Laminate, method for manufacturing laminate, and use of dopant for reducing deterioration of laminate
A laminate with a carbon allotrope and dopant layer structure addresses UV-induced degradation in laminates by using a sacrificial dopant, maintaining electrical conductivity and extending the laminate's lifespan.
Patent Information
- Application Number
- JP2025102613
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2024-06-28
- Filing Date
- 2025-06-18
- Publication Date
- 2026-01-19
AI Technical Summary
Laminates containing carbon nanotubes deteriorate over time due to UV degradation from sunlight, causing increased electrical resistance due to the neutralization of dopants by components from the optically clear adhesive.
A laminate structure with a first layer containing a carbon allotrope and a dopant at a specific concentration, acting as a sacrificial dopant, is used to reduce UV degradation, comprising a second layer of organic material for protection and bonding.
The laminate exhibits reduced UV degradation, maintaining electrical conductivity and longevity by using a sacrificial dopant in the first layer, which acts as a barrier against UV-induced deterioration.
Smart Images
Figure 2026008857000001_ABST
Abstract
Description
[Technical Field]
[0001] The present disclosure relates to laminates, and more particularly to laminates comprising doped carbon allotropes. The present disclosure also relates to methods for making the laminates and the use of dopants to reduce degradation of the laminates. [Background technology]
[0002] Carbon nanotubes can be used to provide functional layers in laminates, for example, in laminated vehicle windshields, carbon nanotubes can be used to provide a heating element in the laminated windshield to serve the purposes of defrosting, de-icing, and defogging.
[0003] Dopants are used to tailor the properties of carbon nanotubes. For example, dopants can improve the electrical conductivity of carbon nanotubes. A layer containing carbon nanotubes and dopants can be laminated to a glass layer using, for example, an optical clear adhesive (OCA) and a tie layer such as polyvinyl butyral (PVB) or thermoplastic polyurethane (TPU).
[0004] One problem with the laminates mentioned above is that they deteriorate over time due to sunlight. This occurs because the optically clear adhesive (pressure-sensitive adhesive) or components that diffuse or leach from the optically clear adhesive (pressure-sensitive adhesive), such as those due to chemical decomposition of the optically clear adhesive (pressure-sensitive adhesive), neutralizes the dopant under the ultraviolet light contained in sunlight. This can be observed as an increase in the electrical resistance of the functional layer. Summary of the Invention
[0005] It is an object of the present disclosure to provide a stack, a method for manufacturing the stack, and a use of the dopant that solves the above-mentioned problems.
[0006] The object of the present disclosure is achieved by a laminate, a manufacturing method and a use having the features set forth in the independent claims. The dependent claims disclose preferred embodiments of the present disclosure.
[0007] The present disclosure provides a laminate including a first layer and a second layer, wherein the first layer includes at least one carbon allotrope and a dopant that improves electrical conductivity of the first layer, and the second layer includes an organic material, and the concentration of the dopant in the first layer is 25 to 1000 nmol / cm 2 In other words, the concentration of the dopant used in the first layer in the laminate of the present disclosure is several times, for example 2 to 50 times, the concentration required to improve the electrical conductivity of the first layer.
[0008] An advantage of the present disclosure is that the excess dopant used in the first layer acts as a sacrificial dopant, thereby reducing the rate of UV degradation of the laminate to an acceptable level that will last over the life of the product in which the laminate is used, such as a vehicle windshield. [Brief explanation of the drawings]
[0009] The present disclosure will be described in detail with reference to specific embodiments with reference to the accompanying drawings. [Figure 1] FIG. 1 is a schematic diagram of a cross section of a laminate according to some embodiments of the present disclosure. [Figure 2] FIG. 2 is a schematic diagram of a cross section of a laminate according to some embodiments of the present disclosure. [Figure 3] FIG. 3 is a schematic diagram of a cross section of a laminate according to some embodiments of the present disclosure.
[0010] Detailed Description of the Invention Laminate The present invention relates to a laminate. As illustrated in FIG. 1, the laminate 1 has a first layer 11 and a second layer 12. For example, the thickness of the first layer is 25 to 400 μm, and the thickness of the second layer is 100 to 1000 μm. The first layer 11 and the second layer 12 are bonded to each other. For example, the laminate 1 can be used in vehicle windshields, vehicle mirrors, vehicle headlights and taillights, vehicle dashboards (e.g., touchscreens and infotainment screens on vehicle dashboards), security and surveillance cameras, and lidars (e.g., lidar sensor covers).
[0011] 2, the laminate 1 includes a first substrate layer 13 in addition to a first layer 11 and a second layer 12. The first substrate layer 13 is a layer made of glass, polyethylene terephthalate (PET), polycarbonate (PC), polyethylene naphthalate (PEN), or cyclic olefin polymer (COP). The second layer 12 is disposed between the first layer 11 and the first substrate layer 13.
[0012] 3, the laminate 1 includes a second substrate layer 14 in addition to a first substrate layer 13. The second substrate layer 14 is a layer made of glass, polyethylene terephthalate (PET), polycarbonate (PC), polyethylene naphthalate, or cyclic olefin polymer (COP). The first layer 11 and the second layer 12 are disposed between the first substrate layer 13 and the second substrate layer 14 to form a sandwich structure.
[0013] According to some embodiments, the sandwich structure includes an additional layer 15, such as an adhesive layer or a reinforcing layer, as illustrated in Figure 3. For example, the sandwich structure can be used as a vehicle windshield, a vehicle mirror, a vehicle headlight cover, a vehicle taillight cover, a touchscreen for use in a vehicle dashboard, an infotainment screen for use in a vehicle dashboard, a security or surveillance camera lens, or a cover for a lidar sensor.
[0014] 1st layer The purpose of the first layer 11 is to act as a functional layer. In other words, the first layer 11 imparts a function to the laminate 1. For example, the first layer 11 functions as a heater in the laminate 1.
[0015] According to some embodiments, the first layer 11 comprises a transparent, flexible polymer film, such as a film made from PET, PC, PEN, or COP. The purpose of the transparent, flexible polymer film is to act as a carrier and support (or support) for any functional moieties of the first layer 11.
[0016] carbon allotropes The first layer 11 includes at least one allotrope of carbon. In this context, the term "allotrope" refers to structurally different forms of the same element, in this case, carbon. According to some embodiments, the at least one carbon allotrope is provided as a thin coating on a transparent, flexible polymer film. For example, the thickness of the coating of the at least one carbon allotrope is 0.2 to 1000 nm.
[0017] Preferably, the at least one carbon allotrope is an electrically conductive carbon allotrope.
[0018] The purpose of the carbon allotrope is to act as a functional moiety in the first layer 11. For example, the carbon allotrope allows the first layer 11 to act as a heater in the stack 1.
[0019] According to some embodiments, the at least one carbon allotrope is a carbon nanotube or graphene, in other words, the first layer 11 comprises a carbon nanotube or graphene.
[0020] Dopant The first layer 11 includes a dopant to increase the electrical conductivity of the first layer 11 .
[0021] According to some embodiments, the dopant comprises a metal ion or a salt thereof.
[0022] According to some embodiments, the dopant comprises a transition metal ion or a salt thereof.
[0023] According to some embodiments, the dopant is a p-type dopant, which is more effective and more stable than, for example, n-type dopants.
[0024] For example, the dopant comprises a cation selected from Ce, Al, Fe, Cu, Sr, Sc, Au, Pt, and Pd, and an anion selected from F, Cl, Br, I, organic acids (e.g., acetate or formate), and their halogenated and sulfonated forms (e.g., triflate, trichloroacetate, or methylsulfonate).
[0025] Preferably, the dopant is a dopant complex formed from a dopant ionic component encapsulated within a polymer matrix. The dopant ionic component is a metal triflate, a metal antimonate, or any combination thereof. The polymer matrix comprises or consists of a hydroxyl-containing polymer. The dopant complex is formed from a dopant ionic component bound to the polymer matrix.
[0026] The concentration of the dopant in the first layer 11 is 25 to 1000 nmol / cm 3 based on the surface area of the first layer 11. 2 and preferably 30 to 500 nmol / cm 2 and more preferably 35 to 200 nmol / cm 2 A low concentration of the dopant does not provide sufficient barrier properties against degradation. A high concentration of the dopant can cause problems, for example, with the solubility of the dopant, leading to crystallization of the dopant, which reduces the transparency of the first layer 11. A high concentration of the dopant can also cause discoloration of the first layer 11.
[0027] 2nd layer The second layer 12 comprises an organic material. The purpose of the second layer 12 is to act as a protective layer in the laminate 1 and to bond an optional first substrate layer 13 to the laminate 1.
[0028] In this context, the term "organic materials" refers to compounds and materials that contain carbon.
[0029] Preferably, the organic material comprises molecules having at least one unshared pair of electrons, in other words, molecules of the organic material have a pair of valence electrons that are not shared with other atoms in a covalent bond.
[0030] According to some embodiments, the organic material is of formula C α H β N γ O δ S ε where α is an integer of 1 to 40, and β, γ, δ, and ε are each independently an integer value in the range of 0 to 20. In other words, the organic material may include a monomer or polymer formed from such an organic component.
[0031] According to some embodiments, the organic material is an optical clear adhesive (OCA).
[0032] According to some embodiments, the organic material is polyvinyl butyral (PVB), thermoplastic polyurethane (TPU), hindered amine light stabilizer (HALS), epoxy resin, or acrylate.
[0033] method The present invention also relates to a method for manufacturing the laminate 1. According to some embodiments, the laminate 1 has a reduced tendency to degradation by UV radiation.
[0034] According to some embodiments, the laminate 1 is a laminate as described above.
[0035] The method includes providing a first layer 11. The purpose of the first layer 11 is to act as a functional layer.
[0036] The first layer 11 includes at least one carbon allotrope. Preferably, the at least one carbon allotrope is an electrically conductive carbon allotrope.
[0037] According to some embodiments, the at least one carbon allotrope is a carbon nanotube or graphene, in other words, the first layer 11 comprises a carbon nanotube or graphene.
[0038] The first layer 11 includes a dopant to improve the electrical conductivity of the first layer 11 .
[0039] According to some embodiments, the dopant comprises a metal ion or a salt thereof.
[0040] According to some embodiments, the dopant comprises a transition metal ion or a salt thereof.
[0041] According to some embodiments, the dopant is a p-type dopant, for example, the dopant comprises a cation selected from Ce, Al, Fe, Cu, Sr, Sc, Au, Pt, and Pd, and an anion selected from F, Cl, Br, I, organic acids (e.g., acetate or formate), and halogenated and sulfonated organic acids such as triflate, trichloroacetate, or methylsulfonate.
[0042] Preferably, the dopant is a dopant complex formed from a dopant ionic component encapsulated within a polymer matrix. The dopant ionic component is a metal triflate, a metal antimonate, or any combination thereof. The polymer matrix comprises or consists of a hydroxyl-containing polymer. The dopant complex is formed from a dopant ionic component bound to the polymer matrix.
[0043] The concentration of the dopant in the first layer 11 is 25 to 1000 nmol / cm 3 based on the surface area of the first layer 11. 2 and preferably 30 to 500 nmol / cm 2 and more preferably 35 to 200 nmol / cm 2 is.
[0044] The manufacturing method includes providing a second layer 12. The purpose of the second layer 12 is to act as a protective layer for the laminate 1 and to bond an optional glass layer to the laminate 1.
[0045] The second layer 12 includes an organic material. Preferably, the organic material includes molecules having at least one unshared electron pair.
[0046] According to some embodiments, the organic material is of formula C α H β N γ O δ S ε where α is an integer of 1 to 40, and β, γ, δ, and ε are each independently an integer value ranging from 0 to 20. In other words, the organic material may include a monomer or polymer formed from such an organic component.
[0047] use The present invention provides a method for reducing degradation of a laminate due to, for example, ultraviolet light, heat, or moisture, comprising: 2 The present invention also relates to the use of dopants in concentrations of
[0048] The laminate 1 has a first layer 11 and a second layer 12. The concentration of the dopant is based on the surface area of the first layer 11.
[0049] The first layer 11 includes at least one carbon allotrope. Preferably, the at least one carbon allotrope is an electrically conductive carbon allotrope.
[0050] According to some embodiments, the at least one carbon allotrope is a carbon nanotube or graphene, in other words, the first layer 11 comprises a carbon nanotube or graphene.
[0051] The dopant is contained in the first layer 11. The purpose of the dopant is to improve the electrical conductivity of the first layer 11.
[0052] According to some embodiments, the dopant comprises a metal ion or a salt thereof.
[0053] According to some embodiments, the dopant comprises a transition metal ion or a salt thereof.
[0054] According to some embodiments, the dopant is a p-type dopant, for example, the dopant comprises a cation selected from Ce, Al, Fe, Cu, Sr, Sc, Au, Pt, and Pd, and an anion selected from F, Cl, Br, I, organic acids (e.g., acetate or formate), and halogenated and sulfonated versions of organic acids such as triflate, trichloroacetate, or methylsulfonate.
[0055] Preferably, the dopant is a dopant complex formed from a dopant ionic component encapsulated within a polymer matrix. The dopant ionic component is a metal triflate, a metal antimonate, or any combination thereof. The polymer matrix comprises or consists of a hydroxyl-containing polymer. The dopant complex forms from the dopant ionic component bound to the polymer matrix.
[0056] The concentration of the dopant in the first layer 11 is 25 to 1000 nmol / cm 3 based on the surface area of the first layer 11. 2 and preferably 30 to 500 nmol / cm 2 and more preferably 35 to 200 nmol / cm 2 is.
[0057] The second layer 12 includes an organic material. Preferably, the organic material includes molecules having at least one unshared electron pair.
[0058] According to some embodiments, the organic material is of formula C α H β N γ O δ S ε where α is an integer of 1 to 40, and β, γ, δ, and ε are each independently an integer value in the range of 0 to 20. In other words, the organic material may include a monomer or polymer formed from such an organic component.
[0059] According to some embodiments, the organic material is an optical clear adhesive (OCA).
[0060] According to some embodiments, the organic material is polyvinyl butyral (PVB), thermoplastic polyurethane (TPU), hindered amine light stabilizer (HALS), epoxy resin, or acrylate.
[0061] Example Example 1 (Reference Example) A laminate was prepared consisting of a polyethylene terephthalate substrate and a carbon nanotube-based heater layer. The heater layer was laminated with polyvinyl butyral. The heater was doped with a p-type dopant complex formed from cerium triflate encapsulated in a copolymer of polyvinylphenol and polymethyl methacrylate. The dopant concentration was 10.0 nmol / cm based on the surface area of the laminate. 2 It was.
[0062] The heater was subjected to accelerated aging at 85°C and 85% relative humidity for 20 hours. The heater resistance was measured before and after accelerated aging using a two-probe multimeter. Before accelerated aging, the heater resistance was 130 ohms. After accelerated aging, the heater resistance was 870 ohms.
[0063] Example 2 (Example of the invention) The heater of Example 2 has a dopant concentration of 100 nmol / cm 3 based on the surface area of the laminate. 2 This was different from the heater of Example 1 in that:
[0064] The heater was subjected to accelerated aging as in Example 1. The resistance of the heater was measured before and after accelerated aging using the same method as in Example 1. Before accelerated aging, the resistance of the heater was 137 ohms. After accelerated aging, the resistance of the heater was 190 ohms.
Claims
1. A laminate (1) having a first layer (11) and a second layer (12), The first layer (11) comprises at least one allotrope of carbon and a dopant for improving the electrical conductivity of the first layer (11); and The second layer comprises an organic material; The dopant concentration of the first layer (11) is 25 to 1000 nmol / cm 3 based on the surface area of the first layer (11). ２ The laminate (1) is:
2. Stack (1) according to claim 1, wherein at least one allotrope of carbon is an electrically conductive carbon allotrope.
3. 3. The laminate (1) according to claim 1 or claim 2, wherein at least one allotrope of carbon is a carbon nanotube or graphene.
4. The laminate (1) according to any one of claims 1 to 3, wherein the organic material comprises a molecule having at least one unshared electron pair.
5. The organic material is of formula C α H β N γ O δ S ε 5. The laminate (1) according to claim 4, wherein α is an integer between 1 and 40, and β, γ, δ, and ε are each independently an integer between 0 and 20.
6. Laminate (1) according to any one of claims 1 to 5, wherein the organic material is polyvinyl butyral or thermoplastic polyurethane.
7. The laminate (1) according to any one of claims 1 to 6, wherein the first layer (11) comprises polyethylene terephthalate.
8. The laminate (1) according to any one of claims 1 to 7, wherein the dopant comprises a metal ion or a salt thereof.
9. Stack (1) according to claim 8, wherein the dopant comprises a transition metal ion or a salt thereof.
10. Stack (1) according to any one of claims 1 to 9, wherein the dopant is a p-type dopant.
11. The laminate (1) according to any one of claims 1 to 10, wherein the laminate (1) comprises a first substrate layer (13).
12. A method for producing a laminate (1) having a first layer (11) and a second layer (12), comprising: providing a first layer (11) comprising at least one allotrope of carbon and a dopant for improving the electrical conductivity of the first layer (11); providing a second layer (12) comprising an organic material; and The concentration of the dopant in the first layer (11) is 25 to 1000 nmol / cm 3 based on the surface area of the first layer (11). ２ The manufacturing method is as follows.
13. 13. A method according to claim 12, wherein the laminate (1) has a reduced tendency to deteriorate.
14. The method according to claim 12 or 13, wherein the laminate (1) is a laminate according to any one of claims 1 to 11.
15. 25 to 1000 nmol / cm for reducing degradation of a laminate having a first layer (11) and a second layer (12). ２ The use of a dopant in a concentration of The first layer (11) comprises at least one allotrope of carbon and a dopant for improving the electrical conductivity of the first layer (11), and The second layer (12) comprises an organic material; The concentration of the dopant is based on the surface area of the first layer.