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CN-122003391-A - Transparent composite material, transparent article and method for producing composite material and transparent article

CN122003391ACN 122003391 ACN122003391 ACN 122003391ACN-122003391-A

Abstract

By introducing an optically invisible or at least almost invisible transparent composite material (9), a bendable transparent cover plate (1) element with an optically homogeneous appearance is provided, the transparent composite material (9) comprising a polymer matrix (13) with dispersed inorganic particles (15, 17), wherein the polymer matrix (13) comprises at least one elastomer, and wherein the composite material (9) comprises <20 vol.% of inorganic particles (15, 17), wherein the Abbe number of the composite material (9) d,comp Is >35, and wherein the condition n d,glass is for the difference between the refractive index n d,glass of the glass (4) as the first material and the refractive index n d,comp of the composite material (9) as the second material )–n d,comp ( ) <0.02 For the ranges from 400 nm to 800 nm every wavelength within the wavelength range [ ] ) The treatment is effective.

Inventors

  • S. Legner
  • H Eisenman
  • XIAO WEI
  • HE FENG
  • F. WAGNER
  • M Hayes - week
  • J. WEBER
  • J. Weshorn

Assignees

  • 肖特股份有限公司
  • 肖特玻璃科技(苏州)有限公司

Dates

Publication Date
20260508
Application Date
20240204
Priority Date
20231011

Claims (17)

  1. 1. Transparent composite (9) comprising a polymer matrix (13) with dispersed inorganic particles (15, 17), wherein the polymer matrix (13) comprises at least one elastomer, and wherein the content of dispersed inorganic particles (15, 17) in the composite (9) is < 20% by volume, wherein the abbe number of the composite (9) d,comp Is >35, the refractive index n d,comp is in the range of 1.4 to 1.7, and the young's modulus is <5 MPa.
  2. 2. The transparent composite (9) according to the preceding claim, wherein the young's modulus of the composite (9) is < 3MPa, preferably <1 MPa.
  3. 3. The transparent composite (9) according to any one of the preceding claims, wherein the refractive index n d,comp of the composite (9) is in the range of 1.45 to 1.7, preferably in the range of 1.48 to 1.7, and/or the abbe number of the composite (9) d,comp Is > 50 and/or < 100.
  4. 4. The transparent composite (9) according to any one of the preceding claims, wherein the polymer matrix (13) comprises at least one of the following features: -the polymer matrix (13) comprises an elastomer with acrylate monomer units, preferably acrylate monomer units comprising aryl substituted acrylates, preferably substituted phenyl acrylates and/or acrylates with cyclic alkyl substituents, preferably norbornyl substituted and/or tetrahydrofurfuryl substituted acrylates; -the polymer matrix (13) is a copolymer comprising at least two different monomer units and/or the polymer matrix comprises at least one monomer unit having at least two polymerizable groups.
  5. 5. The transparent composite (9) according to any one of the preceding claims, wherein the amount of the inorganic particles (15, 17) is < 15 vol.%, preferably < 10 vol.% and/or in the range of 1 to 15 vol.%, preferably 1 to 10 vol.%.
  6. 6. The transparent composite (9) according to any one of the preceding claims, wherein the inorganic particles (15, 17) are selected from TiO 2 、ZrO 2 、Al 2 O 3 , ITO, siN and/or mixtures thereof.
  7. 7. The transparent composite (9) according to any one of the preceding claims, wherein the diameter d 99 of the inorganic particles is < 50 nm, preferably < 30 nm, and most preferably < 15 nm, and/or exhibits a minimum size of at least 2 nm.
  8. 8. The transparent composite (9) according to any one of the preceding claims, wherein the composite (9) comprises a first type of inorganic particles (15) and a second type of inorganic particles (17), wherein the refractive index n d,part1 of the first type of inorganic particles (15) is > 1.6, preferably > 1.7, more preferably > 1.8, and/or the abbe number of the second type of inorganic particles (17) d,part2 Is > 50, preferably > 70, more preferably > 80.
  9. 9. The transparent composite (9) according to any one of the preceding claims, wherein the composite (9) has a refractive index n eff , and wherein the volume fraction f polymer of the polymer matrix in the composite and the volume fraction f i of the at least one or more inorganic particles are selected according to the following equation: Wherein And m is greater than or equal to 1.
  10. 10. A transparent article (1) comprising a first portion having a first material and a second portion comprising the first material and a second material, wherein the first material is a transparent glass (4) or glass ceramic and the second material is a transparent composite material (9) according to any one of the preceding claims, wherein the first material and the second material form at least one interface and the first portion is connected to the second portion.
  11. 11. The transparent article (1) according to claim 10, wherein for each wavelength in the wavelength range from 400 nm to 800 nm Refractive index n glass of the first material ) And the refractive index n comp of the transparent composite material (9) as the second material ) Absolute value of difference between |n glass ( )– n comp ( )| Is < 0.02, preferably < 0.01, more preferably < 0.008, most preferably < 0.004.
  12. 12. Transparent article (1) according to claim 10 or 11, Wherein the absolute value ǀ n 400nm,glass - n 400nm, comp ǀ of the difference in refractive index of the first material (4) and the composite material (9) at a wavelength of 400 nm is < 0.02, preferably < 0.01, more preferably < 0.008, most preferably < 0.004, -And/or wherein the absolute value ǀ n 800nm,glass - n 800nm, comp ǀ of the difference in refractive index of the first material (4) and the composite material (9) at a wavelength of 800 nm is < 0.02, preferably < 0.01, more preferably < 0.008, most preferably < 0.004, -And/or abbe number of the first material (4) d,glass And Abbe number of the composite material (9) d,comp Absolute value of difference of | d, glass - d, comp The i is < 40, preferably < 30, more preferably < 25.
  13. 13. The transparent article (1) according to any one of the preceding claims 10 to 12, wherein the transparent article (1) is a cover element for a display of a mobile device, the cover element comprising at least one first portion (101) consisting of the first material, and at least one second portion (102) comprising the first material and the second material; Wherein the cover element has two main surfaces (3, 5) and the thickness d of the first portion (101), i.e. the distance between the side surfaces (3, 5), is < 2000 μm, preferably < 1000 μm, more preferably < 500 μm.
  14. 14. The transparent article according to claim 13, wherein at least a portion of the first material in the second portion (102) is chemically tempered glass, Having a body portion with a uniform composition having a refractive index n d, glass, bulk , and having a surface portion having a refractive index n d, glass, surface , Wherein n d, glass, bulk <n d , glass, surface is a number selected from the group consisting of, And wherein preferably in said second portion (102) the absolute difference |n glass, surface | for the whole wavelength range between 400 nm and 800 nm ) – n comp ( ) The value of is < 0.02, preferably <0.01, more preferably < 0.008, most preferably < 0.004, And/or therein |n d, glass, bulk – n d, comp | > |n d, glass, surface – n d, comp |。
  15. 15. The transparent article (1) according to claim 12 or 13, wherein at least one second portion (102), preferably a plurality of second portions (102), of the cover element (1) is a bendable portion, and wherein preferably the cover element (1) can be bent in the bendable portion with a bending radius of < 10 mm, preferably < 5mm without breaking.
  16. 16. A method for producing a transparent composite (9) according to any one of claims 1 to 9, wherein the method comprises at least the following steps a) to c): a) Providing monomers, oligomers and/or prepolymers, wherein the monomers, oligomers and/or prepolymers comprise at least one polymerizable group, preferably acrylic groups, B) Providing inorganic particles (15, 17) and dispersing the inorganic particles (15, 17) in the monomer, oligomer and/or prepolymer, C) Filling the dispersion obtained in step b) into a cavity, D) Polymerization of the monomers, oligomers and/or prepolymers is carried out to produce a polymer matrix.
  17. 17. A method for producing a transparent article (1) according to claims 10 to 15, comprising at least the following steps 1) to 4): 1) A structured thin glass (4) is provided, wherein the glass (4) comprises at least one first portion (101) of thickness d and at least one second portion (102) with at least one opening (7), 2) Providing a formulation according to steps a) to b) of claim 16, 3) Applying the formulation of step 2) on the glass (4) such that the opening (7) of the thin glass (4) formed in the second portion (102) of the glass (4) is filled with the formulation, and 4) Curing the formulation under anaerobic conditions to obtain a composite material (9) comprising a polymer matrix (13) and inorganic particles (15, 17).

Description

Transparent composite material, transparent article and method for producing composite material and transparent article Technical Field In general, the present invention relates to a transparent elastic filler material, its use in flexible transparent articles and a method of producing said transparent composite material. In particular, the present invention relates to a transparent flexible article formed by incorporating a transparent flexible composite material into a portion of an inorganic brittle material, wherein the transparent flexible composite material is optically invisible or at least nearly invisible. Background For display applications, bendable glass is of interest. One possibility to make glass flexible is to reduce its thickness. However, this also reduces its impact strength. The reduced strength can be compensated for by a sandwich design that combines more than two thin glass and polymer elements. However, the sandwich structure may have other drawbacks such as a tendency to delaminate or reduced light transmission (light transmission) due to an increased number of interfaces with a refractive index step (REFRACTIVE INDEX STEPS). EP 3 936 485 A1 or US 2022002185 A1 describes thicker glass elements up to a thickness of 1mm or more, which can be bent by structuring the glass along a bending line. The structuring of the glass results in a reduction in the thickness of the glass along the bending line, thereby enabling bending of the glass. In addition to the bend lines, the glass exhibits a higher thickness. Thus, the glass is able to bend, but at the same time retains its impact resistance. However, due to the different glass thicknesses, the structured areas on the curved lines are clearly visible, thereby reducing the available display area. By filling the bendable structure of the inorganic brittle material with an elastic filler material having matching optical properties, the optically uniform appearance (optically homogenous appearance) of the bendable structure (which includes structured areas in the inorganic material) can be reduced, thereby creating an optically uniform appearance of the bendable structure. WO 2021/07643 A1 describes a foldable display made of glass, wherein the display comprises polymer based parts. The polymer-based part includes a polymer having high light transmittance and low haze. In order to reduce the visibility of the polymer-based portion, the refractive index n d of the polymer is adjusted to the refractive index of the glass. However, the visibility of the polymer-based portion may depend on the viewing angle and the wavelength of light. Disclosure of Invention Object of the Invention It is therefore an object of the present invention to provide a transparent material having high flexibility as an elastic filler material for inorganic brittle materials (e.g. glass), wherein the optical properties match those of the inorganic brittle materials over the entire visible spectrum. It is another object of the present invention to provide a transparent flexible article having a uniform optical appearance. It is a further object of the present invention to provide a method of producing such a filler material. Description of the invention The above object of the invention is achieved by the subject matter of the independent claims. Preferred embodiments and variants are subject matter of the dependent claims. By filling the bendable structure of the inorganic brittle material with an elastic filler material, which has matching optical properties over the entire visible wavelength range, i.e. between 400 nm and 800 nm, the optically uniform appearance of the bendable structure (which includes structured areas in the inorganic material) can be reduced. Accordingly, one aspect of the present invention relates to a transparent elastomeric filler material whose optical properties match those of an inorganic brittle material over the entire visible spectrum. Therefore, it is necessary that the light dispersion (optical dispersion) of the filler material matches the light dispersion of the inorganic brittle material. To achieve this, the inorganic brittle material and the elastic filler material should have matched refractive indices and matched abbe numbers. A typical inorganic brittle material is glass. In general, glass exhibits an abbe number between 20 (flint glass) and 60 (crown glass). In most cases, the abbe number increases with the refractive index of the glass. Transparent elastomeric polymers having abbe numbers within a given range are described in the prior art. However, these polymers exhibit typical diffraction indices that are well below those of typical inorganic brittle materials, such as glass used in flexible structures (e.g., cover glass). To overcome this problem, the present invention relates to a transparent composite comprising a transparent polymer matrix with dispersed inorganic particles. The polymer matrix includes at least one elastome