Colored polarizing films, colored polarizing sheets, and colored polarizing lenses, and methods thereof

Abstract

A polarizing film is produced by swelling a polyvinyl alcohol film with water, uniaxially stretching it, dyeing it with an organic dichroic dye, and drying it, wherein a dichroic organic dye composition includes a combination of organic dyes having a dichroic ratio of 13 or higher used in an amount to keep the degree of polarization at 90% or more, and wherein the coloration dye composition comprises a combination of dyes having extremely low dichroic ratios of 4 or less or substantially having no dichroic ratio, laminating at least one layer of a transparent plastic sheet onto at least both sides of the polarizing film, curving the polarizing sheet so as to impart spherical or aspherical surfaces thereto to obtain a polarizing and injecting a transparent resin to the concave surface of the curved polarizing sheet to obtain an injection polarizing lens.

Claims

1. A method for producing a colored polarizing film of a desired color, wherein the method for producing the polarizing film comprises swelling a polyvinyl alcohol film with water, uniaxially stretching it, dyeing it with a dichroic organic dye, and drying it, wherein the dichroic organic dye comprises a dichroic organic dye composition and a coloration organic dye composition, wherein the dichroic organic dye composition comprises a combination of dichroic organic dyes having a dichroic ratio of 13 or higher, used in an amount to keep the degree of polarization at 90% or more, and wherein the coloration organic dye composition comprises a combination of dyes having an extremely low dichroic ratio of 4 or less or substantially having no dichroic ratio, used in an amount yielding a desired dyed color, wherein a target percentage of total light transmission is selected, wherein the dichroic organic dyes of the dichroic organic dye composition are selected such that, when combined, they are substantially colorless, and contribute to obtain a polarizing degree of interest and to provide a percentage of light transmission that exceeds the target percentage of total light transmission, and wherein the dyes of the coloration organic dye composition are selected so as to have a color of interest and selected to have a dichroic ratio and an amount to maintain the polarizing degree of interest while reducing the percentage of light transmission provided by the dichroic organic dyes of the dichroic organic dye composition such that the colored polarizing film has the target percentage of total light transmission.

2. The method for producing the colored polarizing film of claim 1, wherein the dichroic organic dye composition and the coloration organic dye composition are used in an aqueous solution.

3. The method for producing the colored polarizing film of claim 1, wherein the dichroic organic dye composition is used in an amount to obtain the lower limit of the required degree of polarization.

4. The method for producing the colored polarizing film of claim 1, wherein the coloration organic dye composition is used in an amount such that the transmittance of the film is 10% or more and is at least 5% smaller than the transmittance of a polarizing film obtained by using the dichroic organic dye composition only.

5. A colored polarizing sheet that comprises a polarizing film produced by swelling a polyvinyl alcohol film with water, uniaxially stretching it, dyeing it with a dichroic organic dye, and drying it, and transparent plastic sheets attached on both sides of the polarizing film by an adhesive, wherein the dichroic organic dye used in producing the film comprises a dichroic organic dye composition and a coloration organic dye composition, wherein the dichroic organic dye composition comprises a combination of organic dyes having a dichroic ratio of 13 or higher, used in an amount to keep the degree of polarization at 90% or more, and wherein the coloration organic dye composition comprises a combination of dyes having an extremely low dichroic ratio of 4 or less or substantially having no dichroic ratio, used in an amount yielding a desired dyed color, wherein a target percentage of total light transmission is selected, wherein the dichroic organic dyes of the dichroic organic dye composition are selected such that, when combined, they are substantially colorless, and contribute to obtain a polarizing degree of interest and to provide a percentage of light transmission that exceeds the target percentage of total light transmission, and wherein the dyes of the coloration organic dye composition are selected so as to have a color of interest and selected to have a dichroic ratio and an amount to maintain the polarizing degree of interest while reducing the percentage of light transmission provided by the dichroic organic dyes of the dichroic organic dye composition such that the colored polarizing film has the target percentage of total light transmission.

6. The colored polarizing sheet of claim 5, wherein the dichroic organic dye composition and the coloration organic dye composition are used in an aqueous solution.

7. The colored polarizing sheet of claim 5, wherein the dichroic organic dye composition is used in an amount to obtain the lower limit of the required dichroic ratio.

8. The colored polarizing sheet of claim 5, wherein the coloration organic dye composition is used in an amount such that the transmittance of the film is 10% or more and is at least 5% smaller than that the transmittance of a polarizing film obtained by using the dichroic organic dyeing composition only.

9. The colored polarizing sheet of claim 5, wherein the material of at least one of the transparent plastic sheets is one or more selected from the group consisting of: aromatic polycarbonates, polyacrylate, acetylcellulose, polyamide, and a composition of an aromatic polycarbonate and alicyclic polyester.

10. The colored polarizing sheet of claim 5, wherein at least one of the transparent plastic sheets is an aromatic polycarbonate sheet that has a thickness of from 0.1 mm to 1 mm and the sheet provides a retardation value of 3000 nm or higher.

11. The colored polarizing sheet of claim 5, wherein in the adhesive layer is a two-liquid type thermosetting polyurethane resin that consists of a curative agent that comprises a polyurethane prepolymer and a hydroxyl (poly) acrylate.

12. A colored polarizing lens obtained by: laminating with a transparent plastic sheet via an adhesive layer to each surface of a polarizing film that is made by swelling a polyvinyl alcohol resin with water, uniaxially stretching it, dyeing it with a dichroic organic dye, and drying it to obtain a polarizing sheet; curving the polarizing sheet so as to impart spherical or aspherical surfaces thereto to obtain a curved polarizing lens or curving the polarizing sheet so as to impart spherical or aspherical surfaces thereto and injecting a transparent resin onto the concave surface to obtain an injection-molded lens, wherein the dichroic organic dye is made by using a dichroic organic dye composition and a coloration organic composition, wherein the dichroic organic dye composition used to produce the polarizing film comprises a combination of dichroic organic dyes having a dichroic ratio of 13 or higher and is used in an amount to keep the degree of polarization at 90% or more, and wherein the coloration organic dye composition comprises a combination of dyes having an extremely low dichroic ratio of 4 or less or substantially having no dichroic ratio, wherein a target percentage of total light transmission is selected, wherein the dichroic organic dyes of the dichroic organic dye composition are selected such that, when combined, they are substantially colorless, and contribute to obtain a polarizing degree of interest and to provide a percentage of light transmission that exceeds the target percentage of total light transmission, and wherein the dyes of the coloration organic dye composition are selected so as to have a color of interest and selected to have a dichroic ratio and an amount to maintain the polarizing degree of interest while reducing the percentage of light transmission provided by the dichroic organic dyes of the dichroic organic dye composition such that the colored polarizing film has the target percentage of total light transmission, the resulting polarizing film being a polarizing film of a desired color.

13. The colored polarizing lens of claim 12, wherein the polarizing film is dyed by using the dichroic organic dye composition and the coloration organic dye composition in an aqueous solution.

14. The colored polarizing lens of claim 12, wherein the organic dichroic dye composition is used in an amount to obtain the lower-limit of the required dichroic ratio.

15. The colored polarizing lens of claim 12, wherein the coloration organic dye composition is used in an amount so that the transmittance of the film is 10% or more and is at least 5% smaller than the transmittance obtained by using the dichroic organic dyeing composition only.

16. The colored polarizing lens of claim 12, wherein the material of at least one of the transparent plastic sheets is one or more selected from the group consisting of: aromatic polycarbonates, polyacrylate, acetylcellulose, polyamide, and a composition of an aromatic polycarbonate and alicyclic polyester.

17. The colored polarizing lens of claim 12, wherein at least one of the transparent plastic sheets is an aromatic polycarbonate sheet that has a thickness of from 0.1 mm to 1 mm and the sheet provides a retardation value of 3000 nm or higher.

18. The colored polarizing lens of claim 12, wherein the adhesive agent in the adhesive layer is a two-liquid type thermosetting polyurethane resin that consists of a curative agent that comprises a polyurethane polymer and a hydroxyl (poly) acrylate.

19. A method for producing a colored polarizing lens consisting of: laminating with a transparent plastic sheet through an adhesive layer to each surface of a polarizing film that is made by swelling a polyvinyl alcohol resin with water, uniaxially stretching it, dyeing it with a dichroic organic dye, and drying it to obtain a polarizing sheet; curving the polarizing sheet so as to impart spherical or aspherical surfaces thereto to obtain a curved polarizing lens or curving the polarizing sheet so as to impart spherical or aspherical surfaces thereto and injecting a transparent resin onto the concave surface of the curved polarizing sheet to obtain an injection-molded lens; wherein the dichroic organic dye is made by using a dichroic organic dye composition and a coloration organic composition, wherein the dichroic organic dye comprises a dichroic organic dye composition and an coloration organic dye composition, wherein the dichroic organic dye composition comprises a combination of organic dyes having a dichroic ratio of 13 or higher, used in an amount to keep the degree of polarization at 90% or more, and wherein the coloration organic dye composition comprises a combination of dyes having an extremely low dichroic ratio of 4 or less or substantially having no dichroic ratio, wherein a target percentage of total light transmission is selected, wherein the dichroic organic dyes of the dichroic organic dye composition are selected such that, when combined, they are substantially colorless, and contribute to obtain a polarizing degree of interest and to provide a percentage of light transmission that exceeds the target percentage of total light transmission, and wherein the dyes of the coloration organic dye composition are selected so as to have a color of interest and selected to have a dichroic ratio and an amount to maintain the polarizing degree of interest while reducing the percentage of light transmission provided by the dichroic organic dyes of the dichroic organic dye composition such that the colored polarizing film has the target percentage of total light transmission, the resulting coloration polarized film being a desired color and obtained by using a coloration organic dye composition in an amount yielding the desired color.

20. The method for producing the colored polarizing lens of claim 19, wherein the polarizing sheet is dyed by using the dichroic organic dye composition and the coloration organic dye composition in an aqueous solution.

21. The method for producing the colored polarizing lens of claim 19, wherein the organic dichroic dye composition is used in an amount to obtain the lower limit of the dichroic ratio to be required.

22. The method for producing of the colored polarizing lens of claim 19, wherein the coloration organic dye composition is used in an amount such that the transmittance of the film is 10% or more and is at least 5% smaller than the transmittance of a polarizing film obtained by using the dichroic organic dyeing composition only.

23. The method for producing of the colored polarizing lens of claim 19, wherein the material of at least one of the transparent plastic sheets is one or more selected from the group consisting of: aromatic polycarbonates, polyacrylate, acetylcellulose, polyamide, and a composition of an aromatic polycarbonate and alicyclic polyester.

24. The method for producing of the colored polarizing lens of claim 19, wherein at least one of the transparent plastic sheets is an aromatic polycarbonate sheet that has a thickness of from 0.1 mm to 1 mm and the sheet provides a retardation value of 3000 nm or higher.

25. The method for producing a colored polarizing lens of claim 19, wherein the adhesive agent in the adhesive layer is a two-liquid type thermosetting polyurethane resin that consists of a curative agent that comprises a polyurethane polymer and a hydroxyl (poly) acrylate.

Description

EXAMPLES

(1) Producing Colored Polarizing Films

(2) Below, the preferable embodiments in the method for producing the colored polarizing film of the present invention is explained by using Examples 1-6 and Comparative examples 1, 2, and 3.

(3) As shown in Table 1 below, the dichroic organic dye composition and the coloration organic dye composition were prepared.

(4) Examples 2, 4, 5, and 6 of Table 2 are first embodiments for providing polarizing films that have color tones that cannot be obtained by using available dichroic organic dye compositions used in the dyeing process of the conventional polarizing films. Color tones and dichroic ratios are in parentheses after the names of the dyes. The dichroic ratios in the Examples are the values of maximal absorption wavelengths obtained under the conditions to obtain the dichroic ratio of 80 at a wavelength of 600 nm in the polarizing film produced by dyeing it with iodine.

(5) (1) Dichroic Organic Dye Composition

(6) As the dichroic organic dye composition that imparts the degree of polarization to the film, the composition below was used

(7) Dichroic Organic Dye Composition A:

(8) C.I.Direct Blue 237 (blue, 19.9), C.I.Direct Red 81 (red, 22.0), C.I.Direct Orange 39 (yellow, 23.6)

(9) The values in parentheses show the dichroic ratios.

(10) (2) Coloration Organic Dye Composition

(11) As coloration organic dye compositions that impart color tones, the compositions listed below were used.

(12) Coloration Organic Dye Composition a:

(13) C.I.Direct Blue 86 (blue1, 1.5), C.I.Direct Red 227 (red, 1.3), C.I.Mordant Yellow 8 (yellow, 1.7)

(14) Coloration Organic Dye Composition b:

(15) Kayacion Blue CF-BL (blue1, 1.3), Novacron Red C-2G (red, 1.4), C.I Reactive Yellow145 (yellow, 2.6)

(16) (3) Producing Polarizing Film

(17) Polyvinyl alcohol (Kuraray Co., Ltd., trade name: VF-PS#7500) was swollen in water at 35 C. for 270 seconds while being stretched two-fold.

(18) After that, it was dyed in an aqueous solution containing dye compositions disclosed on Table 1 and 10 g/L of an anhydrous sodium sulfate at 35 C. During this process, it was stretched four-fold. This dyed film was immersed in an aqueous solution containing 2.3 g/L of nickel acetate and 4.4 g/L of boric acid at 35 C. for 120 seconds while being stretched 5.6-fold. The film was dried at room temperature for 3 minutes in a state wherein the tension was retained, and then subjected to a heating treatment at 110 C. for 3 minutes, whereby a polarizing film was obtained. The amounts to be used of the dichroic organic dye composition and the coloration organic dye composition are disclosed in Table 1 below.

(19) Next, the transmittance, color tones, degree of polarization, and colors by visual observation of the obtained polarizing films are shown in Table 2. The degree of polarization was obtained by the following formula:
Degree of polarization=100(pmaxpmin)/(wmax+pmin),
wherein, pmax is the maximum value of luminous transmittance measured by the incident of linearly polarized light and pmin is the minimum value of luminous transmittance measured by the incident of linearly polarized light. max and pmin are the values that express Ax and Az as the luminous transmittance.

(20) pmax and pmin are determined by using a spectrophotometer manufactured by Shimadzu Corporation (UV-3600) with an incident light that is vertical polarization.

(21) Its degree of polarization was more than 99%. Thus, it is satisfactory as a practical matter.

(22) TABLE-US-00001 TABLE 1 Compositions and concentrations of dyes Dichroic Concentration in Coloration Concentration in organic dye dyeing solution organic dye dyeing solution composition blue red yellow composition blue red yellow Comparative A 6.96 1.04 1.84 example 1 Comparative A 10.2 5.81 6.80 example 2 Comparative A 2.46 12.2 0.00 example 3 Examples 1 A 0.87 0.10 0.23 a 0.96 0.57 0.92 Examples 2 A 0.87 0.10 0.23 a 12.2 0.12 2.30 Examples 3 A 0.87 0.10 0.23 a 0.12 0.90 0.47 Examples 4 A 0.87 0.10 0.23 b 0.52 0.00 1.55 Examples 5 A 0.87 0.10 0.23 b 0.64 0.00 0.11 Examples 6 A 0.87 0.10 0.23 b 0.07 0.80 0.00

(23) TABLE-US-00002 TABLE 2 Color tones of produced polarizing film Transmittance Color tone Polarization Color by visual (%) L* a* b* degree (%) observation Comparative 14.5 45.0 1.8 1.7 99.9up gray example 1 Comparative 14.6 45.0 8.4 0.8 99.9up greenish gray example 2 Comparative 14.9 45.5 41.0 1.2 99.6 strong purply red example 3 Examples 1 15.6 46.5 1.6 0.4 99.8 gray Examples 2 15.5 46.3 46.4 0.8 99.1 Brilliant bluish green Examples 3 14.1 44.4 31.7 1.5 99.7 dull purply red Examples 4 18.8 50.4 17.9 27.1 99.6 dull yellowish green Examples 5 19.0 50.7 8.6 15.5 99.2 dull greenish blue Examples 6 19.4 51.2 22.6 14.2 99.5 dull reddish purple

(24) As is clearly understood from these examples, in colored polarizing films that are produced by using the dichroic organic dye composition and the coloration organic dichroic dye composition, not depending on the properties of (wavelength) absorbance of the dichroic organic dye composition, but owing to the properties of (wavelength) absorbance of the coloration organic dichroic dye composition, polarizing films that have various color tones can be produced.

(25) Production of Colored Polarizing Sheets and Colored Lens

(26) Examples 7-12 and Comparative Example 4 were embodiments for producing the colored polarizing sheet and the colored polarizing lens from the colored polarizing film of the present invention.

(27) (A) Producing Polarizing Film

(28) As shown in Table 3, the dichroic organic dye composition and the coloration organic dyes composition were prepared. Example 12 was obtained by reducing the transmittance of Example 7 to 12% while the ratio of the absorbed amount of the coloration dye composition used in Example 7 was maintained. The dichroic ratios in the Examples were the values of maximal absorption wavelengths obtained under the conditions to obtain the dichroic ratio of 80 at the wavelength of 600 nm in the polarizing film produced by dyeing it with iodine.

(29) (1) Dichroic Organic Dye Compositions

(30) The dichroic organic dye compositions to impart the degree of polarization were prepared as follows.

(31) Dichroic organic dye composition A: C.I.Direct Blue 237 (blue, 19.9), C.I.DirectRed 81 (red, 22.0), C.I.Direct Orange 39 (yellow, 23.6)

(32) Dichroic organic dye composition B: C.I.Direct Blue 78 (blue, 9.2), C.I.Direct Red 254 (red, 10.9), C.I.Direct Yellow 12 (yellow, 9.0)

(33) (2) Coloration Organic Dye Compositions

(34) The coloration organic dye compositions to impart color tones were prepared as followed.

(35) Coloration organic dye composition a: C.I.Direct Blue 86 (blue 1, 1.5), C.I.Direct Blue 108 (blue 2, 1.6), C.I.Direct Red 225 (red, 2.6), C.I.Mordant Yellow 8 (yellow, 1.7)

(36) Coloration organic dye composition b: C.I.Direct Blue 86 (blue1, 1.5), C.I.Direct Blue 108 (blue 2, 1.6), C.I.Direct Red 227 (red, 1.3), C.I.Mordant Yellow 8 (yellow, 1.7)

(37) Coloration organic dye composition c: C.I.Direct Blue 86 (blue1, 1.5), C.I.Direct Blue 108 (blue 2, 1.6), C.I.Direct Red 225 (red, 2.6), C.I.Mordant Yellow 5 (yellow, 2.3)

(38) Coloration organic dye composition d: C.I.Direct Blue 86 (blue 1, 1.5), C.I.Direct Blue 108 (blue 2, 1.6), C.I.Direct Red 227 (red, 1.3), C.I.Mordant Yellow 5 (yellow, 2.3)

(39) Coloration organic dye composition e: C.I.Reactive Blue 235 (blue 1, 1.1), C.I.AcidRed 336 (red, 1.5), C.I.Reactive Yellow 167 (yellow, 2.2)

(40) (3) Producing Polarizing Film

(41) Polyvinyl alcohol (Kuraray Co., Ltd., trade name: VF-PS#7500) was swollen in water at 35 C. for 270 seconds while being stretched two-fold. After that, it was dyed in an aqueous solution containing dye compositions disclosed on Table 1 and 10 g/L of an anhydrous sodium sulfate at 35 C. During this process, it was stretched four-fold. This dyed film was immersed in an aqueous solution containing 2.3 g/L of nickel acetate and 4.4 g/L of boric acid at 35 C. for 120 seconds while being stretched 5.6-fold. The film was dried at room temperature for 3 minutes in a state wherein the tension was retained and then subjected to a heating treatment at 110 C. for 3 minutes, whereby a polarizing film was obtained.

(42) TABLE-US-00003 TABLE 3 Compositions and concentrations of dyes Dichroic Concentration in Coloration Concentration in organic dye dyeing solution (g/L) organic dye dyeing solution (g/L) composition blue red yellow composition blue 1 blue 2 red yellow Examples 7 A 0.87 0.10 0.23 a 0.12 0.62 0.24 0.61 Examples 8 A 0.87 0.10 0.23 b 0.13 0.51 0.25 0.57 Examples 9 A 0.87 0.10 0.23 c 0.12 0.50 0.22 0.38 Examples 10 A 0.87 0.10 0.23 d 0.13 0.52 0.27 0.43 Examples 11 A 0.87 0.10 0.23 e 0.26 0.19 0.33 Examples 12 A 0.87 0.10 0.23 a 0.70 1.42 0.38 1.40 Comparative B 0.94 0.11 0.13 example 4
(B) Aromatic Polycarbonate Polarizing Sheet

(43) A urethane-based adhesive was applied to the polarizing film obtained in (A) using a bar coater #12, then dried at 70 C. for 10 minutes. After that, an aromatic polycarbonate sheet having a thickness of 0.3 mm and a retardation value of 5500 nm (Mitsubishi Gas Chemical Co., Inc.) was bonded to the polarizing film using a laminating machine so that both the stretch axis of the aromatic polycarbonate sheet and the stretch axis of the polarizing film were in a direction horizontal to the polarizing lens. The adhesive was applied to the polarizing film side of the laminated sheet in the same manner as above, and another aromatic polycarbonate sheet was bonded thereto in the same way, whereby an aromatic polycarbonate polarizing sheet was obtained. The thickness of the coated adhesive after curing was 9 to 11 m.

(44) (C) Measurement of Absorbance of Aromatic Polycarbonate Polarizing Lens

(45) The transmittance and color tone of the prepared aromatic polycarbonate polarizing sheet were measured using a spectrophotometer manufactured by Shimadzu Corporation (UV-3600). The results are shown in Table 4.

(46) (D) Aromatic Polycarbonate Polarizing Lens

(47) The aromatic polycarbonate polarizing sheet obtained in (b) was subjected to the curving process using a mold having a base curve of 7.95 (curvature radius 66.67 mm). In the curving process, the forming was carried out under the following conditions: mold temperature: 137 C., and retention time: 1200 seconds. The base curve as used herein refers to the curvature of the front surface of the lens, and it is a value obtained by dividing 530 by the curvature radius (in millimeters). There were no cracks in the polarizing film of the aromatic polycarbonate polarizing lens after the curving process. The transmittance and color tone of the aromatic polycarbonate polarizing lens after the curving process of samples measured in a manner similar to that in (c), and the color difference E*ab in the CIE1976 (L*a*b*) color space before and after forming are shown in Table 1. The color difference was obtained by the following formula:
Color difference: E*ab=((L*)^2+(a*)^2+(b*)^2^()

(48) TABLE-US-00004 TABLE 4 Color tones of produced polycarbonate polarizing sheet before and after curving process Color Polarization Color Polarization Color difference at Transmittance tone degree Transmittance tone degree curving process (%) L* a* b* (%) (%) L* a* b * (%) Afterbefore Examples 7 19.0 50.7 0.3 3.9 99.2 18.1 49.6 1.1 4.2 99.4 1.8 Examples 8 21.3 53.3 0.6 3.1 98.7 20.0 51.9 0.8 3.0 99.2 1.4 Examples 9 20.0 51.9 1.0 4.4 99.5 19.0 50.7 2.7 3.3 99.6 2.3 Examples 10 20.0 51.8 2.1 3.7 99.1 18.7 50.4 2.6 2.2 99.1 2.1 Examples 11 22.1 54.1 1.0 3.3 98.3 20.6 52.5 1.0 2.2 98.7 1.9 Examples 12 12.7 42.2 6.1 5.3 98.8 12.0 41.3 8.2 4.9 99.6 2.3 Comparative 20.3 52.2 1.8 2.5 99.3 17.4 48.7 0.4 2.4 99.1 3.7 example 4

(49) As is clearly understood from these examples, in the aromatic polycarbonate polarizing sheet that is dyed by using the dichroic organic dye composition only, the color difference before and after the processing steps was 3.7. On the other hand, the aromatic polycarbonate polarizing sheets that are dyed by using the dichroic organic dye composition and the coloration organic dyes composition shows the color differences before and after the processing steps were 1.4 to 2.3. Thus, the polarizing sheet of the present invention shows small changes in color tone and transmittance between before and after the processing steps.

INDUSTRIAL APPLICABILITY

(50) By the present invention, the polarizing films, the polarizing sheets, and the polarizing lenses that have various combinations of degree of polarization and transmittance and desired color tone can be provided in an industrial level.