JP2015036780A - Intrinsic polarizer and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an intrinsic polarizer that is obtained by forming a linear polyvinylene structure in a film comprising a polyhydroxy linear polymer, in which a linear polymer having the linear polyvinylene structure is oriented in the entire film plane of the intrinsic polarizer and at least two regions with different transmittances for visible light are patterned in a single film of the intrinsic polarizer, and to provide a polarizing plate having the polarizer, and a method for manufacturing the patterned intrinsic polarizer.SOLUTION: An intrinsic polarizer is obtained by a method for manufacturing an intrinsic polarizer comprising a film having a polyhydroxy linear polymer having a linear polyvinylene structure. The method includes the following four steps: (1) a primary impregnation step of wholly impregnating the film comprising the polyhydroxy linear polymer with an inorganic acid as a dehydration catalyst; (2) a secondary impregnation step of, after the primary impregnation step, further impregnating the polymer film with the inorganic acid as the dehydration catalyst into a pattern so as to form a pattern of a portion having a high concentration of the inorganic acid; (3) a step of heating the polymer film after completing the secondary impregnation step so as to form the polyvinylene structure in the linear polymer molecules; and (4) a step of stretching the film to orient the film.

Description

  The present invention relates to an intrinsic polarizer, a manufacturing method thereof, a polarizing plate using the intrinsic polarizer, and a display device.

Conventionally, various methods for manufacturing a polarizer in which the polarization characteristics of a polarizing plate are different depending on an in-plane region have been proposed (Patent Documents 1 to 5). However, all of them are polarizers whose absorption axes differ from region to region, and the visible light transmittance can be controlled, and furthermore, a polarizer capable of controlling the visible light transmittance to a fine region with a large area. There was no method for manufacturing in a simple process.
As a different type of polarizer from iodine-based polarizer and dye-based polarizer, there is an intrinsic polarizer (K-type polarizer or KE-type polarizer) that does not require a dichroic dye. The intrinsic polarizer has a polyvinylene structure (also referred to as a polyene structure or a polyene fragment structure) formed by dehydrating a part of a polyhydroxy linear polymer such as polyvinyl alcohol. Intrinsic polarizers exhibit dichroism due to the light-absorbing properties of the stable polyvinylene structure formed in the polymer molecules that make up the film. It has the characteristic that it is excellent in.

  As intrinsic polarizers with patterned polarization characteristics, Patent Documents 4 and 5 describe a pattern in which an acid-donating layer containing a photoacid generator or a thermal acid generator is laminated on a vinyl alcohol polymer film layer, and then a part thereof is peeled off. Intrinsic polarizer in which a polyvinylidene structure is formed only in a part of the film surface by forming a solid acid donating layer or irradiating active energy rays in a pattern using a patterned mask Is disclosed.

JP 63-314503 A JP 2001-215489 A JP2009-193014 JP-A-2005-517974 JP-A-2005-521916

  Usually, the intrinsic polarizer is made to pass a film made of a polyhydroxy linear polymer through a solution containing a dehydration catalyst such as an inorganic acid, impregnating the dehydration catalyst into the film, and then causing a dehydration reaction by heating or the like. Since a polyvinylene structure is formed and a film is stretched and oriented at an appropriate location and then dried, it is conventionally partly provided with different regions having different optical properties and a plurality of light transmittances (polarized light). It was difficult to obtain an intrinsic polarizer having regions having different characteristics. Therefore, in Patent Document 4 or 5, a partially oriented polyvinylene structure is formed by causing a light or thermal acid generator layer to partially exist on the oriented vinyl alcohol polymer layer and applying light or heat. The intrinsic polarizer which has both the area | region which has polarization ability, and the area | region which does not have polarization ability is manufactured. However, an intrinsic polarizer having polarization ability over the entire surface and having a plurality of regions having different polarization performance (light transmittance) has not been developed. In the future, as optical instruments advance, it is expected that such polarizers will be required for intrinsic polarizers as well as dye-based polarizing plates. An object of the present invention is to provide such an intrinsic polarizer.

  As a result of intensive studies to solve the above-mentioned problems, the present inventor, after impregnating a polyhydroxy linear polymer film with a dehydration catalyst in a conventional method for producing an intrinsic polarizer, further, at a desired portion of the film. The film is impregnated with a dehydration catalyst by a means such as applying a solution containing a dehydration catalyst, and a plurality of regions having different dehydration catalyst concentrations are formed on the film. It is found that by forming and orienting a polyvinylene structure therein, an intrinsic polarizer having a plurality of polarizing performances (light transmittances) having different regions can be obtained while the entire film surface has polarizing performances. The present invention has been completed.

That is, this invention relates to the following 1-12 invention.
1. An intrinsic polarizer comprising a polymer film having a chain-like polyvinylene structure oriented in the same direction on the entire surface, and having at least two regions having different visible light transmittances in the film.
2. 2. The intrinsic polarizer according to 1 above, wherein the polyvinylene structure in the polymer molecule is formed by dehydration of a polyhydroxy linear polymer.
3. 3. The intrinsic polarizer according to 1 or 2 above, wherein two or more regions having different visible light transmittances are patterned in a stripe shape.
4). 4. The intrinsic polarizer according to any one of 1 to 3, wherein a difference in visible light average single transmittance between regions having different visible light transmittances is at least 1%.
5. (1) a primary impregnation step of impregnating an entire film made of a polyhydroxy linear polymer with an inorganic acid as a dehydration catalyst;
(2) After the primary impregnation step, further, a secondary impregnation step of impregnating the polymer film in a pattern with an inorganic acid as a dehydration catalyst to form a portion having a high inorganic acid concentration in the pattern,
(3) forming a polyvinylene structure in the linear polymer molecule by heating the polymer film after the secondary impregnation step; and
(4) A film stretching step for orienting the film,
The method for producing an intrinsic polarizer according to any one of 1 to 4 above, which comprises the following four steps.
6). 6. The method for producing an intrinsic polarizer according to 5 above, wherein the inorganic acid concentration of the portion having a high inorganic acid concentration formed in a pattern in the film is at least two different concentrations.
7). 7. The method for producing an intrinsic polarizer according to 6 above, wherein at least two portions having a high concentration of the inorganic acid having different concentrations are formed by application of at least two inorganic acid solutions having different concentrations.
8). In the secondary impregnation step, at least two portions having a high concentration of the inorganic acid having different concentrations are formed by making the film impregnated with the inorganic acid different in each region. 7. The method for producing an intrinsic polarizer as described in 6 above.
9. The primary impregnation step involves impregnating the polymer film with the inorganic acid by immersing the polymer film in an inorganic acid solution either before or simultaneously with the orientation of the polymer or after the orientation. The method for producing an intrinsic polarizer according to any one of claims 8 to 9.
10. The method for producing an intrinsic polarizer according to any one of 5 to 9 above, wherein the inorganic acid is hydrochloric acid.
11. A protective film or a support is bonded to at least one surface of the intrinsic polarizer according to any one of the above 1 to 4 or the intrinsic polarizer obtained by the production method according to any one of claims 5 to 10. Polarizing plate.
12 The intrinsic polarizer as described in any one of said 1-4, the intrinsic polarizer obtained by the manufacturing method as described in any one of said 5-10, or the display apparatus provided with the polarizing plate of said 11 .

  According to the present invention, a region having polarization performance on the entire surface, which has been conventionally difficult to manufacture, and a plurality of visible light transmittances (optical performance, particularly polarization performance) are different in one film. The intrinsic polarizer can be easily manufactured by adding one process to the manufacturing process of the conventional intrinsic polarizer, and can be easily applied to fine patterning, etc. The child is easy to manufacture.

The intrinsic polarizer of the present invention is composed of a polymer film having a chain polyvinylene structure oriented in the same direction on the entire surface, and at least two visible light transmittances (optical performance, in particular, polarized light) in the film. (Performance) has different areas. Hereinafter, in the present specification, the intrinsic polarizer having the characteristics is also simply referred to as “the intrinsic polarizer of the present invention”.
The intrinsic polarizer of the present invention is, for example, a conventional film made of a polyhydroxy linear polymer impregnated with an inorganic acid as a dehydration catalyst (primary impregnation step) and stretching the film (primary stretching step). To give a stretched film containing the inorganic acid and the oriented linear polymer, and then a polyvinylene structure is formed by dehydration from the linear polymer, and if necessary, a second stretch is performed ( Secondary stretching step), in the method for producing the intrinsic polarizer, before forming the polyvinylene structure by dehydration, the stretched film is further formed with an inorganic acid such that a portion having a high inorganic acid concentration is formed in a pattern. It can manufacture by performing the impregnation (second impregnation process). In some cases, the primary and secondary stretching steps may be performed only once, for example, once before or after the formation of the polyvinylene structure. Usually, it is preferable to perform both primary stretching and secondary stretching.
That is, in the method for producing the intrinsic polarizer of the present invention,
(1) a primary impregnation step of impregnating an entire film made of a polyhydroxy linear polymer with an inorganic acid as a dehydration catalyst;
(2) After the primary impregnation step, further, a secondary impregnation step of impregnating the polymer film in a pattern with an inorganic acid as a dehydration catalyst to form a portion having a high inorganic acid concentration in the pattern,
(3) forming a polyvinylene structure in the linear polymer molecule by heating the polymer film after the secondary impregnation step; and
(4) Film stretching process for stretching the film (stretching process)
There are four steps.

The polyvinylene structure contained in the linear polymer in the intrinsic polarizer of the present invention can be usually formed by a dehydration reaction from the polyhydroxy linear polymer. This polyvinylene structure includes a block of chain polyvinylene bonds in which vinylene bonds are continuous. In general, the longer the polyvinylene bond (the greater the number of consecutive vinylene bonds), the longer the block of the polyvinylene bond absorbs light of a longer wavelength, and the greater the number of blocks of the polyvinylene bond, the more light. Absorb. Therefore, by increasing the number of long polyvinylene bond blocks, it is possible to increase the absorption of light on the long wavelength side.
As the polyhydroxy linear polymer, any linear polymer can be used as long as it has a number of hydroxy groups in the molecule and can form a continuous chain of polyvinylidene bonds by dehydration. The polyhydroxy linear polymer may have a substituent other than a hydroxy group as long as the effect of the intrinsic polarizer of the present invention is not lost. Examples of the substituent include a C1-C4 acyloxy group, a C1-C4 alkyl group, a phenyl group, and a carboxy group.
The ratio of substituents other than hydroxy groups is preferably in the range of 0 to 30%, more preferably about 0 to 20%, based on the total number of substituents other than hydroxy groups and hydroxy groups in the polyhydroxy linear polymer. More preferably, it is the range of about 0 to 10%. Usually, a polyhydroxy linear polymer having no substituent other than a hydroxy group is used.
As the polyhydroxy linear polymer, those having a polymerization degree of usually in the range of about 1000 to 10,000 are used, and a preferable degree of polymerization is about 1500 to 7000, more preferably about 2000 to 6000.

  Examples of the polyhydroxy linear polymer include polyvinyl alcohol (hereinafter also referred to as PVA) or a derivative thereof, or a copolymer of polyvinyl acetate and another copolymerizable monomer (polyvinyl acetate copolymer). ) Can be preferably used. Polyvinyl alcohol (PVA) -based polymer (hereinafter also referred to as PVA-based resin) obtained by saponification treatment). As said other copolymerizable monomer, styrene, (meth) acrylic acid or its ester (For example, ester with C1-C4 alcohol) etc. can be mentioned. In the case of a polymer obtained by saponifying the above-mentioned vinyl acetate copolymer or a polymer obtained by acylating a part of hydroxyl groups of polyvinyl alcohol (PVA) with an organic acid (such as an aliphatic organic acid containing 1 to 4 carbon atoms) It is preferable that the polyvinyl alcohol component occupies 70 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more of the constituent components of the polymer.

When a PVA resin film is used as a raw material film for an intrinsic polarizer, a film made of PVA obtained by saponifying polyvinyl acetate, which is a polymer of vinyl acetate, can be copolymerized with vinyl acetate. A film made of a PVA copolymer obtained by saponifying a copolymer (polyvinyl acetate copolymer) with another monomer, or the above PVA or PVA copolymer is converted into an olefin or an unsaturated carboxylic acid. A film made of a PVA modified material modified with an acid (for example, (meth) acrylic acid or the like) is preferred as the PVA resin film.
Examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids such as (meth) acrylic acid; unsaturated carboxylic acid esters such as (meth) acrylate (for example, methyl (meth) acrylate) Olefins such as ethylene, propylene and butylene; vinyl ethers; unsaturated sulfonic acids; unsaturated amines; acrylic acid derivatives such as vinyl acetate: acrylamide; and styrene.
The degree of saponification of the PVA and PVA copolymer is usually about 85 to 100 mol%, preferably 98 to 100 mol%, more preferably 99 to 100 mol%.

As a raw material film used for the intrinsic polarizer of the present invention, a film made of a PVA resin is preferable.
The PVA-based resin film is preferably a resin film in which the main component of the repeating unit in the polymer is PVA and / or a modified product thereof, and the proportion of the PVA and / or the modified product (preferably PVA) is in moles. More preferred are films of polymer in a proportion of at least 50%, preferably 70-100%, more preferably 80-100%, most preferably 90-100%.
As the PVA-based resin used in the intrinsic polarizer of the present invention, those having a polymerization degree in the range of usually about 1000 to 10,000 are used, preferably about 1500 to 7000, more preferably about 2000 to 6000. It is a range.

As a raw material film for the intrinsic polarizer of the present invention, a film made of PVA or a PVA copolymer having the preferred polymerization degree and a preferred saponification degree is preferable, and a film made of PVA having the preferred polymerization degree and a preferred saponification degree. Is particularly preferred.
The thickness of the polyhydroxy linear polymer film used as the material for the intrinsic polarizer is not particularly limited, but is usually about 20 to 150 μm. The film thickness of the intrinsic polarizer of the present invention after the stretching treatment is preferably about 10 to 100 μm, more preferably about 20 to 70 μm, and still more preferably about 25 to 50 μm.

Hereinafter, the manufacturing method of the intrinsic polarizer of this invention is demonstrated.
The intrinsic polarizer of the present invention is, for example, a conventional film made of a polyhydroxy linear polymer impregnated with an inorganic acid as a dehydration catalyst (primary impregnation step) and stretching the film (primary stretching step). To form a stretched film containing the inorganic acid and the oriented linear polymer, and then usually heating the film to cause a dehydration reaction, thereby forming a polyvinylene structure in the linear polymer. In the method for producing an intrinsic polarizer, which is further subjected to the second stretching, if necessary, before the formation of the polyvinylene structure by dehydration, the above-mentioned stretched film is further patterned and the inorganic acid concentration is high. It can manufacture by performing the impregnation (secondary impregnation process) of an inorganic acid so that a part may be formed.
The characteristic of the method for producing an intrinsic polarizer of the present invention is that, in the conventional method for producing an intrinsic polarizer, before forming a polyvinylene structure on a film containing an inorganic acid obtained in the primary impregnation step, a pattern is further formed. In this process, an inorganic acid is impregnated so that a portion with a high concentration of the inorganic acid is formed. By this process, visible light transmittance is obtained in an intrinsic polarizer composed of a single film having polarization performance on the entire surface. A plurality of regions having different (that is, polarization performance) can be formed.
In the method for producing an intrinsic polarizer of the present invention, as described above, the following (1) primary impregnation step of impregnating the entire film made of polyhydroxy linear polymer with an inorganic acid as a dehydration catalyst,
(2) After the primary impregnation step, further, a secondary impregnation step of impregnating the polymer film in a pattern with an inorganic acid as a dehydration catalyst to form a portion having a high inorganic acid concentration in the pattern,
(3) forming a polyvinylene structure in the linear polymer molecule by heating the polymer film after the secondary impregnation step; and
(4) A film stretching step for orienting the film,
These four steps are included.
In addition, if necessary,
(5) A step of treating the film in which the linear polymer is oriented using a curing agent such as boric acid (hereinafter also referred to as “curing agent treatment step”),
In general, it is preferable to include.
The intrinsic polarizer of the present invention can be produced by drying the film obtained above (hereinafter also referred to as “drying step”).
Each step will be described in detail below.

(1) Primary impregnation step The primary impregnation step is a step of impregnating the resin film with an inorganic acid that is a dehydration catalyst. If the acid can be impregnated in the film, the method is particularly It is not limited. Usually, the primary impregnation step is performed by immersing the resin film in a solution containing an inorganic acid, preferably in an aqueous solution containing an inorganic acid. In some cases, the primary impregnation step can also be performed by applying or applying an inorganic acid solution to the film, or by exposing the film to the vapor of the inorganic acid solution.
As the inorganic acid used in the primary impregnation step, inorganic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid and sulfuric acid can be preferably used, and hydrochloric acid is more preferable. Examples of the solvent of the inorganic acid solution include water, a water-soluble organic solvent, and a mixture thereof, and water is preferable.
The inorganic acid concentration in the inorganic acid solution varies depending on the type of acid used. Generally, the acid concentration in the inorganic acid aqueous solution is about 0.001% by mass to 3% by mass. For example, in the case of hydrochloric acid, it is usually 0.01 N or more, preferably 0.045 N or more, and the upper limit is not particularly limited, but is preferably 5 N or less, more preferably 1 default or less. More preferably, it is 0.045 normal -0.5 normal.

Since the immersion time varies depending on the acid concentration and the type of the film, it cannot be determined in general. Generally, it is appropriately selected between about 2 seconds and about 30 minutes.
For example, it can be performed in about 2 to 5 minutes.
The primary impregnation step is usually performed as the first step. Films that have undergone the primary impregnation step usually have an acid solution attached to the film surface, so that they adhere to the film surface by a method such as wiping with a material that can absorb liquids such as paper, fabric, and sponge. It is preferable to remove the inorganic acid solution.
Further, as will be described later, a stretching step may be performed during the primary impregnation step. In that case, the primary impregnation step and the primary stretching step can be completed simultaneously by performing uniaxial stretching (primary stretching) in an inorganic acid solution.

(2) Secondary impregnation step In the secondary impregnation step, the resin film surface subjected to the primary impregnation step is impregnated in a pattern with an inorganic acid which is a dehydration catalyst. A portion having a high inorganic acid concentration (hereinafter, also referred to as “patterned high concentration region”) is formed. In the first impregnation step, the entire surface of the resin film is uniformly impregnated with the dehydration catalyst, whereas the second impregnation step is performed so that a shade pattern is generated depending on the region of the dehydration catalyst content in the resin film. In point, it is greatly different.
As a method of impregnating the resin film with the inorganic acid solution in the second impregnation step, the inorganic acid solution can be brought into contact with only a part of the surface of the resin film. For example, the specific method is not limited. For example, a method of applying or coating an inorganic acid solution in a pattern directly on the surface of the resin film, and a liquid-absorbing substrate such as a fabric and a sponge to absorb the inorganic acid solution and overlaying the substrate on the film The method of putting is mentioned.

As the acid and solvent in the inorganic acid solution used in the secondary impregnation step, any inorganic acid and solvent that can be used in the primary impregnation step can be used. A hydrochloric acid aqueous solution is preferable as the inorganic acid solution used in the second impregnation step. The acid and solvent used in the secondary impregnation step may be the same as or different from the acid and solvent used in the primary impregnation step performed before that.
Although the density | concentration of the inorganic acid solution used by a secondary impregnation process changes with kinds of acid to be used, generally the density | concentration of an inorganic acid solution is about 0.001 mass%-15 mass%. For example, in the case of hydrochloric acid, it is usually 0.01 N or more, preferably 0.05 N or more, and the upper limit is not particularly limited, but is preferably 5 N or less, more preferably 3 defaults or less. More preferably, it is 0.1 normal to 2 normal.
In the above range, by adjusting the acid concentration of the inorganic acid solution, the visible light transmittance can be adjusted in the portion having a high inorganic acid concentration (patterned high concentration region) formed in a pattern on the resin film. it can. The higher the acid concentration of the inorganic acid solution, the higher the concentration of the dehydration catalyst in the patterned high concentration region in the resin film, and the lower the visible light transmittance of the corresponding region in the resulting intrinsic polarizer. This is thought to be because the number of polyvinylene bond blocks formed increases.

The visible light transmittance (polarization characteristics) of each region in the intrinsic polarizer of the present invention is determined by applying the inorganic acid solution to the surface of the resin film and then remaining on the surface in the secondary impregnation step. The time until the liquid is removed from the surface (hereinafter, also referred to as “acid remaining time”), the number of times of application, or the like can be adjusted.
As an example of the secondary impregnation step, when an inorganic acid solution is applied to the surface of the resin film, the coating solution is immediately removed from the surface of the resin film after coating, and the coating solution comes into contact with the resin film. The resin film can be impregnated even by a method such as shortening the time during which the coating liquid is applied, or leaving it for a short time to increase the time during which the coating solution is in contact with the resin film, or by applying a plurality of times. Since the amount of the dehydration catalyst to be changed can be changed, the visible light transmittance of each region can be adjusted. The longer the acid residual time and the more the number of coatings, the greater the amount of dehydration catalyst impregnated in the resin film, and the visible light transmittance in that region can be lowered. This is presumably because when the amount of the dehydration catalyst impregnated in the resin film is increased, the concentration of the dehydration catalyst per polyhydroxy linear polymer is increased, and the number of blocks of polyvinylene bonds formed is increased.
The coating liquid may be removed from the surface of the resin film using, for example, a liquid absorbent material such as paper, fabric, or sponge.

The acid remaining time in the secondary impregnation step varies depending on the concentration of the inorganic acid solution, the coating method of the inorganic acid solution, the type of film, the desired optical properties (eg, visible light transmittance, polarization properties), etc. Although it cannot be determined, the time from application of the inorganic acid solution to removal of the coating solution is usually appropriately between about immediately after application (0 seconds) and until it is naturally dried (5 to 10 minutes). It is selected and is preferably about 1 minute immediately after application, more preferably about 20 seconds immediately after application.
The method for removing the coating liquid from the film surface is not particularly limited. For example, as described above, a method of absorbing the residual inorganic acid solution in a liquid absorbent material such as paper, fabric and sponge, removal by washing described later, removal by jetting high-pressure gas, and the like can be mentioned. Since the residual inorganic acid solution can be prevented from flowing out to other regions, a method of absorbing it in a liquid absorbent material is preferable.

In the secondary impregnation step, in order to form at least two patterned high-concentration regions having different inorganic acid concentrations in the resin film, an inorganic acid solution with a constant concentration is opened at an appropriate interval in the secondary impregnation step. Then, it is applied onto the resin film after the first impregnation treatment step or, if necessary, the concentration of the inorganic acid solution and / or the acid remaining time is varied, so that the concentration of the plurality of inorganic acids is different. An area may be provided.
For example, in the secondary impregnation step, at least two patterns having different inorganic acid concentrations in the resin film are obtained by impregnating each pattern region with an inorganic acid solution using inorganic acid solutions having different concentrations. A high concentration region can be formed. In addition, for the time from the impregnation of the resin film with the inorganic acid solution in the secondary impregnation step to the removal of the inorganic acid solution remaining on the surface, it is also possible to perform at different times in each pattern region, At least two pattern-like high concentration regions having different inorganic acid concentrations in the resin film can be formed.

The pattern of the portion having a high inorganic acid concentration (patterned high concentration region) formed by the secondary impregnation step is not particularly limited. For example, a regular pattern such as a striped pattern in which a plurality of band-like regions having a certain width are sequentially formed, a checkered pattern in which squares having a certain size are alternately formed, or each region is not It may be a pattern having a regular shape.
By passing through the secondary impregnation step, between the pattern-like high concentration region formed in the secondary impregnation step and the region not impregnated with the inorganic acid solution in the secondary impregnation step, and / or At least two regions having different dehydration catalyst concentrations are formed between the two or more pattern-like high concentration regions having different impregnation concentrations formed in the second impregnation step. As a result, in the intrinsic polarizer of the present invention, regions having different visible light transmittances are formed corresponding to these regions.

(3) Heat treatment step In this step, the film subjected to the primary impregnation step and the secondary impregnation step is heated for a certain period of time, thereby dehydrating the polyhydroxy linear polymer forming the film and generating a polyvinylene bond. It is a process to make.
This heat treatment step can be performed before the stretching step as long as it is after the primary impregnation step and the secondary impregnation step, but usually the primary impregnation step, the secondary impregnation step, and It is preferable to perform with respect to the film which performed the primary extending | stretching process process.
There is no problem as long as the temperature in the heat treatment step can generate a polyvinylene bond in the polyhydroxy linear polymer, and the temperature can be usually about 80 to 170 ° C.
In the long wavelength region of 600 to 640 nm, when it is desired to obtain an intrinsic polarizer having excellent absorption characteristics, it is preferable to minimize the time during which the film surface temperature is 125 ° C. or higher. Preferably, the time during which the film surface temperature is 125 ° C. or more and less than 130 ° C. is 0 to 3 seconds, more preferably 0 to 2 seconds, still more preferably about 0 to 1 second, and the film surface temperature is 130 ° C. It is preferable to adjust so as not to exceed. In the heat treatment step, it is preferable to adjust the heating temperature so that the formation of polyvinylene bonds in the polyhydroxy linear polymer is completed mainly when the film surface temperature is 100 ° C. or more and 125 ° C. or less. It is more preferable that the time when the temperature exceeds 120 ° C. is relatively short. By doing in this way, in the long wavelength region of 600 to 640 nm, it is possible to obtain an intrinsic polarizer having high absorbency of polarized light parallel to the absorption axis and high contrast, and favorable optical characteristics in the entire visible light region. This is because an intrinsic polarizer can be manufactured.

The time for the heat treatment process varies depending on the type and output of the heating means, the type of film, the thickness, and the like, and thus cannot be generally described. Usually, it can be appropriately selected between 1 second and 1 hour.
For example, in the long wavelength region of 600 to 640 nm, when it is desired to obtain an intrinsic polarizer with excellent absorption characteristics, the time during which the film surface temperature is 100 ° C. to less than 130 ° C. is about 30 minutes at most, Preferably, it is adjusted to be within about 10 minutes. For example, the time during which the film surface temperature is 100 ° C. to less than 130 ° C. can be as short as 3 minutes or 1 minute. Further, the lower limit of the heating time may be a time until an appropriate polyvinylene bond is formed, and the heating time is usually a time when the film surface temperature is from 100 ° C. to less than 130 ° C. is 10 seconds or more, preferably Is 15 seconds or longer.
As the heating means in the heat treatment step, any means can be used as long as the temperature of the film can be controlled within the above range, and an infrared heater, a convection heater or the like can be used. An infrared heater is preferably used as the heating means.
The “film surface temperature” in the heat treatment step can be measured using a known thermometer capable of measuring the film surface temperature. The thermometer to be used may be a non-contact type or a contact type. For example, a commercially available radiation thermometer or a thermometer using a thermocouple may be used.

(4) Stretching step The stretching step is a step of orienting the resin film constituting the intrinsic polarizer of the present invention. The stretching step can be performed either before or after the formation of the polyvinylene bond by heat treatment, or both. Usually, it is preferable to stretch the resin film both before and after the formation of the polyvinylene bond.
The stretching step (primary stretching step) performed before forming the polyvinylene bond can be performed either before the primary impregnation step, together with the primary impregnation step, or after the primary impregnation step. . When the resin film is stretched together with the primary impregnation step, the film may be stretched in an inorganic acid solution. For example, the film is dipped in an inorganic acid solution, swelled, and then stretched. Further, the film may be stretched before the primary impregnation step, and the primary impregnation step may be performed while maintaining the tension of the film. The stretching step may be performed a plurality of times.
In a preferred embodiment of the present invention, the first stretching (primary stretching step) is performed in the inorganic acid solution together with the first impregnation step. In this first stretching, the film is stretched to a predetermined magnification, for example, about 4 to 10 times. Further, it is more preferable to perform the second stretching process (secondary stretching process) after the heat treatment process (after the formation of the polyvinylene bond). The stretching ratio of the second stretching is preferably 2 times or less. This second stretching can also be performed following the curing agent treatment step (5) described later. This second stretching is usually performed in water.

The stretching method in the stretching step may be either a dry stretching method or a wet stretching method, but a wet stretching method is preferred. In the wet stretching method, a solution using water, a water-soluble organic solvent or a mixed solution of water and a water-soluble organic solvent is usually heated, and the polyvinyl alcohol resin film is stretched while being immersed in the heated solution. Is done.
The temperature of the stretching solution is usually about 30 to 60 ° C. As the stretching method, uniaxial stretching that is usually performed is preferable, and a method of uniaxial stretching between two rolls having different speeds is more preferable. The draw ratio of the film obtained by the stretching treatment with respect to the raw material film is about 4 to 12 times, preferably about 6 to 10 times. When the stretching process is performed a plurality of times, the total stretching ratio may be within the above range.

(5) Curing agent treatment step In a preferred embodiment for producing the intrinsic polarizer of the present invention, a curing agent treatment step is performed. The curing agent treatment step is usually performed by treating the film subjected to the primary impregnation step, the secondary impregnation step, the heat treatment step and the stretching step with a solution containing a curing agent. As the curing agent treatment step, a method of immersing the above film in a solution containing a curing agent is preferable. For example, the solution may be applied to the film.

Examples of the curing agent used in the curing agent treatment step include boron compounds such as boric acid or salts thereof (alkali metal salts such as borax, borax ammonium, etc.), polyvalent aldehydes such as glyoxal or glutaraldehyde, and biuret types. Polyisocyanate compounds such as isocyanurate type or block type, titanium compounds such as titanium oxysulfate, ethylene glycol glycidyl ether and polyamide epichlorohydrin can be used. Usually, boron compounds are preferred, and boric acid is more preferred. As the solvent of the curing agent treatment solution, water, a water-soluble organic solvent, a mixed solvent thereof or the like can be used, but water is preferable.
The curing agent concentration of the curing agent treatment solution varies depending on the type of the curing agent and cannot be generally specified, but is usually about 0.1 to 20% by mass, preferably about 5 to 10% by mass. The temperature of the curing agent treatment solution is preferably 80 to 100 ° C. The treatment time is usually about 30 seconds to 10 minutes, and more preferably about 1 to 5 minutes.
Moreover, the aspect which performs 2nd extending | stretching as described in the term of the extending | stretching process (4) following this hardening | curing agent process is preferable.

In a preferred embodiment of the present invention, boric acid is contained in the resin film when the curing agent treatment is performed in an aqueous boric acid solution. The content of boric acid in the polarizer at this time is obtained by heating the obtained polarizer in pure water to completely dissolve it, adding a phenolphthalein indicator, and performing neutralization titration with an aqueous sodium hydroxide solution. Can be sought.
The boric acid content in the intrinsic polarizer of the present invention is 3 to 30% by weight. The boric acid content in the intrinsic polarizer can be adjusted by the solution concentration, immersion time, solution temperature, stretch ratio, etc. in this step.

(6) Drying process The film subjected to the primary impregnation process, the secondary impregnation process, the heat treatment process and the stretching process, and further the curing agent treatment process as necessary is washed as necessary and then dried. Processed. The lower limit of the drying temperature in the drying step is about 30 ° C or higher, preferably about 40 ° C or higher, and the upper limit is about 80 ° C or lower, preferably about 70 ° C or lower. The drying time may be appropriately set depending on the drying temperature, and is usually about 1 to 20 minutes, preferably about 3 to 15 minutes. What is necessary is just to perform a drying process suitably using well-known heating means, such as an infrared heater.

  After the primary impregnation step, the secondary impregnation step, the heat treatment step, the stretching step, and the curing agent treatment step, for the purpose of removing components deposited on the film surface and attached foreign matters as necessary. The film surface may be cleaned. Usually, it is preferable to wash with water, the temperature of the cleaning liquid is about 10 to 60 ° C., and the cleaning time is about 1 second to 5 minutes. Washing may be performed once or multiple times as necessary.

The intrinsic polarizer of the present invention is, for example, in a preferred embodiment, an inorganic acid solution for a polyhydroxy linear polymer film (preferably a polyvinyl alcohol-based resin film) as a raw material film together with the first impregnation step. The first stretching step is performed, the second impregnation step is performed, the heat treatment step is performed, the curing agent treatment step and the second stretching step are sequentially performed, and then the drying step is performed. Can be manufactured.
The manufacturing method of the intrinsic polarizer of the present invention is not necessarily limited to the manufacturing method according to the order described above, and various modifications can be made.

The intrinsic polarizer of the present invention may contain one or more dichroic dyes from the viewpoint of improving optical properties. By including a dichroic dye having absorption in a specific wavelength region of visible light, it has excellent polarization characteristics in the entire visible light region, and the transmission axes of the two intrinsic polarizers of the present invention are parallel or orthogonal. The hue of the transmitted light when arranged in this way can be a more preferable hue of neutral gray.
The intrinsic polarizer containing a dichroic dye is a complementary color treatment in which a dichroic dye is previously contained in a resin film composed of a polyhydroxy linear polymer as a raw material when the intrinsic polarizer of the present invention is produced according to the production method. Can be obtained. In the complementary color treatment with the dichroic dye, the resin film is converted into a dye solution containing the dichroic dye, preferably a dye solution in which the dichroic dye is dissolved, as in the dye treatment in the method for producing a dye-based polarizer. It can be performed by dipping.
The dichroic dye is a dichroic dye that is used in the production of ordinary dye-based polarizers, as long as it is a dichroic dye that dyes the resin film and is oriented by stretching the polymer. Any of them can be used. In some cases, it is preferable to use a dichroic dye that absorbs blue light, and it is more preferable to use a dichroic dye having a maximum absorption wavelength (λmax) of 350 to 500 nm.

Optical performance of the polarizer and polarizing plate, such as transmittance and polarization degree, can be measured with a spectrophotometer (for example, V-7100 manufactured by JASCO Corporation, U-4100 manufactured by Hitachi, Ltd.).
The “single transmittance” of the intrinsic polarizer or polarizing plate in the present specification is a transmittance when a single intrinsic polarizer (polarizing plate) is used and irradiated with natural light (non-polarized light). JIS Z8701: 1999 Is measured using a spectrophotometer by a method based on the above. “Parallel transmittance” refers to the transmittance when two intrinsic polarizers (polarizing plates) are used and the two intrinsic polarizers (polarizing plates) are overlapped so that their absorption axes are the same. The “orthogonal transmittance” is the transmittance when two intrinsic polarizers (polarizing plates) are used and the two intrinsic polarizers (polarizing plates) are stacked so that their absorption axes are orthogonal to each other. It is.
In the present specification, unless otherwise specified, these “single transmittance”, “parallel transmittance”, and “orthogonal transmittance” are a wavelength range of 380 to 700 nm and a predetermined wavelength interval dλ (here, The spectral transmittance τλ is measured every 5 nm), and the average single transmittance, average parallel transmittance, and average orthogonal transmittance in the visible light region calculated by the following formula (1) are indicated.

In the formula, Pλ represents a spectral distribution of standard light (C light source), yλ represents a 2 ° visual field color matching function, and τλ represents a spectral transmittance.

The intrinsic polarizer of the present invention obtained as described above has the following characteristics.
As described above, the intrinsic polarizer of the present invention comprises a polymer film having a chain polyvinylene structure oriented in the same direction, and has at least two regions having different visible light transmittances in the film. In the intrinsic polarizer of the present invention, since the chain polyvinylene structures contained in the linear polymer are all oriented in the same direction, the direction of the absorption axis is the same in any region. In the secondary impregnation step in the method for producing the intrinsic polarizer of the present invention, the concentration of the inorganic acid solution and the acid residual time are adjusted, and the content of the number of blocks of the formed chain polyvinylene structure is determined for each region. By changing, it is possible to manufacture the intrinsic polarizer of the present invention in which at least two regions having the same absorption axis direction and different only visible light transmittance are patterned in the film plane.
In the intrinsic polarizer of the present invention, among the plurality of regions having different polarization characteristics, the difference in single transmittance between one region and the other region is 1% or more, more preferably 5% or more, still more preferably 10% or more. It is preferable to have at least one combination of two regions. In the intrinsic polarizer of the present invention, among the plurality of regions having different polarization characteristics, the difference in orthogonal transmittance between one region and the other region is 0.03% or more, more preferably 0.05% or more, More preferably, it has at least one combination of two regions that is 0.1% or more.

  The polarizing plate of the present invention is produced by forming a transparent protective layer by attaching a protective film on at least one surface of the intrinsic polarizer of the present invention obtained as described above. The protective film is added for the purpose of improving the water resistance and handling properties of the polarizer. As a raw material for the protective film, a transparent resin having excellent transparency, mechanical strength, thermal stability, moisture barrier property, etc. is particularly preferably used.

Examples of protective films include polyester resins, acetate resins, polyethersulfone resins, polycarbonate resins, polyamide resins, polyimide resins, thermoplastic resins such as polyolefin resins and acrylic resins, and acrylic resins. And films obtained from thermosetting resins such as urethane, acrylic urethane, epoxy and silicone, or ultraviolet curable resins. Examples of the polyolefin resin include non-crystalline polyolefin resins and resins having a polymerized unit of cyclic polyolefin such as norbornene or a polycyclic norbornene monomer. Instead of laminating the protective film, a transparent protective layer may be formed by applying any of the above resins to at least one surface of the polarizer of the present invention.
A preferable protective film used for the polarizing plate of the present invention includes a film made of an acetate resin, and preferably a film made of triacetyl cellulose (TAC).

  The transparent protective film used for the transparent protective layer may be subjected to a treatment for the purpose of hard coat treatment, antireflection treatment, sticking prevention, diffusion or antiglare, etc., as long as the effects of the present invention are not impaired. good. After forming a transparent protective layer on at least one surface of the polarizer of the present invention by laminating a transparent protective film or applying a resin, these treatments may be performed. The film thickness of the transparent protective film is about 0.5 to 200 μm.

After the protective film is bonded to the polarizer of the present invention with an adhesive, the polarizing plate of the present invention can be obtained by drying or heat treatment at an appropriate temperature.
The adhesive used for the adhesive treatment between the polarizer of the present invention and the protective film is not particularly limited. For example, an adhesive made of a vinyl alcohol polymer, boric acid, borax, glutaraldehyde, melamine or the like. Adhesives composed of water-soluble crosslinking agents for vinyl alcohol polymers such as oxalic acid, highly transparent epoxy resins, polyester resins, solvent-based adhesives such as vinyl acetate, acrylic resins, urethane resins, etc. An adhesive resin or the like that can be cured by a polymerization reaction can be used. When producing the polarizing plate of the present invention, it is preferable to use a polyvinyl alcohol-based adhesive.

  The polarizing plate of the present invention can also be used as an optical member by being laminated on an optical layer made of another optical material. Examples of the optical material that can be laminated on the polarizing plate of the present invention include a reflector, a transflective plate, a retardation plate (including a λ plate such as a half-wave plate and a quarter-wave plate), a visual field, and the like. An angle compensation film, a brightness enhancement film, etc. are mentioned.

The polarizing plate of the present invention and various optical members using the polarizing plate of the present invention can be preferably used for various optical devices such as an image display device and a lighting device. For example, appropriate components such as a prism array sheet, a lens array sheet, a light diffusing plate, and a backlight can be arranged in one or more layers at appropriate positions.
When using the polarizing plate of this invention with another optical material member, the adhesion layer for adhere | attaching with another optical member is normally formed in the one side or both sides of the polarizing plate of this invention. As the adhesive layer, an appropriate adhesive substance or adhesive can be used, and there is no particular limitation. Examples thereof include those using an appropriate polymer such as an acrylic polymer, silicone polymer, polyester, polyurethane, polyamide, polyether, fluorine polymer, rubber polymer as a base polymer.

As described above, in the intrinsic polarizer of the present invention, or the polarizing plate including the same, the chain polyvinylene structures in the polyhydroxy linear polymer are all aligned in the same direction, and the number of the chain polyvinylene blocks is the same. Since each region is different, the direction of the absorption axis is the same in all regions, but at least two regions with different visible light transmittance are arranged in a pattern, a characteristic not realized with conventional polarizers Have In addition, since the intrinsic polarizer of the present invention has high durability unique to the intrinsic polarizer, it is considered useful as an intrinsic polarizer and polarizing plate for various optical devices such as an image display device and an illumination device.
Hereinafter, the present invention will be described more specifically with reference to examples.

Example 1
A polyvinyl alcohol resin film (polymerization degree 4000, saponification degree 98 mol% or more, thickness 75 μm) was swollen in a hydrochloric acid temperature of 40 ° C. and a 0.1N hydrochloric acid aqueous solution for 18 seconds, and then the film was added in the hydrochloric acid aqueous solution. Was uniaxially stretched 6.7 times over 105 seconds.
Next, the obtained stretched film was taken out from the hydrochloric acid aqueous solution, and hydrochloric acid remaining on the film surface was removed with a filter paper. Then, a 0.5N hydrochloric acid aqueous solution was applied to the surface of the stretched film by applying a strip-shaped nonwoven fabric containing a 0.5N hydrochloric acid aqueous solution to the stretched film. The applied region is referred to as region 2. Immediately after coating, hydrochloric acid remaining as water droplets on the surface of the stretched film was adsorbed on a filter paper and removed.
Next, in the same manner as described above except that a 1.0 N hydrochloric acid aqueous solution was used, a 1.0 N hydrochloric acid aqueous solution was applied to the region adjacent to the region 2 (region 3) with a nonwoven fabric in the stretched film. Immediately after coating, hydrochloric acid remaining as water droplets on the film surface was adsorbed on a filter paper and removed.
Next, a 1.0 N hydrochloric acid aqueous solution is applied by applying a strip-shaped nonwoven fabric containing a 1.0 N hydrochloric acid aqueous solution to a region (region 4) adjacent to the region 3 and opposite to the region 2 (region 4). did. After 10 seconds had elapsed from the coating, hydrochloric acid remaining as water droplets on the film surface was adsorbed onto the filter paper and removed.

By heating the film subjected to the above treatment with an infrared heater while monitoring the temperature of the film surface with a non-contact type thermocouple temperature sensor (manufactured by FENWAL, product name μIR / c-K), polyvinylene is obtained. A bond was formed. The heating time of the film was 44 seconds, and the maximum temperature reached on the film surface during heating was 120 ° C.
The obtained film was immersed in a 7% by weight boric acid aqueous solution having a liquid temperature of 90 ° C. for 270 seconds to perform boric acid treatment. The boric acid-treated film was stretched 1.04 times in 35 ° C. water over 30 seconds. After the film was washed with running water, moisture on the film surface was removed. Next, using an infrared heater, the film was dried at a film temperature of 60 ° C. for 10 minutes to obtain an intrinsic polarizer whose polarization characteristics were patterned in a stripe shape. At this time, the widths of the regions 2 to 4 in the obtained intrinsic polarizer were about 1.5 to 2.0 cm, respectively. Further, in the obtained intrinsic polarizer, the light absorption axis (transmission axis) in the region where the aqueous hydrochloric acid solution was not applied (region 1) and the regions 2 to 4 were parallel.

Test example (measurement of polarization performance)
About the intrinsic | native polarizer of this invention obtained in the said Example 1, the average single-piece | unit transmittance | permeability and the average orthogonal transmittance | permeability for every area | region of the said areas 1-4 were measured for the spectrophotometer (the JASCO Corporation make, product name V- 7100) under the following conditions.
Measurement wavelength: 380 to 780 nm
Calculation range: 380 to 700 nm
Measurement conditions: scan speed 600 nm / min
In order to measure the transmittance of the specific polarizer only in a specific area, two jigs with 0.8cm x 0.8cm windows are prepared, and the positions of both windows coincide with each other. Thus, a sample for measurement was prepared by sandwiching the intrinsic polarizer. In addition, the measurement light was stopped using a mask having a diameter of 3.2 mm. In this way, the transmittance of a specific region in the intrinsic polarizer can be measured.
When measuring the average single transmittance Ys, a single intrinsic polarizer is sandwiched between the two jigs, and the region to be measured in the intrinsic polarizer and the positions of the windows of both jigs are matched. A sample for measurement was prepared by adjusting the position of the intrinsic polarizer. When measuring the average orthogonal transmittance Yc, two intrinsic polarizers are sandwiched between the two jigs, and the region to be measured in the two intrinsic polarizers and the positions of the windows of both jigs are determined. The measurement samples were prepared by adjusting the positions of the two intrinsic polarizers so that they coincide and the absorption axes of the respective intrinsic polarizers are orthogonal to each other.
The average single transmittance Ys and the average orthogonal transmittance Yc in the visible light region are measured at predetermined wavelength intervals dλ (here, 5 nm) by the spectrophotometer in the wavelength region of 380 to 700 nm using the respective measurement samples. Spectral transmittance τλ was measured and calculated by the following formula (1).

In the equation, Pλ represents a spectral distribution of standard light (C light source), and yλ represents a 2 ° visual field color matching function.
Table 1 below shows the measurement results of the average single transmittance Ys and the average orthogonal transmittance Yc of 380 to 700 nm in each of the regions 1 to 4 for the intrinsic polarizing plate of Example 1.

[Table 1]

Comparative Example 1
An intrinsic polarizer (film thickness: about 40 μm) is taken out from a commercially available polarizing plate including an intrinsic polarizer, and an average single transmittance Ys of 380 to 700 nm is obtained at any seven locations in the film plane of the taken out intrinsic polarizer. The average orthogonal transmittance Yc was measured. The measurement results are shown in Table 2. The numerical value in the item “MAX-MIN” in Table 2 is the difference between the maximum value and the minimum value of the measured values at the seven locations.

[Table 2]

As shown in Table 1, the visible light transmittance in the film is different depending on the method for producing the intrinsic polarizer of the present invention including the secondary impregnation step in which a portion having a high inorganic acid concentration is formed in a pattern in the polymer film. An intrinsic polarizer having regions in a pattern can be produced. Further, it was found that the values of the single transmittance Ys and the orthogonal transmittance Yc in the pattern can be adjusted by changing the concentration of the inorganic acid solution and / or the acid remaining time in the secondary impregnation step.
Furthermore, the intrinsic polarizer of the present invention has the same absorption axis in any region, and the intrinsic polarizer of the present invention obtained by Example 1 has an average single transmittance in the film plane. It had a plurality of regions where Ys was different by at least 3.3% and by a maximum of 14.6%. In addition, the intrinsic polarizer of the present invention obtained in Example 1 has an average orthogonal transmittance Yc as excellent as 0.31% at the maximum, particularly in the region where the inorganic acid is applied in the secondary impregnation step. The intrinsic polarizer of the present invention, which has a remarkably excellent average orthogonal transmittance of 0010 to 0.0056%, has a chain-like polyvinylene structure in the film regularly oriented in the same direction. It was found to be very useful for various optical applications.

The intrinsic polarizer of the present invention and the polarizing plate provided with the intrinsic polarizer have high durability, which is a characteristic of the intrinsic polarizer, and have a chain-like polyvinylene structure oriented in the same direction on the entire surface, so that the directions of the polarization axes are the same. And a patterned intrinsic polarizer having at least two regions having different visible light transmittances. In addition, the intrinsic polarizer of the present invention can be manufactured by a simple process applying a conventional coating technique or printing technique, so that it can be manufactured at a low cost and can cope with a large area.
Furthermore, by applying printing technology, etc., there is a possibility that it can be developed into an intrinsic polarizer having a fine polarization pattern, and by using an intrinsic polarizing plate with finer control of the transmittance in a minute region for a display device For example, it may be used as a means for solving the problem of speckle noise when coherent light is used as a light source.

Claims (12)

  An intrinsic polarizer comprising a polymer film having a chain-like polyvinylene structure oriented in the same direction on the entire surface, and having at least two regions having different visible light transmittances in the film.   The intrinsic polarizer according to claim 1, wherein the polyvinylene structure in the polymer molecule is formed by dehydration of a polyhydroxy linear polymer.   The intrinsic polarizer according to claim 1 or 2, wherein two or more regions having different visible light transmittances are patterned in a stripe shape.   The intrinsic polarizer according to any one of claims 1 to 3, wherein the difference in visible light average single transmittance between regions having different visible light transmittances is at least 1%. (1) a primary impregnation step of impregnating an entire film made of a polyhydroxy linear polymer with an inorganic acid as a dehydration catalyst;
(2) After the primary impregnation step, further, a secondary impregnation step of impregnating the polymer film in a pattern with an inorganic acid as a dehydration catalyst to form a portion having a high inorganic acid concentration in the pattern,
(3) forming a polyvinylene structure in the linear polymer molecule by heating the polymer film after the secondary impregnation step; and
(4) A film stretching step for orienting the film,
5. The method for producing an intrinsic polarizer according to claim 1, comprising the following four steps.   6. The method for producing an intrinsic polarizer according to claim 5, wherein the inorganic acid concentration of the portion having a high inorganic acid concentration formed in a pattern in the film is at least two different concentrations.   The method for producing an intrinsic polarizer according to claim 6, wherein at least two portions having a high concentration of the inorganic acid having different concentrations are formed by coating at least two inorganic acid solutions having different concentrations.   In the secondary impregnation step, at least two portions having a high concentration of the inorganic acid having different concentrations are formed by differently impregnating the film with the inorganic acid for each portion. A method for producing the intrinsic polarizer according to claim 6.   The primary impregnation step impregnates the polymer film with the inorganic acid by immersing the polymer film in an inorganic acid solution before, simultaneously with or after the orientation of the polymer. The manufacturing method of the intrinsic | native polarizer as described in any one of -8.   The method for producing an intrinsic polarizer according to any one of claims 5 to 9, wherein the inorganic acid is hydrochloric acid.   A protective film or a support is stuck on at least one surface of the intrinsic polarizer according to any one of claims 1 to 4 or the intrinsic polarizer obtained by the production method according to any one of claims 5 to 10. Combined polarizing plate.   The intrinsic polarizer as described in any one of Claims 1-4, the intrinsic polarizer obtained by the manufacturing method as described in any one of Claims 5-10, or the polarizing plate of Claim 11. Display device.