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CN-114556609-B - Laminate and organic electroluminescent display device

CN114556609BCN 114556609 BCN114556609 BCN 114556609BCN-114556609-B

Abstract

A laminate comprising a wavelength selective absorption layer and a gas barrier layer directly disposed on at least one surface of the wavelength selective absorption layer, wherein the wavelength selective absorption layer contains a resin, a dye containing at least 1 of 4 specific dyes A to D, and a discoloration inhibitor for the dye, the gas barrier layer contains a crystalline resin, the thickness of the layer is 0.1 to 10 [ mu ] m, and the oxygen transmittance of the layer is 60cc/m 2 day atm or less.

Inventors

  • KUWABARA HIROSHI
  • FUKAGAWA NOBUTAKA
  • SASAKI HIROKI

Assignees

  • 富士胶片株式会社
  • 富士胶片株式会社

Dates

Publication Date
20260421
Application Date
20200930
Priority Date
20190930

Claims (12)

  1. 1. A laminate comprising a wavelength selective absorption layer and a gas barrier layer directly disposed on at least one surface of the wavelength selective absorption layer, wherein the wavelength selective absorption layer comprises a thermoplastic polymer resin, a dye comprising at least 1 of dyes A to D described below, and a discoloration inhibitor for the dye, The gas barrier layer contains a crystalline resin, has a thickness of 0.1-10 [ mu ] m, has an oxygen transmission rate of 60cc/m 2 -day-atm or less, The refractive index difference between adjacent layers in the laminate is 0.15 or less, Dye A is a dye with a main absorption wavelength band at the wavelength of 390-435 nm, Dye B is dye with main absorption wavelength band at the wavelength of 480-520 nm, Dye C is dye with main absorption wavelength band at the wavelength of 580-620 nm, Dye D is dye with main absorption wavelength band at 680-780 nm.
  2. 2. The laminate according to claim 1, wherein the crystallinity of the crystalline resin contained in the gas barrier layer is 25% or more.
  3. 3. The laminate according to claim 1 or 2, wherein the oxygen permeability of the gas barrier layer is 0.001cc/m 2 -day-atm or more and 60cc/m 2 -day-atm or less.
  4. 4. The laminate according to claim 1 or 2, wherein at least one of the dyes B and C is squaraine-based pigment represented by the following general formula (1), General formula (1) In the above formula, a and B each independently represent an aryl group which may have a substituent, a heterocyclic group which may have a substituent, or —ch=g, and G represents a heterocyclic group which may have a substituent.
  5. 5. The laminate according to claim 1 or 2, wherein the dye A is a dye represented by the following general formula (A1), In the above formula, R 1 and R 2 each independently represent an alkyl group or an aryl group, R 3 ～R 6 each independently represent a hydrogen atom or a substituent, and R 5 and R 6 may be bonded to each other to form a 6-membered ring.
  6. 6. The laminate according to claim 1 or 2, wherein the dye D is at least 1 of a dye represented by the following general formula (D1) and a dye represented by the following general formula (1), Wherein R 1A and R 2A each independently represent an alkyl group, an aryl group or a heteroaryl group, R 4A and R 5A each independently represent a heteroaryl group, R 3A and R 6A each independently represent a substituent, X 1 and X 2 each independently represent-BR 21a R 22a ,R 21a and R 22a each independently represent a substituent, R 21a and R 22a may be bonded to each other to form a ring, General formula (1) In the above formula, a and B each independently represent an aryl group which may have a substituent, a heterocyclic group which may have a substituent, or —ch=g, and G represents a heterocyclic group which may have a substituent.
  7. 7. The laminate according to claim 1 or 2, wherein the discoloration inhibitor is represented by the following general formula (IV), In the above formula, R 10 each independently represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, or a group represented by R 18 CO-、R 19 SO 2 -or R 20 NHCO-, R 18 、R 19 and R 20 each independently represents an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group, R 11 and R 12 each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, or an alkenyloxy group, and R 13 ～R 17 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group.
  8. 8. The laminate according to claim 1 or 2, wherein the resin in the wavelength selective absorption layer comprises a polystyrene resin.
  9. 9. The laminate according to claim 1 or 2, wherein the resin in the wavelength selective absorption layer comprises a cyclic polyolefin resin.
  10. 10. The laminate according to claim 1 or 2, wherein the wavelength selective absorption layer contains all 4 of the dyes a to D.
  11. 11. The laminate according to claim 1 or 2, wherein the laminate comprises an ultraviolet absorbing layer and at least 1 layer selected from a binder layer and an adhesive layer, the ultraviolet absorbing layer is disposed on the opposite side of the gas barrier layer from the wavelength selective absorbing layer, and refractive index differences between adjacent layers in the laminate are each 0.05 or less.
  12. 12. An organic electroluminescent display device comprising the laminate according to any one of claims 1 to 11.

Description

Laminate and organic electroluminescent display device Technical Field The present invention relates to a laminate and an organic electroluminescent display device. Background An organic electroluminescence (OLED) display device is a device that displays an image by self-luminescence of an OLED element. Therefore, the liquid crystal display device has advantages such as high contrast ratio, high color reproducibility, wide viewing angle, high-speed response, thin and light weight, and the like, as compared with various display devices such as a liquid crystal display device and a plasma display device. In addition to these advantages, research and development are actively being conducted as a next-generation display device from the aspect of flexibility. On the other hand, when an OLED display device is used in an outdoor or other external light environment, external light is reflected by a metal electrode or the like constituting the OLED display device, and display defects such as a decrease in contrast occur. There is known a technique of suppressing reflection of external light by providing a circularly polarizing plate having an optically anisotropic layer such as a λ/4 retardation film, and in this technique, there is a problem of lowering of brightness. In recent years, a technology of suppressing reflection of external light and a reduction in luminance by providing a light absorbing layer capable of absorbing external light has been studied. For example, patent document 1 describes, as a light absorbing layer provided between a light emitting layer and an antireflection film in a color filter for an OLED of a white light source type, a light absorbing layer containing a carbon black pigment and a dye (pigment) and having a transmittance of 15 to 50% and a haze value of 1.0 or less in a wavelength region of 400nm to 700 nm. Patent document 2 describes, as a light absorption filter in an OLED display device, a light absorption filter that displays an absorption spectrum having a negative correlation with an emission spectrum of a spectrum of each pixel in which a plurality of colors are synthesized, but there is no specific description as to how a target absorption spectrum is realized. Prior art literature Patent literature Patent document 1 Japanese patent application laid-open No. 2017-203810 Patent document 2 Japanese patent application laid-open No. 2014-132522 Patent document 3 International publication No. 2017/014272 Disclosure of Invention Technical problem to be solved by the invention As a result of the study by the present inventors, it is known that the color tone of an image of a 0LED display device is changed in accordance with a coloring material such as a coloring material contained in a light absorbing layer (light absorbing filter) as described in patent document 1, and there is room for improvement in suppression of the color tone change. As a result of further repeated studies, the present inventors have found that a wavelength selective absorption filter containing 4 dyes having a main absorption wavelength band in specific different wavelength regions and having an absorbance Ab (λ) at a wavelength λ nm satisfying a specific relational expression can be applied to an OLED display device while simultaneously suppressing external light reflection and luminance reduction required for the application, and can sufficiently suppress the influence on the original color tone of a display image. However, in the case where the wavelength selective absorption filter is used as an antireflection mechanism for an OLD display device instead of a circular polarizer, the dye in the wavelength selective absorption filter is required to have high light resistance because the polarizer is not provided on the outside of the wavelength selective absorption filter. For example, patent document 3 describes a color correction filter containing 2 kinds of pigments and resins having a great absorption in specific different wavelength regions, as a color correction filter used in a liquid crystal display device using a white LED (LIGHT EMITTING Diode) as a light source. Further, it is described that a gas barrier layer is provided to suppress a decrease in absorption intensity of a dye caused by light irradiation, and more specifically, a color correction filter provided with a gas barrier layer containing SiO x or SiN x as an inorganic material is described. Among materials having gas barrier properties, inorganic materials have a lower oxygen permeability coefficient and a lower hygroscopicity than organic materials, and thus can exhibit more excellent gas barrier properties. On the other hand, from the viewpoint of industrial productivity, a gas barrier layer containing an inorganic material is not suitable. That is, the gas barrier layer of the inorganic material is obtained by laminating inorganic materials such as a Plasma-enhanced chemical Vapor Deposition (Plasma-ENHANCED CHEMICAL Vapor Depositio