured by Sartomer K.K.), and the like. Further, as necessary, there may be mentioned: various epoxy (meth) acrylates, urethane (meth) acrylates, polyester (meth) acrylates, various (meth) acrylate monomers, and the like.
From the viewpoint of satisfying both of the adhesion to a polarizer and the optical durability, the radical polymerizable compound is preferably a monofunctional radical polymerizable compound and a polyfunctional radical polymerizable compound used in combination. In general, it is preferable to use a combination of 3 to 80% by weight of a monofunctional radical polymerizable compound and 20 to 97% by weight of a polyfunctional radical polymerizable compound based on 100% by weight of a radical polymerizable compound.
Form of radical polymerization curing type Forming Material
The radical polymerization curing type forming material can be used in the form of an active energy ray curing type or a thermosetting type forming material. When the active energy ray is an electron beam, the active energy ray-curable material does not need to contain a photopolymerization initiator, but when the active energy ray is ultraviolet light or visible light, the material preferably contains a photopolymerization initiator. On the other hand, when the above-mentioned curable component is used as the thermosetting component, the forming material preferably contains a thermal polymerization initiator.
Photopolymerization initiator
The photopolymerization initiator in the case of using a radical polymerizable compound can be appropriately selected depending on the activation energy ray. In the case of curing by ultraviolet rays or visible light, a photopolymerization initiator that is cleaved by ultraviolet rays or visible light is used. Examples of the photopolymerization initiator include: benzophenone compounds such as benzil, benzophenone, benzoylbenzoic acid, and 3, 3' -dimethyl-4-methoxybenzophenone; aromatic ketone compounds such as 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, α -hydroxy- α, α' -dimethylacetophenone, 2-methyl-2-hydroxypropiophenone, and α -hydroxycyclohexyl phenyl ketone; acetophenone compounds such as methoxyacetophenone, 2-dimethoxy-2-phenylacetophenone, 2-diethoxyacetophenone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, etc.; benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, and anisoin methyl ether; aromatic ketal compounds such as benzil dimethyl ketal; aromatic sulfonyl chloride compounds such as 2-naphthalenesulfonyl chloride; optically active oximes such as 1-phenyl-1, 1-propanedione-2- (o-ethoxycarbonyl) oxime; thioxanthone compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2, 4-dimethylthioxanthone, isopropylthioxanthone, 2, 4-dichlorothioxanthone, 2, 4-diethylthioxanthone, 2, 4-diisopropylthioxanthone and dodecylthioxanthone; camphorquinone; a halogenated ketone; acyl phosphine oxides; acyl phosphonates and the like.
The amount of the photopolymerization initiator is 20 parts by weight or less based on 100 parts by weight of the total amount of the curable components (radical polymerizable compounds). The amount of the photopolymerization initiator is preferably 0.01 to 20 parts by weight, more preferably 0.05 to 10 parts by weight, and still more preferably 0.1 to 5 parts by weight.
In addition, in the case of using a visible light curable type containing a radical polymerizable compound as a curable component, it is particularly preferable to use a photopolymerization initiator having high sensitivity to light of 380nm or more. A photopolymerization initiator highly sensitive to light of 380nm or more will be described later.
As the photopolymerization initiator, a compound represented by the following general formula (1) is preferably used alone; or a combination of a compound represented by the general formula (1) and a photopolymerization initiator having high sensitivity to light of 380nm or more as described later.
[ chemical formula 1]
Figure BDA0001798411230000191
(in the formula, R1And R2represents-H, -CH2CH3-iPr or Cl, R1And R2May be the same or different). When the compound represented by the general formula (1) is used, the compound is not particularly limitedThe adhesion is superior to that when a photopolymerization initiator having high sensitivity to light of 380nm or more is used. Among the compounds represented by the general formula (1), R is particularly preferable1And R2is-CH2CH3Diethyl thioxanthone (ll). The composition ratio of the compound represented by the general formula (1) in the forming material is preferably 0.1 to 5 parts by weight, more preferably 0.5 to 4 parts by weight, and still more preferably 0.9 to 3 parts by weight, based on 100 parts by weight of the total amount of the curable components.
Further, it is preferable to add a polymerization initiation aid as needed. Examples of the polymerization initiation aid include: triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, etc., with ethyl 4-dimethylaminobenzoate being particularly preferred. When the polymerization initiator is used, the amount thereof to be added is usually 0 to 5 parts by weight, preferably 0 to 4 parts by weight, and most preferably 0 to 3 parts by weight, based on 100 parts by weight of the total amount of the curable composition.
Further, a known photopolymerization initiator may be used in combination as necessary. Since the protective film having UV absorption ability does not transmit light of 380nm or less, it is preferable to use a photopolymerization initiator having high sensitivity to light of 380nm or more as the photopolymerization initiator. Specifically, there may be mentioned: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholino) phenyl ] -1-butanone, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide, bis (. eta.5-2, 4-cyclopentadien-1-yl) bis (2, 6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium and the like.
In particular, as the photopolymerization initiator, in addition to the photopolymerization initiator of the general formula (1), a compound represented by the following general formula (2) is preferably further used,
[ chemical formula 2]
Figure BDA0001798411230000201
(in the formula, R3、R4And R5represents-H, -CH3、-CH2CH3-iPr or Cl, R3、R4And R5May be the same or different). As the compound represented by the general formula (2), commercially available 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (trade name: IRGACURE907, manufacturer: BASF) can be suitably used. Further, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone (trade name: IRGACURE369, manufacturer: BASF), 2- (dimethylamino) -2- [ (4-methylphenyl) methyl group]-1- [4- (4-morpholinyl) phenyl]1-butanone (trade name: IRGACURE379, manufacturer: BASF) is preferred because of its high sensitivity.
Thermal polymerization initiator
The thermal polymerization initiator is preferably a thermal polymerization initiator which does not initiate polymerization by thermal cracking. For example, the thermal polymerization initiator is preferably a thermal polymerization initiator having a 10-hour half-life temperature of 65 ℃ or more, and more preferably 75 to 90 ℃. The half-life is an index indicating the decomposition rate of the polymerization initiator, and means a time until the residual amount of the polymerization initiator becomes half. The decomposition temperature at which the half-life is obtained at an arbitrary time and the half-life time at an arbitrary temperature are described in manufacturers' catalog and the like, for example, in "organic peroxide catalog 9 th edition (5/2003)" of japan oil and fat corporation.
Examples of the thermal polymerization initiator include: lauroyl peroxide (10-hour half-life temperature: 64 ℃ C.), benzoyl peroxide (10-hour half-life temperature: 73 ℃ C.), 1-bis (t-butylperoxy) -3,3, 5-trimethylcyclohexane (10-hour half-life temperature: 90 ℃ C.), bis (2-ethylhexyl) peroxydicarbonate (10-hour half-life temperature: 49 ℃ C.), bis (4-t-butylcyclohexyl) peroxydicarbonate, di-sec-butyl peroxydicarbonate (10-hour half-life temperature: 51 ℃ C.), t-butyl peroxyneodecanoate (10-hour half-life temperature: 48 ℃ C.), t-hexyl peroxypivalate, t-butyl peroxypivalate, dilauroyl peroxide (10-hour half-life temperature: 64 ℃ C.), di-n-octanoyl peroxide, 1,3, 3-tetramethylbutyl peroxy2-ethylhexanoate (10-hour half-life temperature: 66 ℃ C.), and the like, Organic peroxides such as bis (4-methylbenzoyl) peroxide, ditoluoyl peroxide (10-hour half-life temperature: 73 ℃), tert-butyl peroxyisobutyrate (10-hour half-life temperature: 81 ℃), and 1, 1-bis (tert-hexyl peroxyde) cyclohexane.
Examples of the thermal polymerization initiator include: 2,2 '-azobisisobutyronitrile (10-hour half-life temperature: 67 ℃), 2' -azobis (2-methylbutyronitrile) (10-hour half-life temperature: 67 ℃), 1-azobis (cyclohexane-1-carbonitrile) (10-hour half-life temperature: 87 ℃) and other azo compounds.
The amount of the thermal polymerization initiator is 0.01 to 20 parts by weight based on 100 parts by weight of the total amount of the curable components (radical polymerizable compounds). The amount of the thermal polymerization initiator is more preferably 0.05 to 10 parts by weight, and still more preferably 0.1 to 3 parts by weight.
Cationic polymerization curing type Forming Material
Examples of the curable component of the cationically polymerizable curable material include compounds having an epoxy group and an oxetanyl group. The compound having an epoxy group is not particularly limited as long as it has at least 2 epoxy groups in the molecule, and various curable epoxy compounds generally known can be used. Examples of the preferable epoxy compound include a compound having at least 2 epoxy groups and at least 1 aromatic ring in a molecule (aromatic epoxy compound); a compound having at least 2 epoxy groups in a molecule, at least 1 of which is formed between adjacent 2 carbon atoms constituting an alicyclic ring (alicyclic epoxy compound), and the like.
Photo cation polymerization initiator
The cationically polymerizable curable material contains the above-described epoxy compound and oxetane compound as curable components, and both are curable by cationic polymerization, and therefore a photo cationic polymerization initiator is blended. The photo cation polymerization initiator generates a cation species or lewis acid by irradiation of active energy rays such as visible light, ultraviolet rays, X-rays, electron beams, etc., thereby initiating a polymerization reaction of an epoxy group or an oxetanyl group.
The application method of the curable forming material (application liquid) can be appropriately selected depending on the viscosity of the curable forming material and the target thickness. Examples of the coating method include: reverse coaters, gravure coaters (direct, reverse, or offset), bar reverse coaters, roll coaters, die coaters, wire wound bar coaters, and the like. Further, the coating may be performed by a dipping method or the like.
< Process (2) >
In the step (2), after the coating step (1), the step (2) of curing or hardening the coating liquid is performed to form a transparent resin layer.
In forming the transparent resin layer, after a coating liquid containing the resin component is applied, the resin component is cured according to the type. The coating liquid containing the resin component is a solution or dispersion in which the resin component is dissolved in a solvent, and may be used in the form of, for example, an aqueous solution, an aqueous dispersion, or a solvent-based solution. The curing is to form a resin layer by removing the solvent from the coating liquid. For example, in the case where the resin component is a polyvinyl alcohol resin, the coating liquid may be used in the form of an aqueous solution, and may be cured by heating or the like. In the case where the resin component is a water-soluble acrylic resin, curing can be performed in the same manner.
The drying temperature is preferably 60 to 200 ℃ in general, and more preferably 70 to 120 ℃. The drying time is preferably 10 to 1800 seconds, and more preferably 20 to 600 seconds.
On the other hand, in the formation of the transparent resin layer, after a coating liquid containing a curable component capable of constituting a resin is applied, the curable component is cured into a resin depending on the type of the curable component. For the coating liquid containing a curable component capable of constituting the resin, a solventless type can be used if the curable component takes the form of a coating liquid. The coating liquid may be a solution obtained by dissolving the curable component in a solvent. When the curable component is in the form of a coating liquid, it may be used in the form of a solution. The solvent may be appropriately selected depending on the curable component to be used. For example, when an acrylic monomer forming an acrylic resin is used as the curable component, and when an epoxy monomer forming an epoxy resin is used, the coating liquid containing the curable component may be cured by irradiation with active energy rays (ultraviolet irradiation) or the like.
The formation of the transparent resin layer using the above-described curable forming material (coating liquid) is performed as follows: a curing-type forming material is applied to one surface of the polarizer and then cured.
The polarizer may be subjected to a surface modification treatment before the application of the curing-type forming material. Specific examples of the treatment include corona treatment, plasma treatment, and saponification treatment.
< curing of the Forming Material >
The curing-type forming material is used as an active energy ray curing-type forming material or a thermosetting-type forming material. The active energy ray-curable forming material may be used in an electron beam-curable type, an ultraviolet-curable type or a visible light-curable type. The above-mentioned embodiment of the curing-type forming material is preferably an active energy ray curing-type forming material as compared with a thermosetting-type forming material from the viewpoint of productivity, and is preferably a visible light curing-type forming material as the active energy ray curing-type forming material from the viewpoint of productivity.
Active energy ray curing type
The active energy ray-curable forming material is formed by applying the active energy ray-curable forming material on a polarizer, and then irradiating the polarizer with active energy rays (e.g., electron beams, ultraviolet rays, and visible light) to cure the active energy ray-curable forming material to form a transparent resin layer. The irradiation direction of the active energy rays (electron beam, ultraviolet ray, visible light, etc.) may be any appropriate direction. The irradiation is preferably from the transparent resin layer 4 side.
Electron Beam curing type
In the electron beam curing type, any appropriate conditions may be employed as long as the irradiation conditions of the electron beam are such that the active energy ray-curable forming material can be cured. For example, the acceleration voltage for electron beam irradiation is preferably 5kV to 300kV, and more preferably 10kV to 250 kV. If the acceleration voltage is less than 5kV, the electron beam may not reach the deepest part of the transparent resin layer and the curing may be insufficient, and if the acceleration voltage is more than 300kV, the penetration force through the sample may be too strong and the protective film or polarizer may be damaged. The dose of the radiation is 5 to 100kGy, and more preferably 10 to 75 kGy. When the irradiation dose is less than 5kGy, the adhesive is insufficiently cured, and when it exceeds 100kGy, the protective film and the polarizer are damaged, the mechanical strength is reduced, yellowing occurs, and predetermined optical characteristics cannot be obtained.
The electron beam irradiation is usually carried out in an inert gas, and may be carried out in an atmosphere with a small amount of oxygen introduced as required.
Ultraviolet curing type and visible light curing type
In the method for producing a polarizing film of the present invention, the active energy ray is preferably an active energy ray containing visible light having a wavelength range of 380nm to 450nm, and particularly preferably an active energy ray containing the largest dose of visible light having a wavelength range of 380nm to 450 nm. As the active energy ray of the present invention, a metal halide lamp in which gallium is sealed, and an LED light source which emits light in a wavelength range of 380 to 440nm are preferable. Alternatively, a light source containing ultraviolet rays and visible light such as a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, an incandescent lamp, a xenon lamp, a halogen lamp, a carbon arc lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, a gallium lamp, an excimer laser, or sunlight may be used, or ultraviolet rays having a wavelength shorter than 380nm may be blocked by a band-pass filter.
Type of Heat curing
On the other hand, the thermosetting type forming material is heated to initiate polymerization by a thermal polymerization initiator, thereby forming a cured product layer. The heating temperature may be set according to the thermal polymerization initiator, and is about 60 to 200 ℃, preferably 80 to 150 ℃.
< Process (3) >
Next, the step (3) of forming the pressure-sensitive adhesive layer on the transparent resin layer may be performed without winding the one-side protective polarizing film with a transparent resin layer obtained in the step (2) in a roll form, to produce a polarizing film with a pressure-sensitive adhesive layer. A separator may be disposed on the adhesive layer of the polarizing film with the adhesive layer.
< adhesive layer >
The pressure-sensitive adhesive layer may be formed using a suitable pressure-sensitive adhesive, and the type thereof is not particularly limited. Examples of the binder include: rubber-based adhesives, acrylic-based adhesives, silicone-based adhesives, urethane-based adhesives, vinyl alkyl ether-based adhesives, polyvinyl alcohol-based adhesives, polyvinyl pyrrolidone-based adhesives, polyacrylamide-based adhesives, cellulose-based adhesives, and the like.
Among these pressure-sensitive adhesives, those excellent in optical transparency, exhibiting suitable adhesive properties such as wettability, cohesiveness and adhesiveness, and excellent in weather resistance, heat resistance and the like can be preferably used. As the adhesive exhibiting such characteristics, an acrylic adhesive can be preferably used.
As a method for forming the pressure-sensitive adhesive layer, the following method can be used: for example, a method in which the adhesive is applied to a separator or the like subjected to a peeling treatment, and the adhesive layer is formed by drying and removing a polymerization solvent or the like, and then transferred to a polarizer; or a method of applying the above adhesive to a polarizer, and drying to remove the polymerization solvent and the like to form an adhesive layer on the polarizer; and so on. In the case of applying the adhesive, one or more solvents other than the polymerization solvent may be added newly as appropriate.
As the separator subjected to the peeling treatment, a silicone release liner can be preferably used. In the step of forming the pressure-sensitive adhesive layer by applying the pressure-sensitive adhesive of the present invention to such a liner and drying the applied pressure-sensitive adhesive, a suitable method can be appropriately employed as a method for drying the pressure-sensitive adhesive according to the purpose. The method of drying the coating film by heating is preferably used. The heating and drying temperature is preferably 40 to 200 ℃, more preferably 50 to 180 ℃, and particularly preferably 70 to 170 ℃. By setting the heating temperature in the above range, an adhesive having excellent adhesive characteristics can be obtained.
The drying time may be suitably employed as appropriate. The drying time is preferably 5 seconds to 20 minutes, more preferably 5 seconds to 10 minutes, and particularly preferably 10 seconds to 5 minutes.
As a method for forming the adhesive layer, various methods can be employed. Specific examples thereof include: roll coating, roll and lick coating, gravure coating, reverse coating, roll brushing, spray coating, dip roll coating, bar coating, blade coating, air knife coating, curtain coating, lip coating, extrusion coating using a die coater, and the like.
The thickness of the adhesive layer is not particularly limited, and is, for example, about 1 to 100 μm. Preferably 2 to 50 μm, more preferably 2 to 40 μm, and further preferably 5 to 35 μm.
When the pressure-sensitive adhesive layer is exposed, the pressure-sensitive adhesive layer can be protected with a sheet (separator) subjected to a peeling treatment until it is actually used.
Examples of the constituent material of the separator include: plastic films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films, porous materials such as paper, cloth, and nonwoven fabrics, and suitable sheets such as nets, foamed sheets, metal foils, and laminates thereof, and the like.
The plastic film is not particularly limited as long as it can protect the pressure-sensitive adhesive layer, and examples thereof include: polyethylene films, polypropylene films, polybutylene films, polybutadiene films, polymethylpentene films, polyvinyl chloride films, vinyl chloride copolymer films, polyethylene terephthalate films, polybutylene terephthalate films, polyurethane films, ethylene-vinyl acetate copolymer films, and the like.
The thickness of the separator is usually 5 to 200 μm, preferably about 5 to 100 μm. The separator may be subjected to mold release and antifouling treatment, or antistatic treatment such as coating type, mixing type, vapor deposition type, or the like, using a mold release agent of silicone type, fluorine-containing type, long chain alkyl type, or fatty acid amide type, silica powder, or the like, as necessary. In particular, the surface of the separator may be appropriately subjected to a release treatment such as a silicone treatment, a long-chain alkyl treatment, or a fluorine treatment, thereby further improving the releasability from the pressure-sensitive adhesive layer.
< surface protective film >
A surface protective film may be provided on the polarizing film of the present invention (including a single-side protective polarizing film, a polarizing film with an adhesive layer). The surface protective film generally has a base film and an adhesive layer, and protects the polarizer by the adhesive layer.
The base film of the surface protective film may be selected from materials having isotropy or near isotropy from the viewpoints of inspection property, manageability, and the like. Examples of the film material include: transparent polymers such as polyester resins such as polyethylene terephthalate films, cellulose resins, acetate resins, polyethersulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, and acrylic resins. Of these, polyester-based resins are preferred. The substrate film may be a laminate of 1 or 2 or more kinds of film materials, or a stretched product of the above film. The thickness of the base film is usually 500 μm or less, preferably 10 to 200 μm.
As the pressure-sensitive adhesive for forming the pressure-sensitive adhesive layer of the surface protective film, a pressure-sensitive adhesive based on a polymer such as a (meth) acrylic polymer, a silicone polymer, a polyester, a polyurethane, a polyamide, a polyether, a fluorine-containing polymer, or a rubber can be suitably selected and used. From the viewpoint of transparency, weather resistance, heat resistance and the like, an acrylic adhesive containing an acrylic polymer as a base polymer is preferred. The thickness of the adhesive layer (dry film thickness) may be determined according to the desired adhesive force. Usually about 1 to 100 μm, preferably 5 to 50 μm.
In the surface protective film, a release treated layer may be provided on the surface of the base film opposite to the surface on which the pressure-sensitive adhesive layer is provided, using a low-adhesion material subjected to a silicone treatment, a long-chain alkyl treatment, a fluorine treatment, or the like.
< other optical layers >
The pressure-sensitive adhesive layer-equipped single-sided protective polarizing film of the present invention can be used in practice as an optical film laminated with other optical layers. The optical layer is not particularly limited, and optical layers that are used for forming liquid crystal display devices and the like may be used, for example, 1 or 2 or more layers of reflective plates, semi-transmissive plates, retardation plates (including 1/2 wave plates, 1/4 wave plates, and the like), viewing angle compensation films, and the like. In particular, a reflective polarizing film or a semi-transmissive polarizing film obtained by further laminating a reflective plate or a semi-transmissive reflective plate on the pressure-sensitive adhesive layer-attached one-side protective polarizing film of the present invention, an elliptical polarizing film or a circular polarizing film obtained by further laminating a phase difference plate on a polarizing film, a wide-angle polarizing film obtained by further laminating a viewing angle compensation film on a polarizing film, or a polarizing film obtained by further laminating a brightness enhancement film on a polarizing film is preferable.
The optical film in which the optical layer is laminated on the pressure-sensitive adhesive layer-attached single-side protective polarizing film of the present invention may be formed by sequentially laminating the optical layers in the production process of a liquid crystal display device or the like, but when the optical film is laminated in advance to form the optical film, there are advantages in that the stability of quality, the assembly work, and the like are excellent, and the production process of the liquid crystal display device or the like can be improved. The lamination may be performed by an appropriate bonding method such as an adhesive layer. When the above-mentioned one-side protective polarizing film with an adhesive layer and other optical films are bonded, their optical axes may be set at an appropriate arrangement angle depending on the desired retardation characteristics and the like.
The pressure-sensitive adhesive layer-equipped single-sided protective polarizing film or optical film of the present invention can be preferably used for formation of various devices such as liquid crystal display devices. The liquid crystal display device can be formed in a conventional manner. That is, the liquid crystal display device can be generally formed by appropriately assembling a liquid crystal cell and a polarizer, a one-side protective polarizing film or an optical film, and components such as an illumination system used as needed, and introducing them into a driver circuit or the like. As the liquid crystal cell, any type of liquid crystal cell such as IPS type, VA type, etc. can be used, but IPS type is particularly preferable.
The pressure-sensitive adhesive layer-attached one-side protective polarizing film or optical film of the present invention can be formed on one side or both sides of a liquid crystal cell, and a liquid crystal display device using a backlight or a reflector in a lighting system can be formed. In this case, the one-side protective polarizing film or optical film with an adhesive layer of the present invention may be disposed on one side or both sides of the liquid crystal cell. In the case of a single-sided protective polarizing film or optical film with an adhesive layer of the present invention provided on both sides, they may be the same material or different materials. Further, in forming a liquid crystal display device, appropriate members such as a diffusion plate, an antiglare layer, an antireflection film, a protective plate, a prism array, a lens array sheet, a light diffusion plate, and a backlight may be disposed in appropriate positions in 1 layer or 2 layers or more.
Examples
The present invention will be described with reference to examples, but the present invention is not limited to the examples shown below. In each example, parts and% are on a weight basis. The following conditions of standing at room temperature, which are not particularly specified, are all 23 ℃ and 65% RH.
< one-sided protective polarizing film >
(production of polarizing mirror)
One surface of a substrate of an amorphous isophthalic acid-copolymerized polyethylene terephthalate (IPA-copolymerized PET) film (thickness: 100 μm) having a water absorption rate of 0.75% and a Tg of 75 ℃ was subjected to corona treatment, and an aqueous solution containing polyvinyl alcohol (polymerization degree 4200, saponification degree 99.2 mol%) and acetoacetyl-modified PVA (polymerization degree 1200, acetoacetyl-modification degree 4.6%, saponification degree 99.0 mol% or more, manufactured by japan synthetic chemical industries, ltd., trade name "GOHSEFIMER Z200") in a ratio of 9:1 was applied to the corona-treated surface at 25 ℃ and dried to form a PVA-based resin layer having a thickness of 11 μm, thereby producing a laminate.
The obtained laminate was subjected to free-end uniaxial stretching (auxiliary stretching treatment in a gas atmosphere) of 2.0 times in the longitudinal direction (longitudinal direction) between rolls having different peripheral speeds in an oven at 120 ℃.
Next, the laminate was immersed in an insolubilization bath (an aqueous boric acid solution prepared by mixing 4 parts by weight of boric acid with 100 parts by weight of water) at a liquid temperature of 30 ℃ for 30 seconds (insolubilization treatment).
Next, the polarizing plate was immersed in a dyeing solution at a liquid temperature of 30 ℃ while adjusting the iodine concentration and the immersion time so as to achieve a predetermined transmittance. In this example, an aqueous iodine solution prepared by adding 0.2 parts by weight of iodine and 1.0 part by weight of potassium iodide to 100 parts by weight of water was immersed for 60 seconds (dyeing treatment).
Subsequently, the substrate was immersed in a crosslinking bath (aqueous boric acid solution prepared 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 ℃ for 30 seconds (crosslinking treatment).
Then, the laminate was immersed in an aqueous boric acid solution (aqueous solution prepared by mixing 4 parts by weight of boric acid and 5 parts by weight of potassium iodide with respect to 100 parts by weight of water) at a liquid temperature of 70 ℃, and uniaxially stretched in the longitudinal direction (longitudinal direction) between rolls having different peripheral speeds so that the total stretching ratio became 5.5 times (stretching treatment in the aqueous solution).
Then, the laminate was immersed in a cleaning bath (aqueous solution containing 4 parts by weight of potassium iodide per 100 parts by weight of water) at a liquid temperature of 30 ℃ (cleaning treatment).
By the above operation, an optical film laminate including a polarizer having a thickness of 5 μm was obtained.
(preparation of protective film)
Protecting the film: the easy-adhesion-treated surface of a (meth) acrylic resin film having a lactone ring structure and having a thickness of 40 μm was subjected to corona treatment and used.
(preparation of adhesive suitable for protective film)
An ultraviolet-curable adhesive was prepared by mixing 40 parts by weight of N-hydroxyethyl acrylamide (HEAA), 60 parts by weight of acryloyl morpholine (ACMO), and 3 parts by weight of a photoinitiator IRGACURE 819 (BASF corporation).
(preparation of Single-sided protective polarizing film)
The ultraviolet-curable adhesive is applied to the surface of the polarizer of the optical film laminate so that the thickness of the cured adhesive layer becomes 0.5 μm, the protective film is bonded thereto, and then ultraviolet rays as active energy rays are irradiated to cure the adhesive. The ultraviolet irradiation uses a gallium-sealed metal halide lamp and an irradiation device: light HAMMER10 manufactured by Fusion UV Systems, valve: v valve, maximum illuminance: 1600mW/cm2Cumulative dose of radiation 1000/mJ/cm2(wavelength 380 to 440nm) and the illuminance of ultraviolet light were measured by using Sola-Check system manufactured by Solatell corporation. Subsequently, the amorphous PET substrate was peeled off to prepare a single-sided protective polarizing film (total thickness: 45.5 μm) using a thin polarizer. The optical properties of the obtained one-side protective polarizing film were single transmittance 42.8% and degree of polarization 99.99%.
< monomer transmittance T and degree of polarization P >
The single-side protective polarizing film obtained was measured for the single-side transmittance T and the degree of polarization P using a spectral transmittance measuring instrument with an integrating sphere (Dot-3 c from mura color technical research institute).
The degree of polarization P is determined by applying the transmittance (parallel transmittance: Tp) when 2 sheets of the same polarizing films are stacked such that their transmission axes are parallel to each other and the transmittance (orthogonal transmittance: Tc) when the polarizing films are stacked such that their transmission axes are orthogonal to each other to the following equation.
Polarization degree P (%) { (Tp-Tc)/(Tp + Tc) }1/2×100
Each transmittance is a transmittance represented by a Y value obtained by measuring a 2-degree field of view (C light source) according to JIS Z8701 and correcting visibility when the fully polarized light obtained by polarizing the polarizer by a glan taylor prism is assumed to be 100%.
(Material for Forming transparent resin layer: coating liquid)
A polyvinyl alcohol resin having a polymerization degree of 2500 and a saponification degree of 99.7 mol% was dissolved in pure water to prepare an aqueous solution (coating liquid) having a solid content of 4 wt% and a viscosity of 60 mPaS.
(preparation of acrylic Polymer)
A4-necked flask equipped with a stirring blade, a thermometer, a nitrogen inlet tube and a cooler was charged with a monomer mixture containing 99 parts of butyl acrylate and 1 part of 4-hydroxybutyl acrylate. Further, 0.1 part of 2, 2' -azobisisobutyronitrile as a polymerization initiator was added together with ethyl acetate to 100 parts of the monomer mixture (solid content), nitrogen gas was introduced while slowly stirring the mixture to replace nitrogen, and then the polymerization reaction was carried out for 7 hours while maintaining the liquid temperature in the flask at about 60 ℃. Then, ethyl acetate was added to the obtained reaction solution to obtain a solution of an acrylic polymer having a solid content concentration of 30% and a weight average molecular weight of 140 ten thousand.
(preparation of adhesive composition)
An acrylic pressure-sensitive adhesive solution was prepared by mixing 0.1 part of trimethylolpropane xylylene diisocyanate (manufactured by Mitsui chemical Co., Ltd.: TakenateD110N), 0.3 part of dibenzoyl peroxide, and 0.075 part of gamma-glycidoxypropyltrimethoxysilane (manufactured by shin-Etsu chemical Co., Ltd.; trade name: KMB-403) with 100 parts of the solid content of the acrylic polymer solution.
(formation of adhesive layer)
Subsequently, the acrylic pressure-sensitive adhesive solution was uniformly applied to the surface of a polyethylene terephthalate film (separator) treated with a silicone-based release agent by a spray coater, and dried in an air-circulating oven at 155 ℃ for 2 minutes to form a pressure-sensitive adhesive layer having a thickness of 20 μm on the surface of the separator.
Example 1
< production of Single-sided protective polarizing film with transparent resin layer >
The material (coating liquid) for forming the transparent resin layer was applied to the surface of the polarizer (polarizer surface without a protective film) of the one-side protective polarizing film transported at 20 m/min using a coating apparatus (specifically, gravure coater) so that the thickness after drying became 1 μm, and then hot-air dried at 85 ℃ for 30 seconds to prepare a one-side protective polarizing film with a transparent resin layer.
< production of polarizing film with adhesive layer >
Next, the pressure-sensitive adhesive layer formed on the release-treated surface of the release sheet (separator) was continuously (specifically, after 18 seconds) laminated on the transparent resin layer without winding the obtained one-side protective polarizing film with a transparent resin layer in a roll form, thereby producing a pressure-sensitive adhesive layer-attached polarizing film. Then, the polarizing film with the adhesive layer was wound to prepare a roll.
In the examples, the film thickness of the transparent resin layer was measured using a device (device for measuring film thickness: optical spectrometer: USB2000+, light source: HL-2000, optical fiber: ZFQ-12796(200 μm reflective fiber), polarizing element: the above-obtained one-side protective polarizing film) in a manufacturing line after the one-side protective polarizing film with a transparent resin layer was manufactured and before the adhesive layer was bonded. The measurement conditions were measurement wavelength: 450 nm-800 nm, refractive index of the transparent resin layer: 1.51. the thickness of the transparent resin layer obtained in the examples was stable and was 1.0. + -. 0.1. mu.m.
Comparative example 1
The one-side protective polarizing film with a transparent resin layer prepared in the same manner as in example was wound to form a roll. Then, continuous drawing from a roll of the one-side protective polarizing film with a transparent resin layer was attempted, but continuous drawing was impossible because the roll was stuck.
Comparative example 2
The one-side protective polarizing film with a transparent resin layer prepared in the same manner as in example was wound with a separator to prepare a roll. Then, although continuous drawing from the roll of the one-side protective polarizing film with a transparent resin layer was attempted, the transparent resin layer had poor adhesion to the separator and was kneaded during conveyance, and therefore, breakage occurred immediately after conveyance.
In the embodiment, the risk of generation of the nano-slit is low, and on the other hand, in the comparative example, the risk of generation of the nano-slit is high.

Claims (9)

1. A method for producing a one-side protective polarizing film with an adhesive layer, the one-side protective polarizing film having a transparent resin layer and an adhesive layer in this order from the polarizer side of the one-side protective polarizing film having a protective film only on one surface of the polarizer,
the thickness of the transparent resin layer is less than 3 μm,
the polarizer contains a polyvinyl alcohol resin, has a thickness of 10 [ mu ] m or less, and is configured so that optical properties represented by a monomer transmittance T and a polarization degree P satisfy the following conditions:
P＞－(100.929T-42.4-1) x 100, wherein T < 42.3, or
P is more than or equal to 99.9, wherein T is more than or equal to 42.3,
the formation of the transparent resin layer and the adhesive layer is performed by the following method:
forming a transparent resin layer by performing a step (1) of applying a coating liquid containing a resin component or a coating liquid containing a curable component capable of constituting a resin layer to the polarizer side of the single-sided protective polarizing film while conveying the single-sided protective polarizing film, and a step (2) of curing or hardening the coating liquid and then,
and (3) forming an adhesive layer on the transparent resin layer without winding the obtained single-sided protective polarizing film with the transparent resin layer in a roll shape.
2. The method for producing a pressure-sensitive adhesive layer-equipped one-side protective polarizing film according to claim 1, wherein a step (4) of measuring the film thickness of the transparent resin layer in a transport line is provided after the step (2) and before the step (3).
3. The method for producing an adhesive layer-attached single-sided protective polarizing film according to claim 2, wherein the step (4) is performed by an optical interference method using a polarizing element at the front end of a light source.
4. The method for producing a one-side protective polarizing film with an adhesive layer according to claim 1, wherein the coating liquid in the step (1) contains a resin component dissolved or dispersed in water, and in the step (2), the transparent resin layer is formed by curing.
5. The method for producing a one-side protective polarizing film with an adhesive layer according to claim 4, wherein the coating liquid containing a resin component is an aqueous solution containing a polyvinyl alcohol resin.
6. The method for producing a one-side protective polarizing film having an adhesive layer according to claim 1, wherein the coating liquid in the step (1) has a viscosity of 1000mPa · s or less at 25 ℃.
7. The method for producing an adhesive layer-equipped one-side protective polarizing film according to claim 1, wherein the polarizer contains boric acid in an amount of 20 wt% or less with respect to the total amount of polarizers.
8. The method for manufacturing an adhesive layer-attached single-sided protective polarizing film according to any one of claims 1 to 7, wherein a separator is laminated on the adhesive layer,
9. the method for manufacturing an adhesive layer-attached one-side protective polarizing film according to claim 8, wherein the adhesive layer-attached one-side protective polarizing film is formed into a roll.
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