JP2003029036A - Low reflection polarizing plate and display device using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a low reflection polarizing plate showing good curling and flatness and excellent display characteristics such as visibility, viewing angle and so on, and to provide a display device which uses the above polarizing plate. SOLUTION: In the low reflection polarizing plate having a polarizing layer held between two transparent supporting bodies (A), (B), the transparent supporting bodies (A), (B) contain cellulose esters. The transparent supporting body (A) has an antireflection layer on the opposite face to the polarizing layer. The film thickness of the supporting bodies (A), (B) is represented by formula (1). The average substitution degree A of the cellulose esters in the supporting body (A) and the average substitution degree B of the cellulose esters in the transparent supporting body (B) are represented by formula (2). (1): film thickness of supporting body (A) <= film thickness of supporting body (B) <= film thickness of supporting body (A)+100 (2): average substitution degree B+0.05 <= average substitution degree A <= average substitution degree B+0.35.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a low reflection polarizing plate provided with an antireflection function and a display device using the same, and more specifically, it can provide high display quality stably for a long period of time. The present invention relates to a low-reflection polarizing plate and a display device using the same.

[0002]

2. Description of the Related Art In recent years, thin and lightweight notebook personal computers have been developed. Along with that, protective films for polarizing plates used in display devices such as liquid crystal display devices are becoming thinner and thinner.
The demand for higher performance is increasing.

Recently, a display having an antireflection function has been widely used to improve visibility. Various kinds of antireflection layers and antiglare layers have been improved in performance depending on the application, and various front plates having these functions can be attached to a polarizer of a liquid crystal display to improve visibility. Therefore, a method of imparting an antireflection function or an antiglare function is used. The optical film used as the front plate is provided with an antireflection layer formed by coating or sputtering.

The antireflection functional layer reduces the reflectance of the surface to reduce the visibility of the reflected image, and is reflected when an image display device such as a liquid crystal display, an organic EL display or a plasma display is used. This is to prevent the reflection of the image from being noticeable.

Further, as a result of recent studies, it has been demanded that a polarizing plate used for a display device is provided with an antireflection function to prevent a reduction in contrast and an image from being reflected. Although it is possible to provide the antireflection layer by various methods, it is becoming difficult to exhibit sufficient performance simply by providing the antireflection layer, as the display device becomes finer. Therefore, there is a demand for urgent development of improvement means.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object thereof is a low reflection polarized light having good curl, flatness, and excellent display characteristics such as visibility and viewing angle. To provide a plate and a display device using the plate.

[0007]

The above objects of the present invention have been achieved by the following constitutions.

In a low reflection polarizing plate having a polarizing layer sandwiched between 1.2 transparent supports A and B, both of the transparent supports A and B contain a cellulose ester, and the transparent support A Has an antireflection layer on the surface opposite to the polarizing layer directly or via another layer, and the film thickness of the transparent support A and the transparent support B is represented by the formula (1). Is a relationship,
The average substitution degree A of the cellulose ester contained in the transparent support A having the antireflection layer and the average substitution degree B of the cellulose ester contained in the transparent support B are represented by the above formula (2). A low-reflection polarizing plate characterized by having a relationship.

2. The transparent supports A and B each have a film thickness of 200 μm or less, and the film thickness difference between the transparent supports (transparent support B film thickness−transparent support A film thickness) is ΔM,
When the difference in the average substitution degree of the cellulose ester used for each (average substitution degree of the cellulose ester used in the transparent support A-average substitution degree of the cellulose ester used in the transparent support B) is ΔS, the above formula ( 3. The low reflection polarizing plate as described in 1 above, which satisfies the condition 3).

3. The low reflection polarizing plate as described in 1 or 2 above, wherein the two transparent supports A and B are biaxially stretched cellulose ester films.

4. In a polarizing plate in which a polarizing layer is sandwiched between two transparent supports A and B, the transparent support A is provided on the surface opposite to the polarizing layer through an actinic radiation curable resin layer to prevent reflection. 4. The low reflection polarizing plate as described in any one of 1 to 3 above, which has a layer, and the transparent support B has an actinic radiation curable resin layer on the surface opposite to the polarizing layer.

5. The film thickness ratio (UVb / UVa) of the film thickness UVa of the actinic radiation curable resin layer of the transparent support A and the film thickness UVb of the actinic radiation curable resin layer of the transparent support B is 0.1 to 1
The low reflection polarizing plate as described in the above item 4, which is 0.

6. 6. The low reflection polarizing plate as described in 4 or 5 above, wherein the film thickness UVb of the actinic radiation curable resin layer of the transparent support B is 1.3 μm or more.

7. The film thickness ratio (UVb / UVa) between the film thickness UVa of the active ray-curable resin layer of the transparent support A and the film thickness UVb of the active ray-curable resin layer of the transparent support B is 0.2 to.
The low reflection polarizing plate as described in the above item 5, wherein the polarizing plate has a value of 0.95.

8. The transparent support A or the transparent support B
Is a metal oxide layer having a carbon content of 0.2 to 5%, and the low reflection polarizing plate as described in any one of the above items 1 to 7.

9. 9. The low reflection polarizing plate as described in any one of 1 to 8 above, wherein the transparent support A has an antireflection layer including a metal oxide layer having a refractive index of 2.0 or more.

10. Item 10. The low-reflection polarizing plate according to any one of Items 1 to 9, wherein the transparent support A has an antireflection layer formed by atmospheric pressure plasma treatment.

1 to 10 characterized in that the average reflectance from 11.450 to 650 nm is less than 0.5%.
The low-reflection polarizing plate according to any one of items.

12. 12. A display device using the low reflection polarizing plate according to any one of items 1 to 11 and arranged so that the transparent support A surface side is the front surface side.

The details of the present invention will be described below. The present inventor uses two cellulose ester films as a polarizing plate protective film, and lowers the degree of substitution of the cellulose ester of the cellulose ester film on the other side with the cellulose ester film on the side on which the antireflection layer is provided. It was found that by doing so, a polarizing plate that can provide high display quality can be obtained. At this time, more preferably, the thickness of the cellulose ester film on the side having the antireflection layer is equal to or thinner than that of the other side, and particularly, the thickness is 200 μm or less, and the transparent support A, B Is ΔM and the difference in the average degree of substitution of the cellulose ester used in the transparent supports A and B is ΔS, the polarizing plate satisfies the relationship of 0.05 + ΔM / 200 <ΔS. It has been newly found that it is preferable.

By setting the conditions defined above,
The characteristics of the polarizing plate hardly change even under high temperature and high humidity conditions, and high display quality can be maintained. More preferably, the cellulose ester film used in the present invention is biaxially stretched, which can provide even better display quality.

More preferably, both transparent supports are provided with an actinic ray curable resin layer, and a polarizing plate having excellent display performance with less problems of warpage during storage is provided. That is.

The present invention is characterized in that the antireflection layer is formed of a metal oxide layer, but it is particularly preferable that the carbon content is 0.2 to 5%, whereby scratch resistance is improved. Can be improved. In particular, it is preferable to have a metal oxide layer having a refractive index of 2.0 or more, and this makes it possible to obtain a film having more excellent display quality.
These antireflection layers are characterized in that they are preferably formed by an atmospheric pressure plasma method and have the above-mentioned structure.
By providing a laminated antireflection layer having more layers, a polarizing plate having excellent durability can be obtained. In particular, when the high refractive index layer of the antireflection layer has a refractive index of 2.0 or more, the antireflection layer having a lower reflectance can be obtained, which is preferable, and the polarizing plate is curled or wavy due to the influence of humidity or the like. However, the polarizing plate of the present invention does not have such a problem and can provide excellent display performance.

In particular, the effect of widening the viewing angle can be obtained with good durability in the liquid crystal cell adopting the vertical alignment method (vertical alignment method). Further, the present invention has made it possible to obtain a low-reflection polarizing plate having excellent display performance without problems such as warpage and waviness during storage, and the present invention has been completed.

The basic structure of the low reflection polarizing plate of the present invention will be described below. FIG. 1 is a configuration diagram showing an example of a typical configuration of the low-reflection polarizing plate of the present invention.

In the low reflection polarizing plate 6 of the present invention, the polarizing layer 1 having a polarizer is sandwiched between two transparent supports A and B. In FIG. 1A, when the low-reflection polarizing plate 6 is used for a display device, the transparent support A mainly on the front surface side is used.
Is provided with a back coat layer 3 on the surface adjacent to the cellulose ester film 2 and the polarizing layer 1, and on the surface opposite to the polarizing layer 1, the actinic radiation curable resin layer 4 and one or more reflection layers. The prevention layer 5 is provided. On the other hand, the transparent support B includes a cellulose ester film 2'and a polarizing layer 1
And a back coat layer 3'provided on the surface adjacent to. As the transparent support B, the cellulose ester film 2 ′ alone may be used without providing the back coat layer 3 ′, but preferably, it has the structure shown in FIG. 1 (a).

FIG. 1B is an example in which the actinic radiation curable resin layer 4 according to the invention of claim 4 is provided on the transparent supports A and B, and the antireflection layer 5 of the transparent support A is shown. The actinic radiation curable resin layer 4 is provided between the film and the cellulose ester film 2, and the actinic radiation curable resin layer 4'is provided on the surface of the transparent support B opposite to the polarizing layer 1.

In the invention according to claim 1, in a low reflection polarizing plate in which a polarizing layer is sandwiched between two transparent supports A and B, both of the transparent supports A and B contain cellulose ester. The transparent support A has an antireflection layer on the surface opposite to the polarizing layer directly or through another layer, and the transparent support B has a film thickness equal to or larger than that of the transparent support A. Body A
The average substitution degree A of the cellulose ester contained in the transparent support A having a film thickness of +100 μm or less and further having an antireflection layer is an average substitution degree B of the cellulose ester contained in the transparent support B + 0.05 or more, and the average. Substitution degree B + 0.
The feature is that it is 35 or less.

In the present invention, the film thickness of each transparent support means, as shown in FIGS. 1A and 1B, in the transparent support A, the antireflection layer 5, the cellulose ester film 2 and the back coat. It means the total film thickness of the layer 3 and, when the actinic radiation curable resin layer 4 is provided, the total film thickness including it. Similarly, in the transparent support B, it means the total film thickness of the cellulose ester film 2 and the back coat layer 3, or the total film thickness when the active ray curable resin layer 4 is added.

Next, the cellulose ester film will be described. Generally, as a transparent support, for example,
Cellulose ester support such as cellulose triacetate, polyester support, polycarbonate support, polystyrene support, and further gelatin, polyvinyl alcohol (PVA), acrylic resin on the upper layer of these supports,
A support or the like coated with a polyester resin, a cellulose ester-based resin or the like is known, and one of the characteristics of the present invention is that it is a cellulose ester film.

In the present invention, the use of a cellulose ester film is preferable in that a laminate having a low reflectance can be obtained. As the cellulose ester, for example, cellulose acetate, cellulose acetate butyrate, and cellulose acetate propionate are preferable, and among them, cellulose acetate butyrate and cellulose acetate propionate are preferably used. The butyryl group forming butyrate may be linear or branched.

Cellulose acetate propionate containing a propionate group as a substituent has excellent water resistance and is useful as a film for liquid crystal image display devices.

Cellulose triacetate is preferably used as the cellulose ester, but in order to obtain a certain level of optical compensation performance, a lower fatty acid cellulose ester having a specific substituent, that is, an acetyl group and a propionyl group is used. Is extremely effective.

The cellulose ester used for producing the cellulose ester film according to the present invention has 2 to 4 carbon atoms.
The acyl group of 1 is included as a substituent, and in particular,
In the invention according to, when the substitution degree of the acetyl group is X and the substitution degree of the propionyl group and / or butyryl group is Y, the average substitution degree in the present invention is represented by X + Y, and the average substitution in the transparent supports A and B is It is characterized in that it is a low reflection polarizing plate in which each functional layer is provided on a film produced using a mixed fatty acid ester of cellulose satisfying the condition of the above formula (2).

Further, in the invention according to claim 2, the film thickness of each of the transparent supports A and B is 200 μm or less, and the film thickness difference between the respective transparent supports (transparent support B film thickness-transparent support). A
The film thickness) is ΔM, and the difference in the average substitution degree of the cellulose ester used for each (average substitution degree of the cellulose ester used in the transparent support A−average substitution degree of the cellulose ester used in the transparent support B) is ΔS. In this case, the condition of the equation (3) is satisfied.

These acyl groups have 2 units of glucose units.
The 3rd, 6th, and 6th positions may be substituted on average, and, for example, 6th position may be substituted at a high ratio.

Here, the substitution degree means a percentage of the so-called bound fatty acid amount, and is a numerical value calculated according to the measurement and calculation of the acetylation degree in ASTM-D817-91 (testing method for cellulose acetate etc.). The acyl group substitution degree can be measured according to ASTM-D817-96. The average substitution degree according to the present invention is the sum of the substitution degrees of the respective acyl groups, and when a plurality of cellulose esters are mixed, they are represented by the average substitution degree.

When the substitution degree of the acetyl group and the acyl group having 3 to 4 carbon atoms is within the above range, there is a characteristic that the retardation becomes larger as the wavelength becomes longer, and good water content and water barrier property are obtained. The provided cellulose ester film support can be obtained.

Particularly, when the average degree of substitution of acetyl groups is less than 2.0, there is little variation in retardation during stretching, which is particularly preferable.

When the cellulose ester film according to the present invention is used, cellulose as a raw material of the cellulose ester is not particularly limited, but for example, cotton linter,
Examples thereof include wood pulp (derived from coniferous trees and hardwood) and kenaf. Moreover, the cellulose ester obtained from them can be mixed and used in an arbitrary ratio, respectively. These cellulose esters are prepared by using a cellulose raw material such as an organic acid such as acetic acid or an organic acid such as methylene chloride when the acylating agent is an acid anhydride (for example, acetic anhydride, propionic anhydride, butyric anhydride). It can be obtained by using a solvent and a protic catalyst such as sulfuric acid. Further, the acylating agent is an acid chloride (CH ₃ COCl, C ₂ H ₅ COCl, C ₃ H ₇ C
OCl), the reaction is carried out using a basic compound such as an amine as a catalyst. Specifically, it can be obtained by referring to the method described in JP-A-10-45804. Further, the cellulose ester that can be used in the present invention is prepared by mixing and reacting the above-mentioned acylating agent in accordance with each degree of substitution, and the cellulose ester has these acyl groups with the hydroxyl groups of the cellulose molecule. react. The cellulose molecule has a structure in which a large number of glucose units are linked, and the glucose unit has three hydroxyl groups. The number of acyl groups introduced into these three hydroxyl groups is called the degree of substitution (mol%). For example, cellulose triacetate has an acetyl group bonded to all three hydroxyl groups of a glucose unit. Actually, the substitution degree is 2.6 to 3.0.

The number average molecular weight of cellulose ester is 7
20,000 to 250,000 has a high mechanical strength when molded, and provides an appropriate dope viscosity, and is more preferably 80,000 to 150,000.

The method for producing these cellulose esters is as follows.
A cellulose ester film produced by a solution casting film forming method is used as the base film, but the solution casting film forming method itself is not particularly limited, and a method generally used in the art, for example, US Patent Second 2,492,9
No. 78, No. 2,739,070, No. 2,739,
069, 2,492,977, 2,33
No. 6,310, No. 2,367,603, No. 2,6
07,704, British Patents 64,071, 73
No. 5,892, Japanese Patent Publication No. 45-9074, No. 49-45.
No. 54, No. 49-5614, No. 60-27562,
The methods described in No. 61-39890, No. 62-4208, etc. can be referred to.

The method for producing a cellulose ester film according to the present invention will be described in more detail below, but the present invention is not limited thereto. Of these, the vertical direction is
The film forming direction (longitudinal direction) of the film and the lateral direction (width direction) mean a direction perpendicular to the film forming direction of the film.

The invention according to claim 3 is characterized in that the cellulose ester film is a film biaxially stretched in the width direction or in the film formation direction.

The preferred stretch ratio of the cellulose ester film is such that the stretch ratio in one direction is 1.01 to 2.0 and the stretch ratio in the other is 1.00 to 2.00. It is more preferable that the stretching ratio in one direction is stretched to 1.00 to 1.50 times, and the stretching ratio in the other direction is stretched to 1.01 to less than 1.50 times. The draw ratio in the direction 1.00 to 1.
It is stretched 25 times and the other stretch ratio is 1.01
It was stretched to less than 1.25 times.

As a result, a cellulose ester film having excellent optical isotropy can be preferably obtained. It is preferable that the width retention or the transverse stretching in the film forming step is performed by a tenter, and a pin tenter or a clip tenter may be used.

The solvent used for preparing the dope solution of the cellulose ester used in the solution casting film-forming method may be used alone or in combination of two or more kinds, but a good solvent of the cellulose ester and a poor solvent are mixed. It is preferable to use it in terms of production efficiency, and it is preferable that the amount of the good solvent is large in terms of the solubility of the cellulose ester. The preferable range of the mixing ratio of the good solvent and the poor solvent is 70 to 98% by mass of the good solvent,
The poor solvent is 30 to 2 mass%.

The good solvent and poor solvent referred to in the present invention are those which dissolve the cellulose ester to be used alone,
Those that swell or do not dissolve by themselves are defined as poor solvents. Therefore, depending on the average degree of acetylation of the cellulose ester, the target of good solvent and poor solvent changes. For example, when acetone is used as a solvent, the amount of bound acetic acid in the cellulose ester of 55% is a good solvent, and the amount of bound acetic acid is 60. % Is a poor solvent.

The organic solvent used for preparing the above dope is preferably one which can dissolve the cellulose ester and has an appropriate boiling point. For example, methylene chloride, methyl acetate, ethyl acetate, amyl acetate, acetone,
Tetrahydrofuran, 1,3-dioxolane, 1,4-
Dioxane, cyclohexanone, ethyl formate, 2,2
2-trifluoroethanol, 2,2,3,3-hexafluoro-1-propanol, 1,3-difluoro-2
-Propanol, 1,1,1,3,3,3-hexafluoro-2-methyl-2-propanol, 1,1,1,
3,3,3-hexafluoro-2-propanol, 2,
2,3,3,3-pentafluoro-1-propanol,
Examples thereof include nitroethane and 1,3-dimethyl-2-imidazolidinone, but organic halogen compounds such as methylene chloride, dioxolane derivatives, methyl acetate, ethyl acetate, acetone and the like are preferable organic solvents (that is, good solvents). As.

Further, as shown in the following film forming step, when the solvent is dried from the web (dope film) formed on the casting support in the solvent evaporation step, the viewpoint of preventing foaming in the web. Therefore, the boiling point of the organic solvent used is preferably 30 to 80 ° C. For example, the boiling point of each good solvent described above is methylene chloride (boiling point 40.4).
C.), methyl acetate (boiling point 56.32 ° C.), acetone (boiling point 56.3 ° C.), ethyl acetate (boiling point 76.82 ° C.) and the like.

Among the above-mentioned good solvents, methylene chloride and methyl acetate, which are excellent in solubility, are preferably used, and in particular, methylene chloride is used for all organic solvents at 5%.
It is preferably contained in an amount of 0 mass% or more.

In addition to the above organic solvent, 0.1 to 30 mass%
It is preferable to include the alcohol having 1 to 4 carbon atoms. Particularly preferably, the alcohol is contained in an amount of 5 to 30% by mass. After casting the above dope on the casting support, when the solvent begins to evaporate and the ratio of alcohol increases, the web (dope film) gels, making the web strong and peeling from the casting support. It also has a role of promoting the dissolution of the cellulose ester of the non-chlorine type organic solvent when it is used as a gelling solvent for facilitating the reaction or when the proportion of alcohol is small.

Examples of the alcohol having 1 to 4 carbon atoms include methanol, ethanol, n-propanol, iso-propanol, n-butanol and sec.
-Butanol, tert-butanol and the like can be mentioned.

Among these alcohols, ethanol is preferable because it has a dope stabilizing effect, has a relatively low boiling point, has good drying properties, and is not toxic. , Ethanol 5
It is preferable to use a solvent containing 30% by mass. Methyl acetate may be used in place of methylene chloride when a solvent containing halogen is avoided due to environmental restrictions.
At this time, it is also preferable to prepare the cellulose ester solution by a cooling dissolution method.

When a cellulose ester film is used as the substrate according to the present invention, the cellulose ester film preferably contains a plasticizer.

The plasticizer which can be used is not particularly limited, and examples thereof include phosphoric acid ester plasticizers, phthalic acid ester plasticizers, trimellitic acid ester plasticizers, pyromellitic acid plasticizers, and glycosyl ester plasticizers. Rate plasticizer,
Citrate ester plasticizers, polyester plasticizers and the like can be preferably used. Examples of the phosphate ester system include triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, tributyl phosphate, and the like, and phthalate ester system such as diethyl phthalate. , Dimethoxyethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate,
Examples of trimellitic acid plasticizers such as butylbenzyl phthalate include tributyl trimellitate, triphenyl trimellitate, triethyl trimellitate, and the like.
Examples of the pyromellitic ester plasticizer include, for example, tetrabutylpyromellitate, tetraphenylpyromellitate, and tetraethylpyromellitate, and examples of the glycolic acid ester include, for example, triacetin, tributyrin, ethylphthalylethyl glycolate, Examples of the citric acid ester plasticizers such as methylphthalylethyl glycolate and butylphthalylbutyl glycolate include:
Triethyl citrate, tri-n-butyl citrate,
Acetyl triethyl citrate, acetyl tri-n-butyl citrate, acetyl tri-n- (2-ethylhexyl) citrate and the like can be preferably used. In addition, examples of the carboxylic acid ester include butyl oleate, methylacetyl ricinoleate, dibutyl sebacate, and various trimellitic acid esters. Further, as the polyester plasticizer, for example, a copolymerized polymer of a dibasic acid such as an aliphatic dibasic acid, an alicyclic dibasic acid, an aromatic dibasic acid and a glycol can be used. The aliphatic dibasic acid is not particularly limited,
For example, adipic acid, sebacic acid, phthalic acid, terephthalic acid, 1,4-cyclohexyldicarboxylic acid, etc. can be used. Examples of glycols include ethylene glycol, diethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,
4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, etc. can be used. These dibasic acids and glycols may be used alone or in combination of two or more.

In particular, a cellulose ester film having additives such as epoxy compounds, rosin compounds, phenol novolac type epoxy resins, cresol novolac type epoxy resins, ketone resins and toluene sulfonamide resins described in Japanese Patent Application No. 2000-338883. It is preferably used.

These plasticizers can be used alone or in combination. The amount of these plasticizers used is 1 with respect to the cellulose ester in view of film performance, processability and the like.
It is preferably about 20% by mass.

Next, the ultraviolet absorber which can be used in the base material according to the present invention will be described. From the viewpoint of preventing deterioration of liquid crystal and the like, the base material according to the present invention preferably contains an ultraviolet absorber.

The ultraviolet absorber which can be used in the present invention has an excellent ability to absorb ultraviolet rays having a wavelength of 370 nm or less and has a wavelength of 400 nm from the viewpoint of good liquid crystal display.
A material that absorbs less visible light is preferably used. Specific examples of the ultraviolet absorber preferably used in the present invention include, for example, oxybenzophenone compounds, benzotriazole compounds, salicylate compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex salt compounds and the like. , But not limited to these. Further, the polymeric ultraviolet absorber described in JP-A-6-148430 is also preferably used.

As the benzotriazole type ultraviolet absorber, a compound represented by the following general formula [1] is preferably used.

[0062]

[Chemical 1]

In the formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, an alkyl group, an alkenyl group, an aryl group, an alkoxyl group, an acyloxy group, Represents an aryloxy group, an alkylthio group, an arylthio group, a mono- or dialkylamino group, an acylamino group or a 5- or 6-membered heterocyclic group, R ₄ and R ₅ are ring-closed to each other to form a 5- or 6-membered carbocycle. May be. Further, each of the above groups may have an arbitrary substituent.

Specific examples of the ultraviolet absorber represented by the general formula [1] are shown below, but the invention is not limited thereto.

UV-1: 2- (2'-hydroxy-5 '
-Methylphenyl) benzotriazole UV-2: 2- (2'-hydroxy-3 ', 5'-di-
tert-Butylphenyl) benzotriazole UV-3: 2- (2'-hydroxy-3'-tert-
Butyl-5'-methylphenyl) benzotriazole UV-4: 2- (2'-hydroxy-3 ', 5'-di-
tert-Butylphenyl) -5-chlorobenzotriazole UV-5: 2- (2'-hydroxy-3 '-(3 ",
4 ", 5", 6 "-tetrahydrophthalimidomethyl)
-5'-Methylphenyl) benzotriazole UV-6: 2,2-methylenebis (4- (1,1,3,3)
3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol) UV-7: 2- (2'-hydroxy-3'-tert-
Butyl-5'-methylphenyl) -5-chlorobenzotriazole UV-8: 2- (2H-benzotriazol-2-yl) -6- (linear and side chain dodecyl) -4-methylphenol (trade name: TINUVIN171, manufactured by Ciba Specialty Chemicals) UV-9: Octyl-3- [3-tert-butyl-4]
-Hydroxy-5- (chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazole- Two
-Yl) phenyl] propionate mixture (trade name:
TINUVIN109, manufactured by Ciba Specialty Chemicals Co., Ltd.) Among the above, as an ultraviolet absorber having a melting point of 20 ° C. or lower, UV-8 has a melting point of −56 ° C., and UV-9 has a normal temperature (25 ° C.). It is a yellow and transparent viscous liquid.

Further, as the benzophenone type ultraviolet absorber which is one of the ultraviolet absorbers which can be used in the present invention, the compound represented by the following general formula [2] is preferably used.

[0067]

[Chemical 2]

In the formula, Y represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxyl group or a phenyl group, and these alkyl group, alkenyl group or phenyl group may have a substituent. A represents a hydrogen atom, an alkyl group, an alkenyl group, a phenyl group, a cycloalkyl group, an alkylcarbonyl group, an alkylsulfonyl group or a -CO (NH) _n-1 -D group, and D represents an alkyl group, an alkenyl group or a substituent. Represents a phenyl group which may have. m and n each represent 1 or 2.

In the general formula [2], the alkyl group represents, for example, a straight-chain or branched aliphatic group having up to 24 carbon atoms, and the alkoxyl group represents, for example, an alkoxyl group having up to 18 carbon atoms and an alkenyl group. Is, for example, an alkenyl group having up to 16 carbon atoms, such as an allyl group, 2
-Represents a butenyl group and the like. Further, as a substituent for an alkyl group, an alkenyl group, or a phenyl group, a halogen atom,
For example, a chlorine atom, a bromine atom, a fluorine atom and the like, a hydroxyl group, a phenyl group, (the phenyl group may be substituted with an alkyl group or a halogen atom) and the like can be mentioned.

Specific examples of the benzophenone compound represented by the general formula [2] are shown below, but the invention is not limited thereto.

UV-10: 2,4-dihydroxybenzophenone UV-11: 2,2'-dihydroxy-4-methoxybenzophenone UV-12: 2-hydroxy-4-methoxy-5-sulfobenzophenone UV-13: bis ( 2-methoxy-4-hydroxy-5
-Benzoylphenylmethane) In each of the above-mentioned ultraviolet absorbers preferably used in the present invention, a benzotriazole-based ultraviolet absorber or a benzophenone-based ultraviolet absorber having high transparency and an excellent effect of preventing deterioration of a polarizing plate or a liquid crystal is A benzotriazole-based UV absorber which causes less unnecessary coloring is particularly preferably used.

The ultraviolet absorbent used in the base material according to the present invention may contain the ultraviolet absorbent having a distribution coefficient of 9.2 or more described in Japanese Patent Application No. 11-295209. The surface quality is excellent, and the alignment layer does not hinder the alignment.
In addition, the coating property is also excellent, and the partition coefficient is particularly 10.1.
It is preferable to use the above ultraviolet absorbers.

When a cellulose ester film containing a plasticizer or an ultraviolet absorber absorbent is used as a base material, it bleeds out and adheres to the plasma-treated part to contaminate the process, which adheres to the film. May cause damage to the base material. If the base material contains cellulose ester and a plasticizer, it may be
By using a base material whose mass change before and after treatment with 0% RH for 50 hours is less than ± 2 mass%, such process contamination can be significantly reduced, which is preferable. Such a cellulose ester film is disclosed in Japanese Patent Application No. 2000-33888.
The cellulose ester film described in 3 or the like is preferably used. Further, preferable ultraviolet absorbers for this purpose include JP-A-6-148430 and Japanese Patent Application No. 2000.
The high molecular weight UV absorbent or the UV absorbent polymer described in −156039 can be preferably used. In particular, the compound represented by formula (1) or formula (2) described in JP-A-6-148430, or Japanese Patent Application No. 20
The general formulas (3), (6),
The polymer ultraviolet absorber represented by (7) is particularly preferably used.

As the optical characteristics of the substrate, those having an in-plane retardation value RO of 0 to 1000 nm are preferably used, and a retardation value Rt in the thickness direction is 0 to 300.
Those of nm are preferably used depending on the application. It is preferable that the wavelength dispersion characteristic R ₆₀₀ / R _{4 50} is 0.7 to 1.3, it particularly preferably 1.0-1.3. Here, R ₄₅₀ is an in-plane retardation due to light having a wavelength of ₄₅₀ nm, and R ₆₀₀ is an in-plane retardation due to light having a wavelength of ₆₀₀ nm.

In the invention according to claim 4, in a polarizing plate in which a polarizing layer is sandwiched between two transparent supports A and B, an actinic ray curable resin is provided on the surface of the transparent support A opposite to the polarizing layer. It is characterized in that it has an antireflection layer through the layer and that the transparent support B has an actinic radiation curable resin layer on the surface opposite to the polarizing layer.

The actinic radiation curable resin layer referred to in the present invention is a layer mainly composed of a resin which is cured by a crosslinking reaction by irradiation with actinic rays such as ultraviolet rays and electron beams. Typical examples of the actinic ray curable resin include an ultraviolet curable resin and an electron beam curable resin, but a resin which is cured by irradiation with an actinic ray other than ultraviolet rays and electron beams may be used. As the ultraviolet curable resin, for example,
Examples thereof include UV-curable acrylic urethane-based resin, UV-curable polyester acrylate-based resin, UV-curable epoxy acrylate-based resin, UV-curable polyol acrylate-based resin, and UV-curable epoxy resin. Further, as specific examples, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate,
Examples thereof include dipentaerythritol hexaacrylate and alkyl-modified dipentaerythritol pentaacrylate.

As the UV-curable acrylic urethane resin, a product obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer is further added to 2-hydroxyethyl acrylate or 2-hydroxyethyl acrylate.
Examples include hydroxyethyl methacrylate (hereinafter, acrylate is referred to as acrylate only including acrylate) and 2-hydroxypropyl acrylate, which are easily formed by reacting an acrylate-based monomer having a hydroxyl group, Those described in JP-A-59-151110 can be used.

Examples of the UV-curable polyester acrylate resin include those which are easily formed by reacting a polyester polyol with 2-hydroxyethyl acrylate or a 2-hydroxy acrylate monomer. Those described in No. 151112 can be used.

Specific examples of the ultraviolet-curable epoxy acrylate resin include epoxy acrylate as an oligomer, a reactive diluent and a photoreaction initiator added thereto, and a reaction product. Kaihei 1-
The one described in No. 105738 can be used.

Specific examples of these photoreaction initiators include benzoin and derivatives, acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone and their derivatives. You may use it with a photosensitizer. The above photoreaction initiator can also be used as a photosensitizer. Further, when the epoxy acrylate-based photoreactive agent is used, a sensitizer such as n-butylamine, triethylamine or tri-n-butylphosphine can be used.

As the resin monomer, for example, a monomer having one unsaturated double bond is methyl acrylate,
Common monomers such as ethyl acrylate, butyl acrylate, benzyl acrylate, cyclohexyl acrylate, vinyl acetate and styrene can be mentioned. Further, as a monomer having two or more unsaturated double bonds, ethylene glycol diacrylate, propylene glycol diacrylate, divinylbenzene, 1,4-
Cyclohexane diacrylate, 1,4-cyclohexyl dimethyl adiacrylate, the above-mentioned trimethylol propane triacrylate, pentaerythritol tetraacrylic ester, etc. can be mentioned.

Further, the monomer may have liquid crystallinity. Examples of commercially available ultraviolet curable resins that can be used in the present invention include, for example, ADEKA OPTOMER KR / BY series: KR-400, KR-410, KR-550, KR.
-566, KR-567, BY-320B (manufactured by Asahi Denka Co., Ltd.); Koei Hard A-101-KK, A-1
01-WS, C-302, C-401-N, C-50
1, M-101, M-102, T-102, D-10
2, NS-101, FT-102Q8, MAG-1-P
20, AG-106, M-101-C (Kouei Chemical Co., Ltd.)
Made); SEIKA BEAM PHC2210 (S), PHC X
-9 (K-3), PHC2213, DP-10, DP-
20, DP-30, P1000, P1100, P120
0, P1300, P1400, P1500, P160
0, SCR900 (manufactured by Dainichiseika Kogyo KK); KRM7
033, KRM7039, KRM7130, KRM71
31, UVECRYL29201, UVECRYL29
202 (manufactured by Daicel UCB Ltd.); RC-5
015, RC-5016, RC-5020, RC-50
31, RC-5100, RC-5102, RC-512
0, RC-5122, RC-5152, RC-517
1, RC-5180, RC-5181 (manufactured by Dainippon Ink and Chemicals, Inc.); Aurex No. 340 Clear (manufactured by China Paint Co., Ltd.); Sunrad H-601 (manufactured by Sanyo Kasei Co., Ltd.); SP-1509, SP-1507
(Showa High Polymer Co., Ltd.); RCC-15C (Grace
Japan Co., Ltd.), Aronix M-6100, M-
8030, M-8060 (manufactured by Toagosei Co., Ltd.) and the like can be appropriately selected and used.

These actinic ray curable resin layers can be applied by a known method. As a light source for forming a cured coating layer by photo-curing a UV-curable resin, any light source that emits UV light can be used without limitation. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, a super high pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, etc. can be used. Irradiation conditions vary depending on each lamp, but the amount of irradiation light is 20 to 1000.
It may be about 0 mJ / cm ² , preferably 50 to 2
It is 000 mJ / cm ² . It can be efficiently formed in the near-ultraviolet region to the visible light region by using a sensitizer having an absorption maximum in that region.

The organic solvent for the ultraviolet-curable resin layer composition coating liquid is appropriately selected from, for example, hydrocarbons, alcohols, ketones, esters, glycol ethers, and other organic solvents, or these are selected. Can be mixed and used. Propylene glycol monoalkyl ether (having 1 to 4 carbon atoms in the alkyl group) or propylene glycol monoalkyl ether acetic acid ester (having 1 to 4 carbon atoms in the alkyl group) or the like is 5% by mass or more, more preferably 5 to 80%. It is preferable to use the above-mentioned organic solvent that is contained by mass% or more.

As a method for applying the ultraviolet-curable resin composition coating solution, a known method used for film formation can be applied. The coating amount is 0.1 to 30μ as a wet film thickness.
m is suitable, and preferably 0.5 to 15 μm.

In the invention according to claim 5, the film thickness ratio (UVb / UVa) between the film thickness UVa of the active ray curable resin layer of the transparent support A and the film thickness UVb of the active ray curable resin layer of the transparent support B.
Is 0.1 to 10 and is further characterized by:
In the invention according to, the film thickness ratio (UVb / UVa) is 0.
The feature is that it is 2 to 0.95. In addition, claim 6
In the invention according to, the film thickness UVb of the actinic radiation curable resin layer of the transparent support B is 1.3 μm or more,
It is preferably 1.5 to 4.0 μm.

The UV-curable resin composition is preferably irradiated with UV rays during or after coating and drying, and the irradiation time is preferably about 0.5 seconds to 5 minutes. From the viewpoint, 3 seconds to 2 minutes are more preferable.

To the cured resin layer thus obtained, in order to prevent blocking and enhance scratch resistance,
Fine particles of an inorganic compound or an organic compound can be added, and the types thereof are almost the same as the fine particles of the matting agent described above. The primary average particle diameter of these fine particle powders is preferably 0.005 to 1 μm and 0.01 to
Particularly preferably, it is 0.1 μm. The ratio of the ultraviolet curable resin composition to the fine particle powder is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin composition.

The UV curable resin layer is JIS B 060.
The center line average surface roughness (Ra) defined by 1 is 1 to 50.
Ra is 0.1 even if it is a clear hard coat layer of nm.
It may be an antiglare layer having a thickness of about 1 μm.

The invention according to claim 8 is characterized in that the transparent support A or the transparent support B has a metal oxide layer having a carbon content of 0.2 to 5%. In the invention, the transparent support A is characterized by having an antireflection layer containing a metal oxide layer having a refractive index of 2.0 or more,
It is preferably a metal oxide layer having a refractive index of 2.1 to 2.6.

The present invention is characterized in that the metal oxide layer is formed directly on the cellulose ester film or on the ultraviolet curable resin layer or the like. It has been found that the use of the metal oxide layer thus formed has the characteristic that pinhole defects are few. It is also a great effect that the number of pinholes does not increase over time.

These metal oxide layers are useful as antireflection layers such as low refractive index layers, medium refractive index layers, and high refractive index layers, or are preferably used as conductive layers and antistatic layers.

The carbon content referred to in the present invention can be determined by the following method. The carbon content of the film of the present invention can be measured using an XPS surface analyzer. The XPS surface analyzer is not particularly limited, and any model can be used.
ESCALAB-20 manufactured by VG Scientific Co., Ltd.
0R was used. Specifically, for example, Mg is used for the X-ray anode, and the output is measured at 600 W (accelerating voltage 15 kV, emission current 40 mA). The energy resolution is set to be 1.5 to 1.7 eV when defined by the half width of a clean Ag3d5 / 2 peak. Before measuring, the thickness of the
It is necessary to etch away the surface layer, which corresponds to a thickness of 20%. For removing the surface layer, it is preferable to use an ion gun that can use rare gas ions, and as the ion species, He, Ne, Ar, Xe, Kr or the like can be used.
First, the binding energy range from 0 eV to 1100 eV is measured at a data acquisition interval of 1.0 eV to determine what element is detected. Next, with respect to all the detected elements except the etching ion species, the data capturing interval is set to 0.2 eV, and a narrow scan is performed on the photoelectron peak that gives the maximum intensity, and the spectrum of each element is measured. The obtained spectrum was analyzed by VAMAS / SCA / JA in order to prevent the difference in the content rate calculation result due to the difference of the measuring device or the computer.
PAN made COMMON DATA PROCESSES
After transferring onto NG SYSTEM (Ver. 2.3), the same software is used to determine the value of carbon content as the atomic concentration. Before performing quantitative processing, C for each element
Calibrate the out Scale and 5
Performs point smoothing processing. In the quantitative processing, the peak area intensity (cps.
eV) was used. For background processing, Shir
The method by ley was used. For the Shirley method, see D.W. A. Shirley, Phys. Rev. , B
5,4709 (1972) can be referred to.

As a method for forming the metal oxide layer according to the present invention, the metal oxide layer may be provided by coating.
Plasma discharge treatment under atmospheric pressure or a pressure in the vicinity thereof is preferably used.

In the invention according to claim 10, the transparent support A
Is characterized by having an antireflection layer formed by atmospheric pressure plasma treatment.

The plasma processing that can be used in the present invention will be described below. An example of the atmospheric pressure plasma discharge treatment apparatus that can be used in the present invention is an apparatus as shown in FIG. In FIG. 2, F is a long-sized base material. Reference numeral 12 is a processing chamber for continuously performing plasma processing under atmospheric pressure or a pressure in the vicinity thereof, and reference numerals 13 and 14 are a pair of electrodes.

The processing chamber 12 is composed of a partitioned processing chamber having an inlet 12A and an outlet 12B for the base material F. Hereinafter, the processing unit will be described as a processing chamber.

In the illustrated example, the preliminary chamber 10 is provided adjacent to the processing chamber 12 on the inlet side of the base material, and the preliminary chamber 11 is provided adjacent to the preliminary chamber 10. A preparatory chamber 17 is also provided adjacent to the processing chamber 12 on the outlet side.

When a spare chamber is provided, as shown in FIG.
There may be a mode in which two are provided on the inlet side of the base material F and one is provided on the outlet side, but the present invention is not limited to this. Alternatively, it may be a mode not provided on the outlet side, or a mode in which two or more are provided on the inlet side and two or more are provided on the outlet side.

In any of the embodiments, the internal pressure in the processing chamber 12 is preferably higher than the internal pressure in the preparatory chamber adjacent to the processing chamber 12, and more preferably 0.30 Pa or more. By thus providing a pressure difference between the processing chamber 12 and the preparatory chamber, it is possible to prevent external air from being mixed in, effectively use the reaction gas, and further improve the processing effect.

When two or more auxiliary chambers are provided adjacent to the processing chamber 12 on the inlet side and two or more auxiliary chambers on the outlet side, the differential pressure between the auxiliary chamber and the adjacent auxiliary chambers is It is preferable that the internal pressure of the preparatory chamber on the side closer to 0.
It is preferable to set it higher than 30 Pa. By providing a pressure difference between the plurality of preparatory chambers as described above, the mixing of external air is more efficiently prevented, the reaction gas can be effectively used, and the treatment effect is further improved.

It is preferable that the preliminary chamber contains at least one component of the processing gas, preferably a rare gas, from the viewpoint of efficient use of the reaction gas and improvement of the processing effect.

It is necessary that the processing chamber 12, the spare chamber, and the spare chambers are partitioned from each other. As the partitioning means, as shown in the drawing, a pair of nip rollers 8 are provided on the inlet side and a pair of nip rollers 8 are provided on the outlet side. A form in which a pair of nip rollers 9 are provided is also preferable.

The nip roller has a function of closing or partitioning while contacting the base material F, but it cannot completely partition the rooms. Therefore, a means for providing a pressure difference as in the present embodiment is effective. It works.

Further, the partitioning means may have a mode in which a predetermined gap is maintained with respect to the base material F and it is not in contact with the base material F. As such a mode, an air curtain system or the like (not shown) can be adopted.

When the spare chamber is not provided, a partition may be provided between the processing chamber and the outside.

In the illustrated example, the pair of electrodes 13 and 14 are composed of a metal base material and a solid dielectric material, and the metal base material is lined with a dielectric material having an inorganic property. It is composed of a combination of ceramics sprayed and coated with a dielectric material that has been sealed with an inorganic material. Here, as the metal base material, metals such as silver, platinum, stainless steel, aluminum and iron can be used, but stainless steel is easy to process.

As the lining material, silicate glass, borate glass, phosphate glass, germanate glass, tellurite glass, aluminate glass, vanadate glass, etc. Can be used. Among them, borate glass is easy to process.

As the ceramics used for thermal spraying,
Alumina is preferable, and as the sealing material, a material obtained by sol-gel reaction of alkoxysilane or the like to be inorganicized is used.

In FIG. 2, a flat plate electrode is used like the pair of electrodes 13 and 14, but one or both electrodes may be a cylindrical electrode, a prismatic electrode, or a roll electrode.

A high frequency power source 15 is connected to one electrode 13 of the pair of electrodes 13 and 14, and the other electrode 14 is connected to the other electrode 14.
Is grounded by a ground 16 and a pair of electrodes 1
It is configured so that an electric field can be applied between 3 and 14.

The present means may cause the substrate to be treated to be charged and dust to be attached thereto. However, the following means for solving the problems do not cause a problem. For example, as the static elimination means, in addition to the ordinary blower type and contact type, which are described in JP-A-7-263173, a plurality of positive and negative ion generation static elimination electrodes and an ion suction electrode are opposed to sandwich the substrate. It is also preferable to use a high-density static elimination system provided with the static eliminator thus made and a positive / negative direct current type static eliminator thereafter. The charge amount of the base material at this time is ± 500.
V or less is preferable. Further, as the dust removing means after the static elimination treatment, a non-contact type jet decompression type dust removing device described in JP-A-7-60211 is preferable, but the dust removing means is not limited to this.

In the present invention, the pressure near atmospheric pressure means 20
Under pressure of ~ 200 kPa, preferably 93-10
It is in the range of 7 kPa.

In this method, one electrode is provided between the opposing electrodes.
It is preferable to apply a high frequency electric field having a frequency in the range of 00 kHz to 150 MHz. In particular, the higher the frequency, the higher the film forming speed, which is preferable.

Further, although such a high frequency electric field generally has a sine waveform, it is also possible to apply a pulsed electric field. This pulsing means that the plasma gas temperature can be changed by changing the ON / OFF duty ratio. Thereby, it may be possible to change the shape of the surface unevenness.

By applying the above-mentioned pulsed electric field, plasma discharge under atmospheric pressure and its vicinity can be generated without a rare gas, and the efficiency of plasma treatment can be improved.

To perform processing using the apparatus shown in FIG. 2, first, the substrate F to be conveyed enters the processing chamber 12, and the surface of the substrate F is treated by the plasma generated by the high frequency electric field in the processing chamber 12. Are continuously processed. Further, it is preferable that before the treatment, the surface of the base material is subjected to static elimination treatment and then dust is removed, because the uniformity of the surface treatment is further improved. As the charge removing means and the dust removing means after the charge removing processing,
Means similar to those described for the above apparatus can be used.

FIG. 3 is a schematic view showing an example of a plasma discharge treatment container installed in the plasma discharge treatment apparatus used in the present invention, with respect to a roll-type electrode 25 that winds the substrate F and conveys and rotates it. A plurality of cylindrical fixed electrodes 26
Are opposed to each other, and are wound around the roll-type electrode 25 and pressed by the nip rollers 65 and 66, the base material F is conveyed into the discharge processing chamber 30 through the guide rollers 64 and 67, and the electrode 25 rotates. Are transported and processed in synchronism with.

FIG. 4 is a schematic view showing another example of the plasma discharge processing container installed in the plasma discharge processing apparatus used in the present invention. In contrast to FIG. 3, a prismatic electrode 36 is used as the fixed electrode. This is an example of the above device, and has the effect of widening the discharge range compared to a cylinder.

Further, FIG. 5 is a perspective view showing an example of a cylindrical roll electrode used in the plasma discharge processing according to the present invention, and FIG. 6 is a fixed type used in the plasma discharge processing according to the present invention. FIG. 7 is a perspective view showing an example of a cylindrical electrode, and FIG. 7 is a perspective view showing an example of a fixed prismatic electrode used in the plasma discharge treatment according to the present invention.

As shown in FIG. 5, the electrode 25 is a combination of a conductive base material 25a such as a metal covered with a dielectric 25b of an inorganic substance by lining, or the same base material 25.
A is coated with a dielectric 25B that has been subjected to pore-sealing treatment with an inorganic material after ceramics thermal spraying. The electrodes 26 and 36 are also configured in the same combination.

Here again, the conductive base material 25a such as metal is used.
Can use metals such as silver, platinum, stainless steel, aluminum, and iron, but stainless steel is easy to process.

FIG. 8 is a schematic view showing an example of a discharge processing apparatus using discharge plasma according to the present invention. In FIG. 8, the electric discharge treatment device section is the same as that in FIG. 4, and is provided with a gas filling means 50, a power supply 40, an electrode cooling unit 60 and the like.

The electrodes 25 and 36 are shown in FIGS. 4, 5 and 6, and the gap between the opposing electrodes 25 and 36 is
For example, it is about 1 mm.

The gas filling means 50 is means for feeding a mixed gas of a rare gas and a reaction gas to the discharge processing chamber 30 to fill the mixed gas, and the mixed gas is helium (He) or argon (A).
The rare gas of r) and oxygen, hydrogen, an organic fluorine compound or a mixed gas thereof are used. It should be noted that it is desirable to discharge with a relatively inexpensive argon gas.

The power supply 40 is composed of conductive electrode portions 25a, 2 and
A voltage is applied to 5A, or 26a, 26A, or 36a, 36A. The electric discharge processing chamber 30 is composed of a processing container 31 made of Pyrex (R) glass.
1 is filled with the mixed gas. In the embodiment, the processing container 31 is made of Pyrex (R) glass, but may be made of metal as long as it is insulated from the electrodes. For example, the inner surface of the aluminum or stainless steel frame may be made of polyimide resin. Etc. may be adhered, and ceramics may be sprayed on the metal frame to provide insulation.

A roll-shaped electrode 25 and a prismatic electrode 36 are arranged at predetermined positions in the processing container 31, and a gas generator 51 is provided.
The mixed gas generated in step 3 is flow-controlled, and is introduced into the processing container 31 of the discharge processing chamber 30 through the air supply port 52.
The inside of 1 is filled with the mixed gas and discharged from the exhaust port 53. Next, a voltage is applied to the electrode 36 by the power source 40,
The electrode 25 is grounded to the ground to generate discharge plasma. Here, the base material F is supplied from the roll-shaped film 61, and the discharge processing chamber 30 is supplied through the guide rollers 64 and 67.
It is conveyed between the inner electrodes 25 and 36 with one surface in contact with the electrode 25. The surface of the base material F is subjected to discharge treatment by discharge plasma during transportation, and then discharged. Here, the surface of the base material F which is not in contact with the electrode 25 is subjected to the electric discharge treatment.

A mixed gas containing a rare gas or an inert gas according to the present invention will be described. The mixed gas according to the present invention preferably contains a rare gas and oxygen or hydrogen. Further, in order to form the metal oxide layer, an organic metal compound such as metal alkoxide is contained. Further, the low refractive index layer or the antiglare layer can be formed by using an organic fluorine compound.

In carrying out the plasma processing method according to the present invention, the gas to be used varies depending on the kind of the thin film to be provided on the substrate, but basically it is an inert gas and the reactivity for forming the thin film. It is a mixed gas of gases. The reactive gas is preferably contained in the mixed gas in an amount of 0.01 to 10% by volume. The thickness of the thin film is 0.1 to 10
A thin film in the range of 00 nm is obtained.

Examples of the above-mentioned inert gas include elements belonging to Group 18 of the periodic table, specifically, helium, neon, argon, krypton, xenon, radon, etc. In order to obtain the effects described in the present invention. Helium and argon are preferably used.

A metal compound layer can be formed by adding an organometallic compound to the reactive gas. For example, Li, Be, B, Na, M as the organometallic compound can be formed.
g, Al, Si, K, Ca, Sc, Ti, V, Cr, M
n, Fe, Co, Ni, Cu, Zn, Ga, Ge, R
b, Sr, Y, Zr, Nb, Mo, Cd, In, Ir,
Sn, Sb, Cs, Ba, La, Hf, Ta, W, T
l, Pb, Bi, Ce, Pr, Nd, Pm, Eu, G
It may include a metal selected from d, Tb, Dy, Ho, Er, Tm, Yb, and Lu. More preferably, these organometallic compounds are selected from metal alkoxides, alkylated metals, and metal complexes.

As the reactive gas, for example, zinc acetylacetonate, triethylindium, trimethylindium, diethylzinc, dimethylzinc, etraethyltin, etramethyltin, di-n-butyltin diacetate,
A metal oxide layer useful as a medium refractive index layer of a conductive film, an antistatic film, or an antireflection film by using a reactive gas containing at least one organometallic compound selected from tetrabutyltin, tetraoctyltin, etc. Can be formed.

Further, by using the fluorine-containing compound gas, it is possible to obtain a water-repellent film which forms a fluorine-containing group on the surface of the substrate to lower the surface energy and obtain a water-repellent surface. Examples of the elemental fluorine-containing compound include fluorinated carbon compounds such as propylene hexafluoride (CF ₃ CFCF ₂ ) and cyclobutane octafluoride (C ₄ F ₈ ). From the viewpoint of safety, propylene hexafluoride and cyclobutane octafluoride that do not generate hydrogen fluoride, which is a harmful gas, are used.

Further, a hydrophilic polymer film can be deposited by performing the treatment in an atmosphere of a monomer having a hydrophilic group and a polymerizable unsaturated bond in the molecule. Examples of the hydrophilic group include a hydroxyl group, a sulfonic acid group, a sulfonate group, a primary or secondary or tertiary amino group, an amide group, 4
Examples thereof include hydrophilic groups such as a primary ammonium group, a carboxylic acid group, and a carboxylic acid group. Also, a hydrophilic polymer film can be similarly deposited by using a monomer having a polyethylene glycol chain.

As the above-mentioned monomer, acrylic acid, methacrylic acid, acrylamide, methacrylamide, N, N
-Dimethylacrylamide, sodium acrylate, sodium methacrylate, potassium acrylate, potassium methacrylate, sodium styrenesulfonate, allyl alcohol, allylamine, polyethylene glycol dimethacrylic acid ester, polyethylene glycol diacrylic acid ester, and the like. At least 1
Seeds can be used.

By using a reactive gas containing an organic fluorine compound, a silicon compound or a titanium compound, the low refractive index layer or the high refractive index layer of the antireflection film can be provided.

As the organic fluorine compound, fluorocarbon gas, fluorohydrocarbon gas and the like are preferably used. Examples of the carbon fluoride gas include carbon tetrafluoride and carbon hexafluoride, specifically, tetrafluoromethane, tetrafluoroethylene, hexafluoropropylene, octafluorocyclobutane, and the like.
As the above-mentioned fluorohydrocarbon gas, difluoromethane,
Examples include tetrafluoroethane, propylene tetrafluoride, propylene trifluoride, and the like.

Further, halogenated fluorocarbon compounds such as trifluoromethane trichloride, monofluorodifluoromethane, difluorotetrafluorocyclobutane and the like, and fluorine-substituted compounds of organic compounds such as alcohols, acids and ketones are used. It can be used, but is not limited thereto. Further, these compounds may have an ethylenically unsaturated group in the molecule. The above compounds may be used alone or in combination.

When the above-mentioned organic fluorine compound is used in the mixed gas, from the viewpoint of forming a uniform thin film on the substrate by the discharge plasma treatment, the content of the organic fluorine compound in the mixed gas is 0.1 to 0.1%. The content is preferably 10% by volume, more preferably 0.1 to 5% by volume.

When the organic fluorine compound according to the present invention is a gas at normal temperature and pressure, it can be used as it is as a constituent component of a mixed gas, so that the method of the present invention can be most easily performed. However, when the organic fluorine compound is a liquid or a solid at room temperature and atmospheric pressure, it may be used after being vaporized by a method such as heating or depressurization, or may be dissolved in a suitable solvent before use. .

When the titanium compound described above is used in the mixed gas, the content of the titanium compound in the mixed gas is 0.1 to 10 volumes from the viewpoint of forming a uniform thin film on the substrate by the discharge plasma treatment. %, More preferably 0.1 to 5% by volume.

The hardness of the thin film can be remarkably improved by adding 0.1 to 10% by volume of hydrogen gas in the mixed gas described above.

Further, by containing 0.01 to 5% by volume of a component selected from oxygen, ozone, hydrogen peroxide, carbon dioxide, carbon monoxide, hydrogen and nitrogen in the mixed gas,
The reaction can be accelerated, and a dense and high-quality thin film can be formed.

As the above-mentioned silicon compound and titanium compound, a metal hydrogen compound and a metal alkoxide are preferable from the viewpoint of handling, and they are free from corrosive and harmful gases.
A metal alkoxide is preferably used because it is less likely to be contaminated during the process.

In order to introduce the above-mentioned silicon compound and titanium compound between the electrodes which are the discharge spaces, both may be in a gas, liquid or solid state at normal temperature and pressure. In the case of gas, it can be introduced into the discharge space as it is, but in the case of liquid or solid, it is used after being vaporized by means such as heating, decompression, ultrasonic irradiation or the like. When a silicon compound or a titanium compound is used after being vaporized by heating, a metal alkoxide that is liquid at room temperature and has a boiling point of 200 ° C. or lower, such as tetraethoxysilane and tetraisopropoxytitanium, is preferably used for forming the antireflection film. The metal alkoxide may be used after diluting it with a solvent, and as the solvent, an organic solvent such as methanol, ethanol, n-hexane, or a mixed solvent thereof can be used. Since these diluting solvents are decomposed into molecules and atoms during the plasma discharge treatment, their influence on the formation of a thin film on the substrate and the composition of the thin film can be almost ignored.

Examples of the silicon compound described above include:
Organometallic compounds such as dimethylsilane and tetramethylsilane, metal hydrogen compounds such as monosilane and disilane, metal halogen compounds such as silane dichloride and silane trichloride,
It is preferable to use alkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and dimethyldiethoxysilane, and organosilanes, but not limited to these. Moreover, these can be used in appropriate combination.

When the silicon compound described above is used in the mixed gas, the content of the silicon compound in the mixed gas is 0.1 to 10 volumes from the viewpoint of forming a uniform thin film on the substrate by the discharge plasma treatment. %, More preferably 0.1 to 5% by volume.

Examples of the titanium compound described above include organometallic compounds such as tetradimethylaminotitanium, metal hydrogen compounds such as monotitanium and dititanium, metal halogen compounds such as titanium dichloride, titanium trichloride and titanium tetrachloride,
Tetraethoxy titanium, tetraisopropoxy titanium,
It is preferable to use a metal alkoxide such as tetrabutoxytitanium, but not limited thereto.

The invention according to claim 11 is characterized in that the low reflectance polarizing plate has an average reflectance of 0.5% or less at 450 to 650 nm, and the minimum reflectance in this range is 0.00 to 0. It is particularly preferably 3%.

In addition to the functional layers described above, each transparent support according to the present invention may be provided with a back coat layer containing fine particles on the back surface side in order to adjust the dynamic friction coefficient of the film. The coefficient of dynamic friction can be adjusted by the size and amount of the fine particles to be added, the material, and the like.

As the fine particles contained in the back coat layer useful in the present invention, there may be mentioned fine particles of an inorganic compound or fine particles of an organic compound. The apparent specific gravity and dispersion method are almost the same.

The amount of the fine particles added to the binder in the back coat layer was 100 parts by weight of the resin, and the amount of the fine particles was 0.
01 to 1 part by mass is preferred, 0.05 to 0.5 part by mass is more preferred, and 0.08 to 0.2 part by mass is most preferred. The larger the added amount, the lower the dynamic friction coefficient, and the smaller the added amount, the lower the haze and the less the agglomerates.

The organic solvent used in the back coat layer is not particularly limited, but since an anti-curl function can be imparted to the back coat layer, an organic solvent that dissolves the base film and the resin of the material of the base film or Organic solvents that swell are useful. These may be appropriately selected depending on the curl degree of the base film, the type of resin, the mixing ratio, the coating amount, and the like.

Examples of the organic solvent which can be used in the back coat layer include benzene, toluene, xylene, dioxane, acetone, methyl ethyl ketone, N, N-dimethylformamide, methyl acetate, ethyl acetate, trichloroethylene, methylene chloride, ethylene chloride, and the like.
Tetrachloroethane, trichloroethane, chloroform or N-methylpyrrolidone, 1,3-dimethyl-2
-Imidazolidinone. Examples of the organic solvent that is not dissolved include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, and n-butanol, but the organic solvent is not particularly limited thereto.

As a method for applying the coating composition for the back coat layer, a gravure coater, a dip coater, a wire bar coater, a reverse coater, an extrusion coater or the like is used, and the coating liquid film thickness (also referred to as wet film thickness) is 1 To 100 μm is preferable, and especially 5 to
30 μm is preferable.

The resin used in the back coat layer is, for example, vinyl chloride / vinyl acetate copolymer, vinyl chloride resin, vinyl acetate resin, copolymer of vinyl acetate and vinyl alcohol, partially hydrolyzed vinyl chloride / vinyl acetate. Vinyl homopolymers or copolymers such as copolymers, vinyl chloride / vinylidene chloride copolymers, vinyl chloride / acrylonitrile copolymers, ethylene / vinyl alcohol copolymers, chlorinated polyvinyl chloride, ethylene / vinyl chloride copolymers, ethylene / vinyl acetate copolymers, cellulose nitrate. , Cellulose acetate propionate, cellulose diacetate, cellulose triacetate, cellulose acetate phthalate,
Cellulose ester resins such as cellulose acetate butyrate resin, copolymers of maleic acid and / or acrylic acid, acrylic acid ester copolymers, acrylonitrile / styrene copolymers, chlorinated polyethylene,
Acrylonitrile / chlorinated polyethylene / styrene copolymer, methyl methacrylate / butadiene / styrene copolymer, acrylic resin, polyvinyl acetal resin, polyvinyl butyral resin, polyester polyurethane resin, polyether polyurethane resin, polycarbonate polyurethane resin, polyester resin, polyether resin, polyamide resin Examples include rubber resins such as amino resins, styrene / butadiene resins and butadiene / acrylonitrile resins, silicone resins, fluorine resins, polymethylmethacrylate, and copolymers of polymethylmethacrylate and polymethylacrylate. It is not limited to these. Particularly preferred is a cellulose resin layer such as cellulose diacetate or cellulose acetate propionate.

For example, by providing the back coat layer as described above, the dynamic friction coefficient can be made 0.9 or less.

The low reflection polarizing plate of the present invention and the display device of the present invention will be described. As the polarizer used in the low-reflection polarizing plate of the present invention, conventionally known ones can be used.
For example, it is possible to use a film made of a hydrophilic polymer such as polyvinyl alcohol, which is treated with a dichroic dye such as iodine and stretched, or a film of a plastic film such as vinyl chloride which is oriented with polyene. it can. The low reflection polarizing plate of the present invention is provided at least on the cell-side surface side of the liquid crystal cell. When provided on both sides, the transparent support A according to the present invention can be attached to the polarizer closer to the liquid crystal cell. From the above, the liquid crystal display device of the present invention can be obtained. The low reflection polarizing plate of the present invention is preferably used for a liquid crystal display device because of its low reflectivity and good ultraviolet ray cutting performance.

[0159]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

Example 1 << Preparation of Cellulose Ester Film >> A cellulose ester film as a base film was prepared according to the method described below.

[Preparation of Dope] (Preparation of Silicon Oxide Dispersion) Aerosil 200V (manufactured by Nippon Aerosil Co., Ltd.) 1 kg Ethanol 9 kg After stirring and mixing the above materials with a dissolver for 30 minutes, a Manton-Gaulin type high-pressure disperser was used. Dispersion was performed.

(Preparation of Additive Solution A) Cellulose acetate propionate (acetyl substitution degree: 1.9, propionyl group substitution degree: 0.7) 4 kg Methylene chloride 76 kg Tinuvin 326 (manufactured by Ciba Specialty Chemicals) 3 kg Tinuvin 109 (Ciba) Specialty Chemicals Co., Ltd.) 4 kg Tinuvin 171 (Ciba Specialty Chemicals Co., Ltd.) 4 kg The above materials were placed in a closed container and completely dissolved and filtered while heating and stirring. To this, 9 kg of the above silicon oxide dispersion was added with stirring, and the mixture was further stirred for 30 minutes and then filtered to prepare an addition liquid A.

[Preparation of Dope A] Triphenyl phosphate 15 kg Ethylphthalylethyl glycolate 5 kg Methylene chloride 640 kg Ethanol 120 kg Cellulose acetate propionate (acetyl substitution degree: 1.90, propionyl group substitution degree 0.70, average substitution) 2.60) 220 kg The above materials were sequentially charged into a closed container with stirring, and completely dissolved and mixed while heating and stirring. The dope was cooled to a temperature at which it was cast, left standing overnight, and subjected to a defoaming operation. Then, the solution was added to Azumi Filter Paper No. Filtered using 244. Further, the additive liquid A was added at a ratio of 2 kg per 100 kg of this solution, sufficiently mixed with an in-line mixer (Toray static type in-tube mixer Hi-Mixer SWJ), and then filtered to prepare a dope A.

[Preparation of Dope B] The cellulose acetate propionate (acetyl substitution degree: 1.90, propionyl group substitution degree 0.70) used in the above-mentioned additive liquid A and dope A was replaced with cellulose acetate propionate (acetyl substitution). Degree: 2.00, propionyl group substitution degree 0.8
The additive liquid B and the dope B were prepared in the same manner except that the average substitution degree was changed to 0 and the average substitution degree was 2.80).

[Preparation of Dope C] Cellulose acetate propionate (acetyl substitution degree: 1.90, propionyl group substitution degree: 0.70) used in the above-mentioned additive liquid A and dope A was mixed with cellulose acetate (acetyl substitution degree:
An additive solution C and a dope C were prepared in the same manner except that the procedure was changed to 2.66).

[Preparation of Dope D] The cellulose acetate propionate (acetyl substitution degree: 1.9, propionyl group substitution degree: 0.
7) to cellulose acetate (acetyl substitution degree: 2.7
Additive liquid D and dope D were prepared in the same manner except that the content was changed to 0).

[Preparation of Dope E] The cellulose acetate propionate (acetyl substitution degree: 1.9, propionyl group substitution degree: 0.
7) to cellulose acetate (acetyl substitution degree: 2.7
Additive solution E and dope E were prepared in the same manner except that the procedure was changed to 5).

[Preparation of Dope F] The cellulose acetate propionate (acetyl substitution degree: 1.9, propionyl group substitution degree: 0.
7) to cellulose acetate (acetyl substitution degree: 2.8
An additive solution F and a dope F were prepared in the same manner except that the procedure was changed to 5).

[Preparation of Dope G] Additive liquid A and dope A
In the same manner as in Example 1, except that the cellulose acetate propionate (acetyl substitution degree: 1.9, propionyl group substitution degree: 0.7) used in Example 2 was changed to cellulose acetate (acetyl substitution degree: 2.90). Dope G was prepared.

[Preparation of Dope H] Additive liquid A and dope A
In the same manner as in Example 2, except that the cellulose acetate propionate (acetyl substitution degree: 1.9, propionyl group substitution degree: 0.7) used in Example 2 was changed to cellulose acetate (acetyl substitution degree: 2.50). H was prepared.

(Measurement of degree of substitution of cellulose ester)
The degree of substitution of the cellulose ester used in the preparation of each of the above dopes A to H is ASTM-D817-96.
The measurement was performed according to the method specified in 1.

[Preparation of Cellulose Ester Film]
(Production of Cellulose Ester Film 1) Using the dope A prepared above, a transparent support 1 was prepared as follows.

After the dope A was filtered, it was uniformly cast on a stainless band support at 30 ° C. at a dope temperature of 35 ° C. using a belt casting device. Then, after drying to a peelable range, the web was peeled from the stainless band support. The residual solvent amount of the web at this time was 80%.

After peeling from the stainless band support,
After drying while roll-conveying in a drying zone of 85 ° C., when the residual solvent amount became less than 35% by mass, 2
9 while stretching 1.07 times in the TD direction (width direction) and 1.01 times in the MD direction (film forming direction) with an axial stretching tenter.
After drying at 0 ° C., the width grip is released, the drying is completed in the drying zone at 125 ° C. while being transported by roll, and the both ends of the film are knurled to have a width of 10 mm and a height of 8 μm, and a film thickness of 41 μm. A cellulose ester film 1 was produced. The film width was 1300 mm and the winding length was 2000 m. The amount of residual solvent during winding is 0.1
It was less than mass%.

(Production of Cellulose Ester Films 2 to 30) In the production of the above-mentioned cellulose ester film 1, the same procedure was performed except that the kind of dope, the stretching ratio and the film thickness in the biaxial stretching tenter were changed as shown in Table 1. Thus, cellulose ester films 2 to 30 were produced.

(Measurement of Retardation Value: Rt) Using an automatic birefringence meter KOBRA-21ADH (manufactured by Oji Scientific Instruments Co., Ltd.) in an environment of 23 ° C. and 55% RH,
Three-dimensional refractive index measurement is performed at a wavelength of 590 nm,
The refractive indices nx, ny and nz were obtained. The retardation value (Rt) was calculated according to the following (formula A).

Rt = ((nx + ny) / 2−nz) × d (Formula A) In the formula, nx is the refractive index of the film in the direction parallel to the film forming direction in the film plane. ny is the refractive index of the film in the direction perpendicular to the film forming direction. nz is the refractive index in the thickness direction of the film. d represents the thickness (nm) of the film, respectively.

(Measurement of Retardation Value: RO) The refractive indices nx and ny were determined by the same method as above. The retardation value (RO) in the surface direction according to the following (formula B)
Was calculated.

RO = (nx-ny) × d (Formula B) In the formula, nx is the refractive index in the direction in which the refractive index in the film surface is the largest, and ny is the refractive index in the film surface in the direction perpendicular to nx. , D represent the thickness (nm) of the film, respectively.

[0180]

[Table 1]

<< Preparation of Transparent Support >> [Preparation of Transparent Support 1C] The above-prepared cellulose ester film 1 is provided with a back coat layer, a clear hard coat layer and an antireflection layer described below to form a transparent support. 1C was produced.

(Coating of Backcoat Layer) The following backcoat layer coating composition 1 was used to prepare a cellulose ester film a.
Surface (side that was in contact with the belt support during casting film formation (b
The surface opposite to the surface) was extrusion-coated to a wet film thickness of 13 μm and dried at a drying temperature of 80 ° C. to form a back coat layer.

<Backcoat Layer Coating Composition 1> Acetone 30 parts by mass Ethyl acetate 45 parts by mass Isopropyl alcohol 10 parts by mass Diacetyl cellulose 0.5 parts by mass Ultrafine particle silica 2% acetone dispersion (Aerosil 200V: manufactured by Nippon Aerosil Co., Ltd.) 0.11 parts by mass (coating of a clear hard coat layer) Further, on the surface b of the transparent support 1 (side surface where the dope was in contact with the belt support during casting film formation), the following clear hard coat layer coating composition 1 was extrusion-coated to a wet film thickness of 13 μm, then dried in a drying unit set at 80 ° C., and then 1
UV irradiation at 18 mJ / cm ² and dry film thickness of 3.5μ
A clear hard coat layer having a center line average surface roughness (Ra) of m of 8 nm was provided.

<Clear hard coat layer (actinic ray curable resin layer) coating composition 1> Dipentaerythritol hexaacrylate monomer 60 parts by mass Dipentaerythritol hexaacrylate dimer 20 parts by mass Dipentaerythritol hexaacrylate trimer The above components 20 parts by mass Dimethoxybenzophenone photoinitiator 4 parts by mass Methyl ethyl ketone 75 parts by mass Propylene glycol monomethyl ether 75 parts by mass Furthermore, an antireflection layer is provided on the clear hard coat layer according to the following procedure, and the transparent support 1C is provided. (A transparent support having C added thereto has a clear hard coat layer and an antireflection layer).

(Formation of Antireflection Layer) Using the plasma discharge treatment apparatus shown in FIG. 2, an antireflection layer was formed on the clear hard coat layer. Details of forming the antireflection layer are shown below.

Two plasma discharge treatment vessels as shown in FIG. 2 were installed in the plasma discharge treatment apparatus, and continuous atmospheric pressure plasma treatment was carried out on the clear hard coat layer of the transparent support to successively form a tin oxide layer. (Refractive index 1.7, film thickness 69 nm, carbon content 0.3%), titanium oxide layer (refractive index 2.14,
Thickness 110 nm, carbon content 0.4%, silicon oxide layer (refractive index 1.45, thickness 87 nm, carbon content 0.2)
%).

<Measurement of Carbon Content> The carbon content of the film of the present invention was measured using an XPS surface analyzer. As the XPS surface analyzer, ESCALAB-200R manufactured by VG Scientific Co., Ltd. was used.
Mg was used for the X-ray anode, and the output was measured at 600 W (accelerating voltage 15 kV, emission current 40 mA). The energy resolution was set to be 1.5 to 1.7 eV when defined by the full width at half maximum of a clean Ag3d5 / 2 peak. Before the measurement, the surface layer corresponding to 10 to 20% of the film thickness was removed by etching. To remove the surface layer, Ar ion etching was used to remove the surface layer. First, the binding energy range from 0 eV to 1100 eV was measured at a data acquisition interval of 1.0 eV to determine what element was detected. Next, for all the detected elements except the etching ion species, the data capturing interval was set to 0.2 eV, a narrow scan was performed on the photoelectron peak giving the maximum intensity, and the spectrum of each element was measured. The obtained spectrum was analyzed by VAMAS in order to prevent the difference in the content rate calculation result due to the difference of the measuring device or the computer.
-COMCADATA PR made by SCA-JAPAN
After transferring to OCESSING SYSTEM (Ver.2.3), the same software was used to calculate the carbon content value by atomic concentration (atomicconcentrat).
Ion). Prior to the quantitative treatment, the Count Scale was calibrated for each element, and a 5-point smoothing treatment was performed. In the quantification process, the peak area intensity with the background removed was used.

<Plasma Discharge Treatment> Plasma discharge treatment was carried out by the following procedure. In the plasma discharge treatment apparatus shown in FIG. 3, as a roll electrode 25, a stainless steel jacket roll base material having a cooling function by cooling water (cooling function is not shown in FIG. 2) is ceramic sprayed with 1 mm of alumina. After coating, a solution prepared by diluting tetramethoxysilane with ethyl acetate was applied, dried, and then cured by UV irradiation to be cured, and a roll electrode having a dielectric material subjected to a sealing treatment was manufactured and grounded. On the other hand, as the application electrode 26, a hollow stainless steel pipe is coated with the same dielectric as the above under the same conditions to form an electrode group facing each other, and the required film thicknesses of the low refractive index layer and the high refractive index layer are respectively set. Adjusted to obtain. The power source used for generating the discharge plasma was a high frequency power source manufactured by JEOL Ltd., and a continuous frequency of 13.56 MHz and a power of 15 W / cm ² were supplied. However, the roll electrode was rotated in synchronization with the conveyance of the substrate using a drive.

The composition of the mixed gas (reaction gas) used for the plasma treatment is described below. (Reaction Gas for Forming Tin Oxide Layer) Argon is 98.7%, hydrogen gas is 1%, and tetrabutyltin vapor is 0.3%.

(Titanium oxide layer forming reaction gas) Argon is 98.7%, hydrogen gas is 1%, and tetraisopropoxytitanium vapor is 0.3%.

(Reaction Gas for Forming Silicon Oxide Layer) Argon is 98.7%, hydrogen gas is 1%, and tetramethoxysilane vapor is 0.3%.

[Preparation of Transparent Supports 2C to 30C] Similar to the preparation of the transparent support 1C, each layer described above is coated on the cellulose ester films 2 to 30 and further plasma-treated to give a transparent support. The bodies 2C to 30C were produced.

Cellulose ester films 1 to 3
0, transparent supports 1C to 30C all have a haze of 0
It was 0.2%. The haze is measured by ASTM-
It was measured according to D1003-52.

<< Preparation of Polarizing Plate >> Polarization was carried out by the transparent support A (back coat layer, clear hard coat layer and antireflection layer) and the transparent support B (cellulose ester film alone) with the combinations shown in Tables 2 and 3. Polarizing plates 1 to 34 having a structure sandwiching layers were produced by the method described below.

The transparent support A and the transparent support B were treated with a 1 mol / L NaOH aqueous solution at 50 ° C. for 1 minute to saponify the surfaces. In the saponification treatment, a protective film (thickness: 50 μm) made of polyethylene terephthalate having a removable adhesive was attached to the antireflection layer surface of the transparent support A to protect it from alkali. A polarizing layer made of stretched polyvinyl alcohol doped with iodine was sandwiched between the backcoat layer side of the transparent support A subjected to saponification treatment and the transparent support B to obtain a polarizing plate. In this way, the polarizing plates 1 to 34 shown in Tables 2 and 3 were produced.

<< Evaluation of Polarizing Plate >> The following evaluation was performed on each polarizing plate prepared as described above.

(Evaluation of curl / planarity) Each of the above-prepared polarizing plates was cut into a size of 10 cm × 10 cm, and the temperature was kept at 60 ° C. for 90 minutes.
After being left in an atmosphere of% RH for 48 hours, changes in curl degree and flatness were evaluated according to a conventional method, and judgment was made according to the following criteria.

⊚: No curl is observed and no deterioration of flatness is observed. ○: Weak curl is observed, but no significant deterioration of flatness is observed. Δ: Curling degree is high, but practically no problem. X: The curl degree is remarkably increased and the flatness is deteriorated (measurement of reflectance). The spectral reflectance of the low-reflectivity laminate is 5 degrees regular reflection using a spectrophotometer U-4000 type (manufactured by Hitachi Ltd.). The reflectance was measured under the conditions. Measurement, after roughening the back side of the observation side, perform light absorption treatment using a black spray, to prevent the reflection of light on the back side of the film,
The reflectance (for wavelengths of 400 nm to 700 nm) was measured. The average reflectance was calculated in the range of 450 nm to 650 nm.

FIG. 9 shows, as an example, the reflection spectrum data of the polarizing plate 2 produced above. (Evaluation of visibility) Each polarizing plate prepared above was attached to a liquid crystal panel for evaluation. At this time, the antireflection layer was arranged so as to face outward.

The polarizing plates on both the front and back sides of a color liquid crystal display (MODEL VL-1530S manufactured by Fujitsu Ltd.) were peeled off, and each of the above-prepared polarizing plates was attached so that the absorption axis was the same as the original polarizing plate. It was 40 ℃, 9
After standing for 1 month at 0% RH, the contrast of the screen was visually evaluated, and the visibility was determined according to the criteria described below.

⊚: No decrease in contrast is observed ∘: A slight decrease in contrast is observed in the peripheral area of the screen Δ: A decrease in contrast is observed in the peripheral area of the screen ×: Significant decrease in contrast is observed Each of the above The evaluation results are shown in Tables 2 and 3.

[0202]

[Table 2]

[0203]

[Table 3]

As is clear from Tables 2 and 3, the low-reflection polarizing plate of the present invention has better curl and flatness than the comparative example, and is excellent in visibility.

Example 2 << Preparation of Transparent Support A >> (Preparation of Transparent Support 24A) A back coat layer was provided on the a-side of the cellulose ester film 24 in the same manner as in Example 1. Further, an antiglare layer having a predetermined film thickness was formed on the b side by the following method.

The following coating composition 2 was extrusion coated,
Then, after drying in a drying unit set at 80 ° C., 120
Ultraviolet irradiation was performed at mJ / cm ² to provide an antiglare layer (center line average roughness Ra: 0.3 μm) having a dry film thickness of 4 μm.

<Coating Composition 2: Preparation of Coating Solution for Preparing Antiglare Layer> Ethyl acetate 50 parts by mass Methyl ethyl ketone 50 parts by mass Isopropyl alcohol 50 parts by mass Sylysia 431 (average particle size 2.5 μm, manufactured by Fuji Silysia Chemical Ltd.) 2. 5 parts by mass Aerosil R972V (average particle size: 16 nm, manufactured by Nippon Aerosil Co., Ltd.) 2 parts by mass or more are stirred with a high-speed stirrer (TK homomixer, manufactured by Tokushu Kika Kogyo Co., Ltd.), and then a collision type disperser (Manton Gorin, After dispersion with Gorin Co., Ltd., the following components were added to prepare coating composition 2.

Dipentaerythritol hexaacrylate monomer 60 parts by mass Dipentaerythritol hexaacrylate dimer 20 parts by mass Dipentaerythritol hexaacrylate trimer 20 parts by mass Dimethoxybenzophenone photoinitiator 4 parts by mass (transparent Supports 15A, 20A, 22A, 23A, 25A
Production of the transparent support 24A in the production of the transparent support 24A, the cellulose ester film 24 is changed to cellulose ester films 15, 20, 22, 23, 25, and the transparent support 15A having an antiglare layer having a film thickness shown in Table 4. , 20A, 2
2A, 23A and 25A were produced. The film thickness was adjusted by increasing or decreasing the wet film thickness during coating and diluting the coating composition 2. The dilution was performed without changing the solvent ratio of the coating composition 2.

Then, in the same manner as in Example 1, each transparent support was continuously subjected to atmospheric pressure plasma treatment on the formed antiglare layer to sequentially form a tin oxide layer (refractive index 1.7, film. Thickness 69 nm, carbon content 0.3%), titanium oxide layer (refractive index 2.14, film thickness 110 nm, carbon content 0.4%)
And a silicon oxide layer (refractive index 1.45, film thickness 87 nm, carbon content 0.2%).

<< Preparation of Transparent Support B >> (Preparation of Transparent Support 6B) A back coat layer was formed on the a-side of the cellulose ester film 6 in the same manner as in Example 1, and the coating composition described below was formed on the b-side. No. 3 was extrusion coated, then dried in a drying section set at 80 ° C., 118
After irradiating with ultraviolet light at mJ / cm ² , a clear hard coat layer having the constitution described below is provided to give a transparent support 6B.
Was produced.

As the transparent support 6B, 6 kinds having different dry film thickness of the clear hard coat layer as shown in Table 4 were prepared.

<Clear hard coat layer (actinic ray curable resin layer) coating composition 3> Dipentaerythritol hexaacrylate monomer 60 parts by mass Dipentaerythritol hexaacrylate dimer 20 parts by mass Dipentaerythritol hexaacrylate trimer Ingredients 20 parts by mass Dimethoxybenzophenone photoinitiator 4 parts by mass Methyl ethyl ketone 75 parts by mass Propylene glycol monomethyl ether 75 parts by mass (Preparation of transparent support 4B, 5B, 14B) Cellulose ester film in preparation of transparent support 6B 6
Instead of cellulose ester film 4,
5 and 14 were used, and the dry film thickness of the clear hard coat layer shown in Table 4 was changed, and the transparent support 4 having different dry film thickness of the clear hard coat layer was similarly prepared.
B, 5B and 14B were produced.

<< Preparation of Polarizing Plates >> Using the combinations shown in Table 4, polarizing plates 35 to 61 each having a structure in which a polarizing layer is sandwiched between a transparent support A and a transparent support B are prepared by the method described in Example 1. did.

<< Evaluation of Polarizing Plate >> (Evaluation of Curling / Flatness and Reflectance) Each polarizing plate prepared above was evaluated according to the method described in Example 1.

(Evaluation Method of Viewing Angle) With respect to each of the above-prepared polarizing plates, the viewing angle was measured according to the method described below.

The polarizing plates on both the front and back sides of a color liquid crystal display (MODEL VL-1530S manufactured by Fujitsu Ltd.) were peeled off so that each polarizing plate prepared in the example became the same as the original polarizing plate with the absorption axis. Stuck to. 40 this
After standing at 90 ° C. and 90% RH for 1 month, the viewing angle was measured by EZ-contrast manufactured by ELDIM. The viewing angle is in the viewing angle range of the surface in the direction of an angle of 45 degrees (the surface inclined at an angle of 45 degrees from the upper left to the lower right of the panel) with respect to the panel surface showing a contrast ratio of 10 or more when displaying white and black on the liquid crystal panel. An evaluation was made.

[0217] ⊚: Viewing angle in the oblique direction of 45 degrees is 120 to 130 degrees ◯: Viewing angle in the oblique 45 degree direction is less than 110 to 120 degrees. Δ: Viewing angle in the oblique 45 ° direction is 100 to less than 110 ° ×: Viewing angle in the direction of 45 degrees obliquely is less than 100 degrees Table 4 shows each evaluation result obtained as described above.

[0218]

[Table 4]

As is clear from Table 4, it was confirmed that the polarizing plate of the present invention was excellent in curl and flatness and had a wide viewing angle as compared with the polarizing plate of the comparative example. I was able to read even the letters.

[0220]

According to the present invention, it is possible to provide a low-reflection polarizing plate having excellent curl and flatness and excellent display characteristics such as visibility and viewing angle, and a display device using the same.

[Brief description of drawings]

FIG. 1 is a configuration diagram showing an example of a typical configuration of a low-reflection polarizing plate of the present invention.

FIG. 2 is a sectional view showing an example of an atmospheric pressure plasma discharge treatment apparatus used in the present invention.

FIG. 3 is a schematic view showing an example of a plasma discharge treatment container installed in the plasma discharge treatment apparatus used in the present invention.

FIG. 4 is a schematic view showing another example of the plasma discharge treatment container installed in the plasma discharge treatment apparatus used in the present invention.

FIG. 5 is a perspective view showing an example of a cylindrical roll electrode used for plasma discharge treatment according to the present invention.

FIG. 6 is a perspective view showing an example of a fixed cylindrical electrode used for plasma discharge processing according to the present invention.

FIG. 7 is a perspective view showing an example of a fixed prismatic electrode used in the plasma discharge treatment according to the present invention.

FIG. 8 is a schematic view showing an example of a discharge processing apparatus using discharge plasma according to the present invention.

FIG. 9 shows an example of a reflection spectrum of the low-reflection polarizing plate of the present invention.

[Explanation of symbols]

1 Polarizing Layer 2, 2'Cellulose Ester Film 3, 3'Backcoat Layer 4, 4'Actinic Ray Curing Resin Layer 5 Antireflection Layer A Transparent Support B Transparent Support 6 Low Reflection Polarizing Plate F Substrate 8, 9 Nip Roller 10, 11, 17 Preliminary chamber 12 Processing chamber 13, 14 Electrode 15 High frequency power source 25, 26, 36 Electrode 25a, 25A, 26a, 26A, 36a, 36A Conductive base material 25b, 26b, 36b such as metal Lining treated dielectric 25B, 26B, 36B Ceramic coating processing dielectric material 30 Discharge processing chamber 31 Processing container 40 High frequency power supply 50 Gas filling means 51 Gas generator 52 Gas supply port (reaction gas introduction port) 53 Exhaust port 54 Partition plate 60 Electrode cooling unit 61 Film 65, 66 Nip rollers 64, 67 Guide rollers

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) // C08L 1:10 C08L 1:10

Claims (12)

[Claims] 1. A low-reflection polarizing plate having a polarizing layer sandwiched between two transparent supports A and B.
Each of B contains a cellulose ester, the transparent support A has an antireflection layer on the surface opposite to the polarizing layer directly or through another layer, and the transparent support A and the transparent support B
And the average substitution degree A of the cellulose ester contained in the transparent support A having an antireflection layer and the transparent support B are contained in the transparent support B. A low-reflection polarizing plate characterized in that the average substitution degree B of the cellulose ester has a relationship represented by the following formula (2). Formula (1) Thickness of transparent support A (μm) ≦ thickness of transparent support B (μ
m) ≦ film thickness of transparent support A + 100 (μm) Formula (2) Average substitution degree B + 0.05 ≦ average substitution degree A ≦ average substitution degree B
+0.35 2. The transparent supports A and B each have a film thickness of 200 μm or less, and the film thickness difference (transparent support B film thickness−transparent support A film thickness) between the transparent supports is ΔM. When the difference in the average substitution degree of the cellulose ester used in each (average substitution degree of the cellulose ester used in the transparent support A-average substitution degree of the cellulose ester used in the transparent support B) is ΔS, The low-reflection polarizing plate according to claim 1, wherein the condition of expression (3) is satisfied. Formula (3) 0.05 + ΔM / 200 <ΔS 3. The low-reflection polarizing plate according to claim 1, wherein the two transparent supports A and B are biaxially stretched cellulose ester films. 4. A polarizing plate in which a polarizing layer is sandwiched between two transparent supports A and B, and the transparent support A is on the surface opposite to the polarizing layer via an actinic radiation curable resin layer to prevent reflection. The low-reflection polarizing plate according to any one of claims 1 to 3, which has a layer, and the transparent support B has an actinic radiation curable resin layer on a surface opposite to the polarizing layer. 5. The film thickness ratio (UVb / UVa) between the film thickness UVa of the actinic radiation curable resin layer of the transparent support A and the film thickness UVb of the actinic radiation curable resin layer of the transparent support B is 0.1. -10
The low-reflection polarizing plate according to claim 4, wherein 6. The low reflection polarizing plate according to claim 4, wherein the film thickness UVb of the actinic radiation curable resin layer of the transparent support B is 1.3 μm or more. 7. The film thickness ratio (UVb / UVa) between the film thickness UVa of the actinic radiation curable resin layer of the transparent support A and the film thickness UVb of the actinic radiation curable resin layer of the transparent support B is 0.2. ~ 0.
The low reflection polarizing plate according to claim 5, which is 95. 8. The transparent support A or the transparent support B
Has a metal oxide layer having a carbon content of 0.2 to 5%, and the low reflection polarizing plate according to claim 1. 9. The low reflection as claimed in claim 1, wherein the transparent support A has an antireflection layer containing a metal oxide layer having a refractive index of 2.0 or more. Polarizer. 10. The low reflection polarizing plate according to claim 1, wherein the transparent support A has an antireflection layer formed by atmospheric pressure plasma treatment. 11. The average reflectance between 450 and 650 nm is:
It is less than 0.5%, The low reflection polarizing plate according to any one of claims 1 to 10. 12. A display device comprising the low reflection polarizing plate according to claim 1 and arranged so that the transparent support A side is a front side.