JP2002356566A - Polymer film and base sheet for display element thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer film having a retardation value of 5 nm or below even if in a broad sight angle, endurable in production conditions of an active matrix LCD, and also endurable in a liquid crystal itself. SOLUTION: A monomer has two or more functional acryloyl group and/or methacryloyl group. The polymer film is produced by heat-treatment of a the polymer film obtained by crosslinking the monomer, and therefore this polymer has the retardation value of 5 nm or below in the sight angle of 50 deg.C or below.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polymer film used for a substrate for a display element such as an active matrix LCD (hereinafter abbreviated as AMLCD), an optical disk, and an optical waveguide.

[0002]

2. Description of the Related Art Liquid crystals, plasma displays, electroluminescence (EL), fluorescent display tubes, light emitting diodes
It is required that the material of the display substrate such as the optical disk, the optical disk, and the material for the optical waveguide have a low retardation value. In particular, the AMLCD display substrate has a problem that the color tone varies depending on the viewing angle, and it is required that the retardation value be low even when the viewing angle is large. Preferably, the retardation value is 5 nm over a wide viewing angle.
The following is preferred. In general, in the case of a polymer film, there is a tendency that the retardation value tends to be large from the residual strain at the time of molding, and when the viewing angle is large even in the case of a low retardation film,
The retardation value was quite large. For this reason, when the liquid crystal display screen using the polymer film as a base material is viewed from an oblique direction, a color different from the color when viewed from the front may be seen.

[0003]

Under such circumstances, the present inventors have found that the retardation value is 5 nm or less even at a wide viewing angle, and that the liquid crystal itself can withstand the manufacturing conditions in the AMLCD manufacturing process. It is thought that if a polymer film that is resistant to the problem can be provided, a base film (substrate) for an AMLCD display element substrate with an improved viewing angle can be provided. Of the present invention. In addition, the present invention can also be used as a material for an optical disk and an optical waveguide, for example.

[0004]

That is, the present invention provides:
(1) 5 nm retardation within a viewing angle of 50 °
(2) a polymer film characterized by the following:
(3) a polymer film for a display element, wherein the retardation at a viewing angle of 50 ° or less is 5 nm or less;
The polymer film according to (1) or (2), comprising a polymer having a Tg of 150 ° C. or higher, (4) a wavelength of 500 n
m, wherein the light transmittance of the polymer film is 85% or more, (5) dimethyl sulfoxide resistance, tetramethyl ammonium hydroxide resistance, (5) the polymer film according to any one of (1) to (3), And the polymer film according to any one of (1) to (4), wherein the polymer has three or more functional acryloyl groups and / or methacryloyl. (7) The polymer film according to any one of (1) to (5), which is obtained by heat-treating a polymer obtained by crosslinking a monomer having a group. Is obtained by heat-treating a polymer obtained by crosslinking a monomer having a bifunctional acryloyl group and / or methacryloyl group (1).
-The polymer film according to any one of (5),
(8) The polymer is obtained by mixing one or more monomers having a bifunctional or higher acryloyl group and / or methacryloyl group with one or more monomers having a monofunctional or higher acryloyl group and / or a methacryloyl group. The polymer film according to any one of (1) to (5), wherein the polymer film is obtained by heat-treating a polymer obtained by crosslinking, and (9) the bifunctional acryloyl group. And / or the polymer film according to (7) or (8), wherein the monomer having a methacryloyl group is a monomer described in the general formula (1).

[0005]

Embedded image

(10) The polymer film according to (7) or (8), wherein the monomer having a bifunctional acryloyl group and / or methacryloyl group is a monomer represented by the general formula (2):

[0007]

Embedded image

(11) The polymer film according to (7) or (8), wherein the monomer having a bifunctional acryloyl group and / or methacryloyl group is a monomer represented by the general formula (3):

[0009]

Embedded image (In the general formula (3), R ² is —H, an alkyl group, —OR ⁵ ,
Or — (CH ₂ ) _n OH, where R ⁵ is —H or an alkyl group, n = 1 to 8, and each of R ³ and R ⁴ is —H or —CH _3.

(12) The polymer film according to (7) or (8), wherein the monomer having a bifunctional acryloyl group and / or methacryloyl group is a monomer represented by the general formula (4):

[0011]

Embedded image

(13) The monomer having a bifunctional acryloyl group and / or methacryloyl group is represented by the following (A)
(1) to (A-3), the polymer film according to (7) or (8), (A-1) a di (meth) acrylate having a group containing one monocyclic aliphatic ring (A- 2) di (meth) acrylate having a group containing two monocyclic aliphatic rings (A-3) di (meth) acrylate having a diphenylsulfide group (14) acryloyl group and / or (A-1) The monomers having a methacryloyl group are represented by the general formulas (5) to (8)
The polymer film according to item (13), which is the monomer described above,

[0013]

Embedded image (In the formula (5), R ¹ is a hydrogen atom or a methyl group.)

[0014]

Embedded image (In the formula (6), R ² is a hydrogen atom or a methyl group.)

[0015]

Embedded image (In the formula (7), R ³ is a hydrogen atom or a methyl group.)

[0016]

Embedded image (In the formula (8), R ⁴ is a hydrogen atom or a methyl group.)

(15) The monomer having the acryloyl group and / or methacryloyl group of the above (A-2) is represented by the following general formula:
The polymer film according to (13) or (14), which is the monomer according to (9),

[0018]

Embedded image (In the formula (9), R ⁵ is a hydrogen atom or a methyl group, R ⁶ ~
R ¹³ is a hydrogen atom or a hydrocarbon group having 1 to 16 carbon atoms, which may be the same or different. )

(16) The monomer according to any one of (13) to (15), wherein the monomer having an acryloyl group and / or a methacryloyl group of (A-3) is a monomer described in the general formula (10). Polymer film,

[0020]

Embedded image (In the formula (10), R ¹⁴ is a hydrogen atom or a methyl group;
¹⁵ is an alkylene group, and R ^{16 to} R ¹⁹ are a hydrogen atom or carbon atom 1
To 16 hydrocarbon groups, which may be the same or different. n is an integer of 0 to 2. )

(17) The polymer film according to (7) or (8), wherein the monomer having a bifunctional acryloyl group and / or methacryloyl group is a monomer described in the general formula (11).

[0022]

Embedded image (R ¹ is an alkylene group, R ² is a hydrogen atom or a methyl group, a
And b are each independently an integer of 1 to 5. )

(18) Any of (1) to (17)
A substrate for a display element using the polymer film according to Item 1, (19) A substrate for a thin film transistor display element using the polymer film according to any one of (1) to (17). It is.

[0024]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A polymer film having a retardation of 5 nm or less at a viewing angle of 50 ° or less can be obtained by heat-treating a polymer film obtained by polymerizing an acrylic acid monomer, for example, as described later. In a display element substrate application which is considered as one of the applications of the present invention, it is necessary to simultaneously satisfy the required performance as a substrate. That is, although the heat resistance required for the substrate material has been considerably relaxed, especially the environmental temperature in the AMLCD manufacturing process may still exceed 150 ° C. in some cases and may exceed 200 ° C. From this point, the polymer for display element is used. Has a glass transition temperature of 150 ° C. or higher, preferably 200 ° C. or higher. Transparency is also one of the important properties as long as it is for display devices, and it is desirable that the light transmittance at a wavelength of 500 nm be 85% or more. Furthermore, in the photolithography process, even a carefully prepared laminated film often enters a gap between the solvent-resistant barrier and the base film and erodes the base film. In the step of injecting the liquid crystal, the liquid crystal is injected by partially immersing the two substrates bonded together at an interval in the liquid crystal. The entry of liquid crystal is conceivable. Therefore, it is required that the polymer film for a display element can withstand the immersion of the liquid in these two steps at the same time.

DMS as a solvent for removing resist of the present invention
O and TMAH, a developer for photolithography
With Tg of 1
50 ° C. Desirably a polymer for a display element at 200 ° C. or higher, and a polymer for a display element from which a polymer film having a light transmittance of 85% or more at a wavelength of 500 nm is obtained,
For example, a polymer obtained by crosslinking a monomer having a bifunctional or higher acryloyl group and / or a methacryloyl group can be used.

The polymer film of the present invention obtained by crosslinking a monomer having a bifunctional or higher functional acryloyl group and / or methacryloyl group can be obtained by subjecting the acryloyl group and / or methacryloyl group of the monomer to electron beam crosslinking or thermal crosslinking.
A film can be formed by ultraviolet (UV) crosslinking or the like. In the case of thermal crosslinking, a peroxide is used, and in the case of ultraviolet crosslinking, a photopolymerization initiator and a photoinitiator are used as polymerization initiators. Further, in a polymer obtained by crosslinking the monomer having an acryloyl group and / or a methacryloyl group, a thermal polymerization inhibitor such as hydroquinone and benzoquinone, a leveling agent such as polyalkyl acrylate and silicone oil, a glass fiber, a fine particle A filler such as silica having a diameter can be mixed. It is also possible to form a film by mixing one or more polymers having the bifunctional or higher acryloyl group and / or methacryloyl group and one or more polymers having the monofunctional or higher acryloyl group and / or methacryloyl group. This method is effective in increasing the toughness of the film. By using the varnish-like substance thus obtained to form a film by a casting method and performing the following heat treatment, the retardation value in a wide viewing angle range can be reduced.

The reduction of the retardation value of a formed film by heat treatment is described in, for example, JP-A-07-168169, and is known. If the retardation value of is high,
The retardation value after the reduction was high, and the limit was about 15 nm. In the present invention, it has been found that the heat treatment of a film having a low retardation value before heat treatment can realize a retardation of 5 nm or less within a viewing angle of 50 °. An example of a film having a low retardation value of the film before the heat treatment is a polymer obtained by crosslinking a monomer containing at least a monomer having a bifunctional or higher acryloyl group and / or a methacryloyl group.

As the treatment method, a single-wafer heat treatment method,
A continuous heat treatment method using a device in which a dryer is arranged between rolls, a heat treatment method in a state of being wound around a core, and the like can be considered.
For example, in the case of a film obtained by casting, as a single-wafer heat treatment method, a method in which a single-wafer film placed on a plate or suspended with one side fixed in a dryer around heat, or dried. A method of continuously flowing a single sheet film suspended on a plate or fixed on one side in the machine can be considered. In the case of performing the heat treatment continuously, it is preferable that the heat treatment can be performed in a short time. Therefore, it is preferable to set the heat treatment temperature relatively high. The plate used for the heat treatment may be a glass substrate, a stainless steel substrate, or the like. However, there is no restriction as long as the material does not soften or deteriorate at the processing temperature, the substrate surface is smooth, and the heat conduction is uniform and good. Absent.

The thickness of the heat-resistant optical film according to the present invention is 10 μm to 500 μm, and more preferably 50 μm to 400 μm.
Is preferred in terms of processability and flexibility. Also,
The surface roughness of the film in the present invention is preferably 0.5 μm or less, and more preferably 0.1 μm or less. When the surface roughness is larger than 0.5 μm, display unevenness caused by a change in the liquid crystal cell gap due to unevenness of the electrode film surface is more remarkably confirmed than display unevenness caused by retardation of the transparent electrode film. If the polymer film obtained as described above is subjected to, for example, a silicon oxide-based gas / water vapor barrier, it can be used as a substrate for an AMLCD display device.

[0030]

Embodiments will be described below in accordance with embodiments. <Example 1> 10 g of isocyanuric acid EO-modified triacrylate (manufactured by Toagosei Co., Ltd.) was added to 0.1 g of Irgakya 184.
The varnish prepared by adding (manufactured by Ciba Specialty Chemicals) was stirred at 50 to 70 ° C. for 10 to 20 minutes, and then a varnish in a 0.4 mm thick frame formed on a release-treated glass plate was injected. . After the release-treated glass was placed on the top, UV light of about 500 mJ / cm ² was irradiated from both sides to cure, and the film was separated from the glass to obtain a polymer film. This was heat-treated on a stainless steel plate at 200 ° C. for 60 minutes.

<Example 2> The same method as in Example 1 was used except that the heat treatment temperature was 250 ° C. <Example 3> The same method as in Example 1 was used except that a glass plate was used instead of the stainless steel plate used in Example 1. <Example 4> The same method as in Example 2 was used except that a glass plate was used instead of the stainless steel plate used in Example 2. <Example 5> A polymer film was prepared in the same manner as in each of the examples, and one side of the film was sandwiched by clips, and heat treatment was performed by suspending in a similar temperature atmosphere for the same time as in Example 1. <Example 6> The same method as in Example 5 was used except that the heat treatment temperature was 250 ° C. <Example 7> X ¹ and X ^{2 in} the general formula (1) are both -CH
To ₂ OCOCHCH ₂ a is diacrylate monomer (Toagosei) 10 g, after the Irugakyaa 184 varnish was prepared by adding (Ciba Specialty Chemicals) of 0.1 g, was stirred for 10-20 min at 50-70 ° C., away A varnish in a 0.4 mm thick frame created on the glass plate subjected to the mold treatment was injected. After the release-treated glass was placed on the top, UV light of about 500 mJ / cm ² was irradiated from both sides to cure, and the film was separated from the glass to obtain a polymer film. This was heat-treated on a stainless steel plate at 275 ° C. for 3 hours.

Example 8 A device was manufactured in the same manner as in Example 7, except that the heat treatment temperature was set at 300 ° C. <Example 9> A glass plate was used instead of the stainless steel plate used in Example 7, and a heat treatment was performed in the same manner as in Example 7. Example 10 A heat treatment was performed in the same manner as in Example 8 except that a glass plate was used instead of the stainless steel plate used in Example 8. <Example 11> A polymer film was prepared in the same manner as in each example, and one side thereof was clipped and heat-treated by suspending in a similar temperature atmosphere for the same time as in Example 7. <Example 12> The same method as in Example 11 was used except that the heat treatment temperature was 300 ° C. <Example 13> X ³ and X ^{4 in} the general formula (2) are each —CH ₂
OCOCHCH ₂ , 5-ethyl-2 wherein R ¹ is an ethyl group
-(2-hydroxy-1,1-dimethylethyl) -5-
To 10 g of (hydroxymethyl) -1,3-dioxane diacrylate (manufactured by Nippon Kayaku), 0.1 g of Irgacya 18
A varnish prepared by adding No. 4 (manufactured by Ciba Specialty Chemical) was prepared in the same manner as in Example 7, and heat-treated. <Example 14> In the general formula (3), R ² is -CH ₂ CH ₂ O
Isocyanuric acid EO wherein each of H, R ³ and R ⁴ is —H
A varnish prepared by adding 0.1 g of Irgacare 184 (manufactured by Ciba Specialty Chemicals) to 10 g of modified diacrylate (manufactured by Toagosei) was prepared in the same manner as in Example 7, and heat-treated.

Embodiment 15 In the general formula (4),
A varnish prepared by adding 0.1 g of Irgacare 184 (manufactured by Ciba Specialty Chemicals) to 10 g of an acrylate (manufactured by Kuraray) having a structure in which X, R ¹ , and R ² are all hydrogen and p is 0 was prepared. 7, and a heat treatment was performed. Example 16 In the general formula (4), X represents —CH ₂ O
COCH = CH ₂ , R ¹ and R ² are both hydrogen and p is 0.
A varnish prepared by adding Irgacare 184 (manufactured by Ciba Specialty Chemical Co.) was prepared in the same manner as in Example 7, and heat-treated. Example 17 In the general formula (4), 0.1 g of Irgacare 184 (manufactured by Ciba Specialty Chemical) is added to 10 g of acrylate (manufactured by Kuraray) having a structure in which X, R ¹ , and R ² are all hydrogen and p is 1. ) Was prepared in the same manner as in Example 7, and heat treatment was performed. Example 18 In the general formula (4), X represents —CH ₂ O
COCH = CH ₂ , R ¹ , R ² are both hydrogen and p is 1;
A varnish prepared by adding Irgacare 184 (manufactured by Ciba Specialty Chemical Co.) was prepared in the same manner as in Example 7, and heat-treated. Example 19 A varnish prepared by adding 0.1 g of Irgacare 184 (manufactured by Ciba Specialty Chemicals) to 10 g of a mixture of 5 g of the acrylate of Example 15 and 5 g of the acrylate of Example 17 was prepared in the same manner as in Example 7. In addition, a heat treatment was performed. <Example 20> A varnish prepared by adding 0.1 g of Irgacare 184 (manufactured by Ciba Specialty Chemicals) to 10 g of a mixture of 5 g of the acrylate of Example 17 and 5 g of the acrylate of Example 18 was prepared in the same manner as in Example 7. In addition, a heat treatment was performed. <Example 21> 5 g of the acrylate of Example 15 and 5 g of EO-modified isocyanuric acid triacrylate (manufactured by Toagosei)
A varnish prepared by adding 0.1 g of Irgacare 184 (manufactured by Ciba Specialty Chemical) to 10 g of the above mixture was prepared in the same manner as in Example 7, and heat-treated.

Example 22 Acrylate of Example 15
To 10 g, 0.2 g of perhexa 2 as a peroxide crosslinking agent
5B (manufactured by Shikoku Chemicals) was added to prepare a varnish. After stirring at room temperature for 10 minutes, the varnish was poured into a 0.4 mm-thick frame formed on a release-treated glass plate, and the release-treated glass plate was placed from above, and then set at 110 ° C. It was placed in a dryer for 3 hours to cure. After curing, the film was peeled off from the glass plate to obtain a sample. This was heat-treated in the same manner as in Example 7. <Example 23> 10 g of the acrylate of Example 15 was poured into a 0.4 mm-thick frame formed on a release-treated glass plate, and the release-treated glass plate was placed on the upper portion. It was cured by irradiation with an electron beam of 500 kGy. After curing, the film was peeled off from the glass plate to obtain a sample. This was heat-treated in the same manner as in Example 7. <Example 24> After heating and dissolving 10 g of 1,3-cyclohexanediol diacrylate monomer (manufactured by Toagosei Co., Ltd.) in which R1 in the general formula (5) is a hydrogen atom at 80 to 100 ° C, 0.1 g of Irgacare 184 ( Varnish prepared by adding Ciba Specialty Chemical Co., Ltd.)
After stirring for 20 minutes, a varnish in a 0.4 mm thick frame formed on the glass plate subjected to the release treatment was injected. After placing the release-treated glass from the top, about 500 mJ /
The film was cured by irradiating it with UV light of ² cm ² , and the film was peeled from the glass to obtain a polymer film. This was heat-treated on a stainless steel plate at 230 ° C. for 3 hours.

<Example 25> The same procedure as in Example 24 was carried out except that the heat treatment temperature was 275 ° C. Example 26 A solar cell was produced in the same manner as in Example 24 except that a glass plate was used instead of the stainless steel plate used in Example 24. <Example 27> The same method as in Example 25 was used except that a glass plate was used instead of the stainless steel plate used in Example 25. <Example 28> A polymer film was prepared in the same manner as in each example, and one side thereof was clipped.
Heat treatment was performed by suspending in a similar temperature atmosphere. <Example 29> Except that the heat treatment temperature was set to 300 ° C, it was manufactured in the same manner as in Example 28.

Example 30 10 g of 1,3-cyclohexanediol diacrylate monomer (manufactured by Toagosei Co., Ltd.) in which R1 in the general formula (5) is a hydrogen atom was used at 80 to 100 ° C.
Varnish prepared by adding 0.1 g of Irgacare 184 (manufactured by Ciba Specialty Chemical) and 0.05 g of 1,1-bis (t-butylperoxy) 2-methylcyclohexane (Nippon Oil & Fats) Example 24
A heat treatment was performed in the same manner as described above. <Example 31> 10 g of 1,2-cyclohexanedimethanol diacrylate monomer (manufactured by Toagosei Co., Ltd.) in which R2 of the general formula (6) is a hydrogen atom was heated and dissolved at 80 to 100 ° C, and then 0.1 g of Irgacya 184 was obtained. A varnish prepared by adding (manufactured by Ciba Specialty Chemicals) was prepared in the same manner as in Example 24, and heat-treated. <Example 32> 10 g of 1,3-cyclopentanediol diacrylate monomer (manufactured by Toagosei Co., Ltd.) in which R 3 is a hydrogen atom in the general formula (7) is heated and dissolved at 80 to 100 ° C, and then 0.1 g of Irgacair 184 is obtained. A varnish prepared by adding (manufactured by Ciba Specialty Chemicals) was prepared in the same manner as in Example 24, and heat-treated. Example 33 10 g of 1,3-cyclopentanedimethanol diacrylate monomer (manufactured by Toagosei Co., Ltd.) in which R4 in formula (8) is a hydrogen atom was heated and dissolved at 80 to 100 ° C., and then 0.1 g of Irgacya was dissolved. A varnish prepared by adding 184 (manufactured by Ciba Specialty Chemicals) was prepared in the same manner as in Example 24, and heat-treated.

Example 34 R5 to R13 of the formula (9)
Is a hydrogen atom, 10 g of 4,4 ′-(1-methyl-ethylidene) biscyclohexanol diacrylate monomer (manufactured by Toagosei Co., Ltd.) is heated and dissolved at 120 to 140 ° C., and then 0.1 g of Irgacare 184 (Ciba Specialty Chemical) Was prepared in the same manner as in Example 24, and heat treatment was performed. Example 35 R14 and R16 of General Formula (10)
To 19 are hydrogen atoms.
10 g of-(2-hydroxyethoxy) phenyl "sulfide diacrylate monomer (produced by Toagosei)
After heating and dissolving at ~ 140 ° C, 0.1 g of Irgaya Care 1
A varnish prepared by adding 84 (manufactured by Ciba Specialty Chemicals) was prepared in the same manner as in Example 24, and heat-treated. <Example 36> In the general formula (11), 0.1 g of Irgacya 184 (Ciba Specialty) is added to 10 g of an acrylate (manufactured by Toagosei Co., Ltd.) in which R ₁ is an ethylene group and R ₂ is all hydrogen and a and b are 1. A varnish prepared by adding a chemical (manufactured by Chemical Co., Ltd.) was prepared in the same manner as in Example 7, and heat-treated. <Example 37> Varnish prepared by adding 0.1 g of Irgacare 184 (manufactured by Ciba Specialty Chemical) to 10 g of a mixture of 5 g of the acrylate of Example 36 and 5 g of bis (hydroxymethyl) tricyclodecanediacrylate (Toagosei). Was manufactured in the same manner as in Example 7, and heat treatment was performed.

Example 38 Acrylate of Example 36
To 10 g, 0.2 g of perhexa 2 as a peroxide crosslinking agent
5B (manufactured by Shikoku Chemicals) was added to prepare a varnish. About 1
After stirring for 〜１０10 minutes, the varnish was poured into a 0.4 mm-thick frame created on the release-treated glass plate, the release-treated glass plate was placed from above, and then dried at 150 ° C. Cured for 3 hours in machine. After curing, the film was peeled off from the glass plate to obtain a sample. This was heat-treated in the same manner as in Example 7. <Example 39> 10 g of the acrylate of Example 36 was poured into a 0.4 mm-thick frame formed on a release-treated glass plate, and the release-treated glass plate was placed on the upper portion. It was cured by irradiation with an electron beam of 500 kGy. After curing, the film was peeled off from the glass plate to obtain a sample. This was heat-treated in the same manner as in Example 7. Example 40 In the general formula (11), 0.1 g of Irgacya 184 (to 10 g of acrylate (manufactured by Toagosei Co., Ltd.) having a structure in which R ₁ is an isopropylene group, R ₂ is all hydrogen, and a and b are 1) Made by Ciba Specialty Chemical)
Was prepared in the same manner as in Example 7, and heat treatment was performed.

<Comparative Example 1> A polymer film was prepared in the same manner as in Example 1, and no heat treatment was performed. Comparative Example 2 A film having a thickness of about 0.4 mm was obtained by a melt extrusion method using a polyether sulfone resin (manufactured by Sumitomo Chemical Co., Ltd.). <Comparative Example 3> The film obtained in Comparative Example 2 was subjected to a heat treatment temperature of 2
The heat treatment was performed in the same manner as in Example 9 except that the temperature was changed to 20 ° C. <Comparative Example 4> The film obtained in Comparative Example 2 was heat-treated by the method shown in Example 9.

With respect to the sample prepared as described above,
The film thickness and the retardation value at a viewing angle of 0 {10 20 30 30 40 50} were measured by the following evaluation methods. Evaluation method Film thickness: The center of the film (retardation measurement point) was measured with a micrometer. Retardation: Measured with an automatic birefringence meter KOBURA-21H (manufactured by Oji Scientific). Tg: The maximum value of tan δ at 1 Hz of a viscoelasticity measuring device DMS-210 (manufactured by Seiko Instruments) was defined as Tg. Resistance to resist stripping solution: immersion of sample in dimethyl sulfoxide (DMSO) solution at 40 ° C.
Leave for a minute. After taking out the sample, the external appearance was visually observed. Resistance to developer: A sample is put into a 15% aqueous solution of tetramethylammonium hydroxide (TMAH) at 24 ° C. and left for 60 minutes. After taking out the sample, the appearance is visually observed. Alignment agent resistance: A sample is placed on a spin coater. After dropping CRD-8201 (manufactured by Sumitomo Bakelite) on the surface, spin coating was performed at 2500 rpm. 180
After drying at 60 ° C. for 60 minutes, the appearance was visually observed. Liquid crystal resistance: ZLI-4 manufactured by Merck on the surface of the substrate
792 is dropped. Put in an oven at 120 ° C. and leave for 60 minutes. After taking out the sample, observe the appearance visually.

The evaluation results are shown in Tables 1 to 6.

[Table 1]

[0042]

[Table 2]

[0043]

[Table 3]

[0044]

[Table 4]

[0045]

[Table 5]

[0046]

[Table 6]

As shown in Tables 1 to 5, when a polymer film obtained by crosslinking a polymer film having a monomer having a bifunctional or more acryloyl group and / or a methacryloyl group was cross-linked (Examples 1 to 40), all of the visual fields were observed. When the angle was in the range of 0 to 50 °, the retardation value was 5 nm or less. On the other hand, when the same film was not heat-treated (Comparative Example 1), when the viewing angle exceeded 40 °, the retardation value became 5 nm or more. Further, when an extruded product of polyether sulfone was used as a film material (Comparative Example 2)
In Nos. To 5), the retardation value was high irrespective of the presence or absence of the heat treatment, and the viewing angle at which the retardation value was 5 nm or less when the heat treatment was performed at a high temperature was up to about 10 °.

Example 41 A sheet-like substrate was prepared by the method shown in Example 3, and a silicon oxide-based inorganic layer was deposited as an oxygen and water vapor barrier. Using this as a polymer substrate, a thin film transistor (hereinafter abbreviated as TFT) array was produced in accordance with the method described in Japanese Patent Application Laid-Open No. 10-512104. During this manufacturing process, DM
When TMAH was used as a developer for SO and photolithography, no denaturation such as blistering or clouding was observed on the polymer substrate. Further, a color filter substrate was produced by the same photolithography technique. At this time, DMSO and TMAH were used.
As in the case of the FT array, no denaturation such as blistering or clouding was observed. Next, after washing both substrates of the TFT and the color filter, an alignment film treatment was performed, an epoxy adhesive was applied to the color filter side by screen printing, and a spacer was sprayed on the TFT substrate, and then the two were adhered to each other. Thereafter, liquid crystal was injected from the previously opened gap between the substrates by a vacuum injection method. As is well known, the liquid crystal injection method is a method in which a gap (opening) between both substrates is immersed in liquid crystal and injected by a pressure difference, and a substrate portion around the opening is always immersed in liquid crystal. After this operation, no denaturation was observed on both substrates. Further, when a liquid crystal module was assembled using the liquid crystal cell manufactured as described above, and the presence or absence of color unevenness was observed at a viewing angle of 50 °, no color unevenness occurred. It was proved that a simple TFT liquid crystal cell could be obtained.

Example 42 A sheet-like substrate was prepared by the method shown in Example 9, and a silicon oxide-based inorganic layer was deposited as an oxygen and water vapor barrier. Using this as a polymer substrate, a thin film transistor (hereinafter abbreviated as TFT) array was produced in accordance with the method described in Japanese Patent Application Laid-Open No. 10-512104. During this manufacturing process, DM
When TMAH was used as a developer for SO and photolithography, no denaturation such as blistering or clouding was observed on the polymer substrate. Further, a color filter substrate was produced by the same photolithography technique. At this time, DMSO and TMAH were used.
As in the case of the FT array, no denaturation such as blistering or clouding was observed. Next, after washing both substrates of the TFT and the color filter, an alignment film treatment was performed, an epoxy adhesive was applied to the color filter side by screen printing, and a spacer was sprayed on the TFT substrate, and then the two were adhered to each other. Thereafter, liquid crystal was injected from the previously opened gap between the substrates by a vacuum injection method. As is well known, the liquid crystal injection method is a method in which a gap (opening) between both substrates is immersed in liquid crystal and injected by a pressure difference, and a substrate portion around the opening is always immersed in liquid crystal. After this operation, no denaturation was observed on both substrates. Further, when a liquid crystal module was assembled using the liquid crystal cell manufactured as described above, and the presence or absence of color unevenness was observed at a viewing angle of 50 °, no color unevenness occurred. It was proved that a simple TFT liquid crystal cell could be obtained.

Example 43 A sheet-like substrate was prepared by the method shown in Example 17, and a silicon oxide-based inorganic layer was deposited as an oxygen and water vapor barrier. Using this as a polymer substrate, a thin film transistor (hereinafter abbreviated as TFT) array was produced in accordance with the method described in Japanese Patent Application Laid-Open No. 10-512104. During this manufacturing process, D
TMAH as a developer for MSO and photolithography
However, denaturation such as blistering and clouding was not observed on the polymer substrate. Further, a color filter substrate was produced by the same photolithography technique. At this time, DMSO and TMAH were used.
As in the case of the FT array, no denaturation such as blistering or clouding was observed. Next, after washing both substrates of the TFT and the color filter, an alignment film treatment was performed, an epoxy adhesive was applied to the color filter side by screen printing, and a spacer was sprayed on the TFT substrate, and then the two were adhered to each other. Thereafter, liquid crystal was injected from the previously opened gap between the substrates by a vacuum injection method. As is well known, the liquid crystal injection method is a method in which a gap (opening) between both substrates is immersed in liquid crystal and injected by a pressure difference, and a substrate portion around the opening is always immersed in liquid crystal. After this operation, no denaturation was observed on both substrates. Further, when a liquid crystal module was assembled using the liquid crystal cell manufactured as described above, and the presence or absence of color unevenness was observed at a viewing angle of 50 °, no color unevenness occurred. It was proved that a simple TFT liquid crystal cell could be obtained.

Example 44 A sheet-like substrate was prepared by the method shown in Example 26, and a silicon oxide-based inorganic layer was deposited as an oxygen and water vapor barrier. Using this as a polymer substrate, a thin film transistor (hereinafter abbreviated as TFT) array was produced in accordance with the method described in Japanese Patent Application Laid-Open No. 10-512104. During this manufacturing process, D
TMAH as a developer for MSO and photolithography
However, denaturation such as blistering and clouding was not observed on the polymer substrate. Further, a color filter substrate was produced by the same photolithography technique. At this time, DMSO and TMAH were used.
As in the case of the FT array, no denaturation such as blistering or clouding was observed. Next, after washing both substrates of the TFT and the color filter, an alignment film treatment was performed, an epoxy adhesive was applied to the color filter side by screen printing, and a spacer was sprayed on the TFT substrate, and then the two were adhered to each other. Thereafter, liquid crystal was injected from the previously opened gap between the substrates by a vacuum injection method. As is well known, the liquid crystal injection method is a method in which a gap (opening) between both substrates is immersed in liquid crystal and injected by a pressure difference, and a substrate portion around the opening is always immersed in liquid crystal. After this operation, no denaturation was observed on both substrates. Further, when a liquid crystal module was assembled using the liquid crystal cell manufactured as described above, and the presence or absence of color unevenness was observed at a viewing angle of 50 °, no color unevenness occurred. It was proved that a simple TFT liquid crystal cell could be obtained.

Example 45 A sheet-like substrate was prepared by the method shown in Example 36, and a silicon oxide-based inorganic layer was deposited as an oxygen and water vapor barrier. Using this as a polymer substrate, a thin film transistor (hereinafter abbreviated as TFT) array was produced in accordance with the method described in Japanese Patent Publication No. 10-512104. During this manufacturing process, D
TMAH as a developer for MSO and photolithography
However, denaturation such as blistering and clouding was not observed on the polymer substrate. Further, a color filter substrate was produced by the same photolithography technique. At this time, DMSO and TMAH were used.
As in the case of the FT array, no denaturation such as blistering or clouding was observed. Next, after washing both substrates of the TFT and the color filter, an alignment film treatment was performed, an epoxy adhesive was applied to the color filter side by screen printing, and a spacer was sprayed on the TFT substrate, and then the two were adhered to each other. Thereafter, liquid crystal was injected from the previously opened gap between the substrates by a vacuum injection method. As is well known, the liquid crystal injection method is a method in which a gap (opening) between both substrates is immersed in liquid crystal and injected by a pressure difference, and a substrate portion around the opening is always immersed in liquid crystal. After this operation, no denaturation was observed on both substrates. Further, when a liquid crystal module was assembled using the liquid crystal cell manufactured as described above, and the presence or absence of color unevenness was observed at a viewing angle of 50 °, no color unevenness occurred. It was proved that a simple TFT liquid crystal cell could be obtained.

[0053]

As described above, the polymer film of the present invention has a characteristic that its retardation value is 5 nm or less at a wide viewing angle, and is a resist removal solvent dimethyl sulfoxide and a photolithography developer. Since it has both solvent resistance to tetramethylammonium hydroxide and liquid crystal resistance, and is excellent in heat resistance and transparency, it is particularly suitable for use as a display element substrate for AMLCD. Conventionally, there has been no polymer film intended for such a purpose, and the required characteristics have been maintained by a multi-layered laminated material structure. It is possible to provide a good AMLCD display substrate by overcoming swelling and peeling due to high penetration of a solvent into the interlayer, and is extremely useful in the electronics industry.

 ──────────────────────────────────────────────────続 き Continuing from the front page (31) Priority claim number Japanese Patent Application 2001-35760 (P2001-35760) (32) Priority date February 13, 2001 (2001.2.13) (33) Priority claim country Japan (JP) (31) Priority claim number Japanese Patent Application No. 2001-95605 (P2001-95605) (32) Priority date March 29, 2001 (2001. 3.29) (33) Priority claim country Japan (JP) F term (reference) 2H090 JB03 JB13 JD08 LA04 4F071 AA33 AA86 AF01 AF02 AF29 AF30 AF31 AH19 4J100 AL66P BA08P BA51P BC03P BC04P BC12P BC43P BC48P BC58P BC75P CA01 CA23 GC29 JA32 JA35 JA36

Claims (19)

[Claims] 1. A polymer film having a retardation of 5 nm or less at a viewing angle of 50 ° or less. 2. A polymer film for a display element, wherein the retardation at a viewing angle of 50 ° or less is 5 nm or less. 3. The polymer film according to claim 1, wherein the polymer film has a Tg of 150 ° C. or higher. 4. The polymer film according to claim 1, wherein a light transmittance at a wavelength of 500 nm is 85% or more. 5. The polymer film according to claim 1, which has resistance to dimethyl sulfoxide, resistance to tetramethylammonium hydroxide, and resistance to liquid crystal. 6. The polymer according to claim 1, wherein the polymer is obtained by heat-treating a polymer obtained by crosslinking a monomer having three or more functional acryloyl groups and / or methacryloyl groups. The polymer film according to any one of the above items. 7. The polymer according to claim 1, wherein the polymer is obtained by heat-treating a polymer obtained by crosslinking a monomer having a bifunctional acryloyl group and / or methacryloyl group. Or the polymer film of item 1. 8. The polymer comprises one or more monomers having a bifunctional or higher acryloyl group and / or methacryloyl group and one or more monomers having a monofunctional or higher acryloyl group and / or a methacryloyl group. The polymer film according to any one of claims 1 to 5, wherein the polymer film is obtained by heat-treating a polymer obtained by mixing and then crosslinking. 9. The polymer film according to claim 7, wherein the monomer having a bifunctional acryloyl group and / or methacryloyl group is a monomer represented by the general formula (1). Embedded image 10. The polymer film according to claim 7, wherein the monomer having a bifunctional acryloyl group and / or methacryloyl group is a monomer represented by the general formula (2). Embedded image 11. The polymer film according to claim 7, wherein the monomer having a bifunctional acryloyl group and / or methacryloyl group is a monomer represented by the general formula (3). Embedded image (In the general formula (3), R ² is —H, an alkyl group, —OR ⁵ ,
Or — (CH ₂ ) _n OH, where R ⁵ is —H or an alkyl group, n = 1 to 8, and each of R ³ and R ⁴ is —H or —CH _3. 12. The polymer film according to claim 7, wherein the monomer having a bifunctional acryloyl group and / or methacryloyl group is a monomer represented by the general formula (4). Embedded image 13. The monomer having a bifunctional acryloyl group and / or methacryloyl group is represented by the following (A-1) to (A-
9. The polymer film according to claim 7, which is 3). (A-1) Di (meth) acrylate having a group containing one unitary aliphatic ring (A-2) di (meth) acrylate having a group containing two unitary aliphatic rings (A-3 ) Di (meth) acrylate having a diphenyl sulfide group 14. The monomer having the acryloyl group and / or methacryloyl group of the above (A-1) is represented by the following general formula (5):
The polymer film according to claim 13, which is the monomer according to (8). Embedded image (In the formula (5), R ¹ is a hydrogen atom or a methyl group.) (In the formula (6), R ² is a hydrogen atom or a methyl group.) (In the formula (7), R ³ is a hydrogen atom or a methyl group.) (In the formula (8), R ⁴ is a hydrogen atom or a methyl group.) 15. The polymer film according to claim 13, wherein the monomer having an acryloyl group and / or a methacryloyl group of (A-2) is a monomer represented by the general formula (9). Embedded image (In the formula (9), R ⁵ is a hydrogen atom or a methyl group, R ⁶ ~
R ¹³ is a hydrogen atom or a hydrocarbon group having 1 to 16 carbon atoms, which may be the same or different. ) 16. The monomer (A-3) having an acryloyl group and / or a methacryloyl group represented by the general formula (10):
The monomer according to any one of claims 13 to 15,
Item 7. The polymer film according to item 1. Embedded image (In the formula (10), R ¹⁴ is a hydrogen atom or a methyl group;
¹⁵ is an alkylene group, and R ^{16 to} R ¹⁹ are a hydrogen atom or carbon atom 1
To 16 hydrocarbon groups, which may be the same or different. n is an integer of 0 to 2. ) 17. The monomer having a bifunctional acryloyl group and / or methacryloyl group represented by the general formula (1)
9. The polymer film according to claim 7, which is the monomer described in 1). Embedded image (R ¹ is an alkylene group, R ² is a hydrogen atom or a methyl group, a
And b are each independently an integer of 1 to 5. ) 18. A display element substrate using the polymer film according to claim 1. Description: 19. A substrate for a thin film transistor display element, comprising the polymer film according to claim 1. Description: