Laminate and method for producing laminate

Abstract

This disclosure relates to a laminate (1). The laminate (1) includes a first layer (11) containing at least one carbon allotrope and a dopant. The laminate (1) includes a second layer (12) comprising an organic material. The concentration of the dopant in the first layer (11) based on the surface area of ​​the first layer (11) is from 25 nmol / cm² to 1000 nmol / cm². This disclosure also relates to a method of manufacturing the laminate (1). The method includes providing a first layer (11) comprising at least one carbon allotrope and a dopant. The method includes providing a second layer (12) comprising an organic material. The concentration of the dopant in the first layer (11) is from 25 nmol / cm² to 1000 nmol / cm². This invention also relates to the use of dopant in reducing degradation of laminates, wherein the concentration of the dopant is from 25 nmol / cm² to 1000 nmol / cm².

Description

[Technical Field]

[0001] This disclosure relates to laminates, and more particularly to laminates containing doped carbon allotropes. This disclosure further relates to methods for manufacturing laminates, and uses to reduce dopants that contribute to the degradation of laminates. [Previous Technology]

[0002] Carbon nanotubes can be used to provide functional layers for laminated panels. For example, in laminated automotive windshields, carbon nanotubes can be used to provide heating units for the laminated windshields to achieve purposes such as defrosting, de-icing, and preventing fogging.

[0003] Dopants are used to adjust the properties of carbon nanotubes. For example, dopants can improve the conductivity of carbon nanotubes. Layers containing carbon nanotubes and dopants can be laminated with glass layers, and the lamination method uses optically transparent adhesives and bonding layers such as polyvinyl butyral (PVB) or thermoplastic polyurethane (TPU).

[0004] A related problem with the above-described lamination method is that the laminate degrades over time due to sunlight. This is because the optically transparent adhesive, or components that diffuse or escape from it (e.g., due to the chemical decomposition of the optically transparent adhesive), will neutralize dopants under ultraviolet radiation in sunlight. This can be observed as an increase in the resistance of the functional layers. [Summary of the Invention]

[0005] The purpose of this disclosure is to provide a laminate, a method for manufacturing a laminate, and the use of dopants to overcome the above-mentioned problems.

[0006] The present disclosure is made possible by a laminate, method, and use characterized by the contents described in the independent claims of the patent claims. Preferred embodiments of the present disclosure are disclosed in the appendices to the claims.

[0007] This disclosure is based on the idea of ​​providing a laminate comprising a first layer and a second layer, the first layer comprising at least one carbon allotrope and a dopant to improve the conductivity of the first layer, and the second layer comprising an organic material, wherein the dopant concentration in the first layer (11) is from 25 nmol / cm² to 1000 nmol / cm². In other words, the dopant concentration used in the first layer of the laminate of this disclosure is several times (e.g., 2 to 50 times) the concentration required to improve the conductivity of the first layer.

[0008] One of the advantages of this disclosure is that the excess dopant used in the first layer can act as a sacrificial dopant. This reduces the degradation rate of the laminate caused by ultraviolet radiation to an acceptable level, such as beyond the service life of products using laminates (e.g., automotive windshields).

Implementation Method

[0010] Laminated board

[0011] This disclosure relates to laminates. The laminate 1 includes a first layer 11 and a second layer 12, as shown in FIG1. ​​For example, the thickness of the first layer is 25 micrometers to 400 micrometers, and the thickness of the second layer is 100 micrometers to 1000 micrometers. The first layer 11 and the second layer 12 are bonded together. For example, the laminate 1 can be used in automotive windshields, automotive rearview mirrors, automotive headlights and taillights, automotive dashboards (such as touchscreens and infotainment screens used in automotive dashboards), security and surveillance cameras, and laser radar (such as laser radar sensor covers).

[0012] In some embodiments, the laminate 1 includes a first substrate layer 13 in addition to the first layer 11 and the second layer 12, as shown in FIG2. The first substrate layer 13 is a layer composed 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.

[0013] In some embodiments, the laminate 1 includes a second substrate layer 14 in addition to the first substrate layer 13, as shown in FIG3. The second substrate layer 14 is a layer composed of glass, polyethylene terephthalate (PET), polycarbonate (PC), polyethylene naphthalate (PEN), 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.

[0014] In some embodiments, the sandwich structure includes other layers 15 such as adhesive layers or reinforcing layers, as shown in FIG3. For example, the sandwich structure may be used as a car windshield, a car rearview mirror, a car headlight cover, a car taillight cover, a touch screen in a car dashboard, an infotainment screen in a car dashboard, a lens in a security or surveillance camera, or a lidar sensor cover.

[0015] First Floor

[0016] The purpose of the first layer 11 is to serve as a functional layer. In other words, the first layer 11 provides the function of the laminate 1. For example, the first layer 11 serves as a heater in the laminate 1.

[0017] In some embodiments, the first layer 11 comprises a transparent, flexible polymer film, such as a film composed of PET, PC, PEN, or COP. The purpose of the transparent, flexible film is to serve as a carrier or support for any functional part of the first layer 11.

[0018] Allotropes of carbon

[0019] The first layer 11 includes at least one carbon allotrope. In this context, "allotrope" refers to the same element (in this example, carbon) with different structural forms. In some embodiments, the at least one carbon allotrope serves as a thin coating on a transparent flexible polymer film. For example, the coating thickness of the at least one carbon allotrope is from 0.2 nm to 1000 nm.

[0020] The at least one carbon allotrope is preferably a conductive carbon allotrope.

[0021] The purpose of the carbon allotrope is to serve as a functional part in the first layer 11. For example, the carbon allotrope can make the first layer 11 a heater in the laminate 1.

[0022] In some embodiments, at least one carbon allotrope is a carbon nanotube or graphene. In other words, the first layer 11 comprises carbon nanotubes or graphene.

[0023] Dopant

[0024] The first layer 11 includes dopants used to improve the conductivity of the first layer 11.

[0025] In some embodiments, the dopant includes metal ions or salts thereof.

[0026] In some embodiments, the dopant includes transition metal ions or salts thereof.

[0027] In some embodiments, the dopant is a p-type dopant. P-type dopants are more effective and more stable than n-type dopants.

[0028] For example, dopants include cations selected from cerium, aluminum, iron, copper, strontium, scandium, gold, platinum, and palladium; and anions selected from fluorine, chlorine, bromine, iodine, organic acids (such as acetate or formate), and halogenated or sulfonated organic acids (such as trifluoromethanesulfonate, trichloroacetate, or methanesulfonate).

[0029] The dopant is preferably a dopant complex formed by sealing the dopant ion component in a polymer matrix, wherein the dopant ion component is a metal trifluoromethanesulfonate, a metal antimonate, or any combination thereof, and the polymer matrix includes or is composed of a hydroxyl-containing polymer, and wherein the dopant complex is formed by coupling the dopant ion component to the polymer matrix.

[0030] The concentration of dopant in the first layer 11, based on the surface area of ​​the first layer 11, is from 25 nmol / cm² to 1000 nmol / cm², more preferably from 30 nmol / cm² to 500 nmol / cm², and even more preferably from 35 nmol / cm² to 200 nmol / cm². If the dopant concentration is too low, sufficient barrier properties cannot be provided to resist degradation. If the dopant concentration is too high, problems such as dopant solubility issues may arise, which may cause dopant crystallization and reduce the transparency of the first layer 11. High concentrations of dopant may also cause discoloration of the first layer 11.

[0031] Second Layer

[0032] The second layer 12 includes an organic material. The purpose of the second layer 12 is to serve as a protective layer in the laminate 1 and to bond the first substrate layer 13, which may be used as appropriate, to the laminate 1.

[0033] In this content, the term "organic material" refers to carbon-containing compounds and materials.

[0034] Organic materials preferably include molecules that have at least one lone pair of electrons. In other words, the molecules of organic materials have a pair of valence electrons that are not shared with another atom in a covalent bond.

[0035] In some embodiments, the organic material comprises a plurality of organic parts having the chemical formula CαHβNγOδSε, wherein α is an integer from 1 to 40, and β, γ, δ, and ε are each independently an integer from 0 to 20. In other words, the organic material may include monomers or polymers composed of these organic parts.

[0036] In some embodiments, the organic material is optically transparent adhesive (OCA).

[0037] In some embodiments, the organic material is polyvinyl butyral (PVB), thermoplastic polyurethane (TPU), hindered amine light stabilizer (HALS), epoxy resin, or acrylate.

[0038] Method

[0039] The present invention also relates to a method for producing a laminate. In some embodiments, the laminate 1 tends to decrease due to degradation by ultraviolet light.

[0040] In some embodiments, the laminate 1 is the laminate described above.

[0041] The method includes providing a first layer 11. The purpose of the first layer 11 is to serve as a functional layer.

[0042] The first layer 11 includes at least one carbon allotrope. The at least one carbon allotrope is preferably a conductive carbon allotrope.

[0043] In some embodiments, at least one carbon allotrope is a carbon nanotube or graphene. In other words, the first layer 11 comprises carbon nanotubes or graphene.

[0044] The first layer 11 includes dopants used to improve the conductivity of the first layer 11.

[0045] In some embodiments, the dopant includes metal ions or salts thereof.

[0046] In some embodiments, the dopant includes transition metal ions or salts thereof.

[0047] In some embodiments, the dopant is a p-type dopant. For example, the dopant includes cations selected from cerium, aluminum, iron, copper, strontium, scandium, gold, platinum, and palladium; and anions selected from fluorine, chlorine, bromine, iodine, organic acids (such as acetate or formate), and halogenated or sulfonated organic acids (such as trifluoromethanesulfonate, trichloroacetate, or methanesulfonate).

[0048] The dopant is preferably a dopant complex formed by sealing the dopant ion component in a polymer matrix, wherein the dopant ion component is a metal trifluoromethanesulfonate, a metal antimonate, or any combination thereof, and the polymer matrix includes or is composed of a hydroxyl-containing polymer, and wherein the dopant complex is formed by coupling the dopant ion component to the polymer matrix.

[0049] The dopant concentration in the first layer 11 based on the surface area of ​​the first layer 11 is from 25 nmol / cm2 to 1000 nmol / cm2, more preferably from 30 nmol / cm2 to 500 nmol / cm2, and even more preferably from 35 nmol / cm2 to 200 nmol / cm2.

[0050] The method includes providing a second layer 12. The purpose of the second layer 12 is to serve as a protective layer in the laminate 1 and to bond glass layers, as appropriate, to the laminate 1.

[0051] The second layer 12 includes organic materials. The organic materials preferably include molecules that have at least one lone pair of electrons.

[0052] In some embodiments, the organic material comprises a plurality of organic parts having the chemical formula CαHβNγOδSε, wherein α is an integer from 1 to 40, and β, γ, δ, and ε are each independently an integer from 0 to 20. In other words, the organic material may include monomers or polymers composed of these organic parts.

[0053] Application

[0054] The present invention also relates to the use of dopants to reduce degradation of laminates, wherein the concentration of the dopants is from 25 nmol / cm2 to 1000 nmol / cm2, and the cause of degradation of the laminates is ultraviolet light, heat, or moisture.

[0055] The laminate 1 includes 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.

[0056] The first layer 11 includes at least one carbon allotrope. The at least one carbon allotrope is preferably a conductive carbon allotrope.

[0057] In some embodiments, at least one carbon allotrope is a carbon nanotube or graphene. In other words, the first layer 11 comprises carbon nanotubes or graphene.

[0058] The dopant is contained in the first layer 11. The purpose of the dopant is to improve the conductivity of the first layer 11.

[0059] In some embodiments, the dopant includes metal ions or salts thereof.

[0060] In some embodiments, the dopant includes transition metal ions or salts thereof.

[0061] In some embodiments, the dopant is a p-type dopant. For example, the dopant includes cations selected from cerium, aluminum, iron, copper, strontium, scandium, gold, platinum, and palladium; and anions selected from fluorine, chlorine, bromine, iodine, organic acids (such as acetate or formate), and halogenated or sulfonated organic acids (such as trifluoromethanesulfonate, trichloroacetate, or methanesulfonate).

[0062] The dopant is preferably a dopant complex formed by sealing the dopant ion component in a polymer matrix, wherein the dopant ion component is a metal trifluoromethanesulfonate, a metal antimonate, or any combination thereof, and the polymer matrix includes or is composed of a hydroxyl-containing polymer, and wherein the dopant complex is formed by coupling the dopant ion component to the polymer matrix.

[0063] The dopant concentration in the first layer 11 based on the surface area of ​​the first layer 11 is from 25 nmol / cm2 to 1000 nmol / cm2, more preferably from 30 nmol / cm2 to 500 nmol / cm2, and even more preferably from 35 nmol / cm2 to 200 nmol / cm2.

[0064] The second layer 12 includes organic materials. The organic materials preferably include molecules that have at least one lone pair of electrons.

[0065] In some embodiments, the organic material comprises a plurality of organic parts having the chemical formula CαHβNγOδSε, wherein α is an integer from 1 to 40, and β, γ, δ, and ε are each independently an integer from 0 to 20. In other words, the organic material may include monomers or polymers composed of these organic parts.

[0066] In some embodiments, the organic material is optically transparent adhesive (OCA).

[0067] In some embodiments, the organic material is polyvinyl butyral (PVB), thermoplastic polyurethane (TPU), hindered amine light stabilizer (HALS), epoxy resin, or acrylate.

[0068] Example

[0069] Example 1 (Reference Example)

[0070] A laminate is provided, comprising a polyethylene terephthalate substrate and a heater layer primarily composed of transparent carbon nanotubes laminated with polyvinyl butyral. The heater is doped with a p-type dopant composite consisting of cerium trifluoromethanesulfonate sealed in a copolymer of polyvinylphenol and polymethyl methacrylate.

[0071] The heater was exposed to a temperature of 85°C and a relative humidity of 85% for 20 hours of accelerated aging. The heater resistance was measured before and after accelerated aging using a two-point probe multimeter. Before accelerated aging, the heater resistance was 130 ohms. After accelerated aging, the heater resistance was 870 ohms.

[0072] Example 2 (Invention Example)

[0073] The difference between the heater of Example 2 and the heater of Example 1 is that the dopant concentration based on the surface area of ​​the laminate is 100 nmol / cm2.

[0074] The heater was exposed to the accelerated aging conditions of Example 1. The heater resistance was measured before and after accelerated aging using the same method as in Example 1. Before accelerated aging, the heater resistance was 137 ohms. After accelerated aging, the heater resistance was 190 ohms. [Simplified Explanation of the Diagram]

[0009] This disclosure is described in detail with reference to specific embodiments and the accompanying drawings. Figure 1 is a cross-sectional view of a laminated plate in some embodiments of this disclosure. Figure 2 is a cross-sectional view of a laminated plate in some embodiments of this disclosure. Figure 3 is a cross-sectional view of a laminated plate in some embodiments of this disclosure.

Claims

1. A laminated plate (1), characterized in that the laminated plate (1) comprises: A first layer (11) comprising a transparent and flexible polymer film, at least one carbon allotrope, and a dopant for improving the conductivity of the first layer (11); a second layer (12) comprising an organic material, wherein the organic material neutralizes the dopant under ultraviolet irradiation; and a first substrate layer (13), wherein the concentration of the dopant in the first layer (11) is from 25 nmol / cm2 to 1000 nmol / cm2 based on the surface area of ​​the first layer (11); and wherein the second layer (12) is disposed between the first layer (11) and the first substrate layer (13).

2. The laminate (1) as claimed in claim 1, characterized in that the at least one carbon allotrope is a conductive carbon allotrope.

3. The laminate (1) as claimed in claim 1 or 2, characterized in that the at least one carbon allotrope is a carbon nanotube or graphene.

4. The laminate (1) as claimed in claim 1 or 2, characterized in that the organic material comprises molecules having at least one lone pair of electrons.

5. The laminate (1) as claimed in claim 4, characterized in that the organic material comprises a plurality of organic parts having the chemical formula CαHβNγOδSε, wherein α is an integer from 1 to 40, and β, γ, δ, and ε are each an integer from 0 to 20 independently.

6. The laminate (1) as claimed in claim 1 or 2, characterized in that the organic material is polyvinyl butyral or thermoplastic polyurethane.

7. The laminate (1) as claimed in claim 1 or 2, characterized in that the transparent flexible polymer film of the first layer (11) comprises polyethylene terephthalate.

8. The laminate (1) as claimed in claim 1 or 2, characterized in that the dopant comprises metal ions or salts thereof.

9. The laminate (1) as claimed in claim 8, characterized in that the dopant comprises a transition metal ion or a salt thereof.

10. The laminate (1) as claimed in claim 1 or 2, characterized in that the dopant is a p-type dopant.

11. A method for manufacturing a laminate (1) according to any one of claims 1 to 10, characterized in that the method comprises: The first layer (11) is provided, comprising the transparent and flexible polymer film, at least one carbon allotrope, and a dopant used to improve the conductivity of the first layer (11); the second layer (12) is provided, comprising the organic material, wherein the organic material will neutralize the dopant under ultraviolet irradiation; and the first substrate layer (13) is provided; wherein the concentration of the dopant in the first layer (11) based on the surface area of ​​the first layer (11) is from 25 nmol / cm2 to 1000 nmol / cm2, and wherein the second layer (12) is disposed between the first layer (11) and the first substrate layer (13).

12. A method for manufacturing the laminate (1) as described in claim 11, characterized in that the degradation of the laminate (1) tends to decrease.

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