Quantum dot pigment and preparation method thereof, quantum dot paint and quantum dot coating

Abstract

The invention relates to a quantum dot pigment and a preparation method thereof, a quantum dot coating and a quantum dot coating. The quantum dots are modified and then dissolved and dispersed in an oily or aqueous organic solvent to obtain a quantum dot solution, and the obtained quantum dot solution is used as a pigment to be applied to coating materials such as paint and paint. According to the quantum dot pigment, multi-color developing of the pigment with the same chemical component can be achieved, on one hand, the growth process of the quantum dots is controlled based on the size effect of the quantum dots, the quantum dots of different sizes are prepared, and the colors are regulated and controlled through the sizes of the quantum dots; on the other hand, the thickness of the quantum dot coating can be adjusted by controlling the technological process of coating and film forming, and the thickness of the quantum dot coating can also adjust and control the color.

Description

Technical Field

[0001] The present invention relates to the technical field of coatings, and in particular to a quantum dot pigment and a preparation method thereof, a quantum dot coating, and a quantum dot coating. Background Art

[0002] Paint is a substance that can be applied to the surface of an object to form a solid film layer with protective, decorative or special properties. It is widely used in the fields of construction, industry, automobiles, homes, etc. According to its main functions and uses, it can be divided into decorative paints, protective paints and functional paints. The composition of paints usually includes film-forming substances, pigments, fillers, solvents and additives, so that the paint can have a variety of application scenarios. Among them, pigments can give the paint color and opacity, and also provide certain anti-corrosion and anti-ultraviolet functions. However, in some special applications, traditional pigments face challenges and limitations in color adjustment. Summary of the invention

[0003] The present invention provides a quantum dot pigment and a preparation method thereof, a quantum dot paint, and a quantum dot coating. Based on the unique multi-color properties of quantum dots, they are used in combination with paints. By simultaneously modifying the resin material and quantum dots in the paint, the quantum dot paint is given more excellent color adjustment properties.

[0004] In order to solve the above technical problems, the present invention adopts the following technical solutions:

[0005] First aspect

[0006] The present application provides a quantum dot pigment, which includes quantum dots and a first organic solvent.

[0007] In one embodiment, the first organic solvent is an alkane solvent, the ligand of the quantum dots is lipophilic, and the quantum dot pigment is an oily quantum dot pigment.

[0008] In one embodiment, the first organic solvent is an amide solvent, the ligand of the quantum dots is hydrophilic, and the quantum dot pigment is a water-based quantum dot pigment.

[0009] In one embodiment, the quantum dot pigment further includes a resin, the quantum dots are uniformly dispersed in the resin to form a quantum dot-resin composite, and the quantum dot-resin composite is dissolved in the first organic solvent.

[0010] In this embodiment, the concentration of the quantum dots in the first organic solvent is 0.1-500 mg / mL.

[0011] Second aspect

[0012] The present invention provides a method for preparing a quantum dot pigment, comprising the following steps:

[0013] S10, preparation of quantum dots;

[0014] S20, dissolving and dispersing the quantum dots in an alkane solvent, fully mixing, then adding an extraction solvent, and centrifuging to obtain oily quantum dots;

[0015] S30, dissolving and dispersing the oily quantum dots in a lipophilic organic solvent to obtain an oily quantum dot pigment.

[0016] The present invention provides a method for preparing a quantum dot pigment, comprising the following steps:

[0017] S10, preparation of quantum dots;

[0018] S20, dissolving and dispersing the quantum dots in an alkane solvent, fully mixing, then adding an extraction solvent, and centrifuging to obtain oily quantum dots;

[0019] S30, dissolving the oily quantum dots and adding an organic solvent with a hydrophilic group, fully mixing to complete ligand conversion, then adding an extraction solvent, and centrifuging to obtain water-based quantum dots;

[0020] S40, dissolving and dispersing the water-based quantum dots in a hydrophilic organic solvent to obtain a water-based quantum dot pigment.

[0021] In one embodiment, in step S40, it is necessary to first disperse the aqueous quantum dots in a resin to form a quantum dot-resin complex, and then disperse the quantum dot-resin complex in an organic solvent having a hydrophilic group.

[0022] In one embodiment, in step S40, the concentration of the quantum dots in the organic solvent with hydrophilic groups is controlled to be 0.1-500 mg / mL.

[0023] In one embodiment, steps S20 to S40 are all performed under yellow light conditions.

[0024] The third aspect

[0025] The present invention provides a quantum dot coating, comprising:

[0026] A coating solution comprises a coating and a second organic solvent, wherein the coating is dissolved in the second organic solvent; and

[0027] A quantum dot pigment as described in any of the above structural embodiments or a quantum dot pigment prepared by any of the method embodiments;

[0028] Wherein, the coating solution and the quantum dot pigment are uniformly mixed.

[0029] In one of the embodiments, the concentration of the quantum dots in the coating solution is 2-50 wt %.

[0030] In one embodiment, the second organic solvent is the same as the first organic solvent.

[0031] The fourth aspect

[0032] The present application provides a quantum dot coating, including the quantum dot coating as described in any of the foregoing embodiments, wherein the quantum dot coating is prepared by coating the quantum dot coating on a substrate.

[0033] It can be seen from the above technical solutions that the embodiments of the present invention have at least the following advantages and positive effects:

[0034] The embodiment of the present invention provides a quantum dot pigment and a preparation method thereof, a quantum dot coating, and a quantum dot coating. The quantum dots are modified and dissolved and dispersed in an oily or aqueous organic solvent to obtain a quantum dot solution, and the obtained quantum dot solution is used as a pigment in coating materials such as coatings and paints. The quantum dot pigment of the present application can achieve colorful color display of pigments with the same chemical component: on the one hand, based on the size effect of quantum dots, the quantum dot growth process is controlled to prepare quantum dots of different sizes, and the color is controlled by the size of the quantum dots; on the other hand, the thickness of the quantum dot coating can be adjusted by controlling the coating film forming process, and the thickness of the quantum dot coating can also control the color. Traditional quantum dot pigments are achieved by combining natural or artificial pigments of various chemical components to achieve quantum dot color display, while the quantum dot pigment of the present application can adjust the color by adjusting the size of the quantum dots and the thickness of the quantum dot coating based on the size effect and optical properties of the quantum dots, so as to achieve colorful color display of the same chemical component. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the structures shown in these drawings without paying creative work.

[0036] Figure 1 This is a schematic diagram of the components of a quantum dot pigment according to an embodiment of the present application;

[0037] Figure 2 This is a schematic diagram of components of another embodiment of the quantum dot pigment of the present application;

[0038] Figure 3 A flow chart of preparing oily quantum dot pigment according to one embodiment of the present application;

[0039] Figure 4 This is a flow chart of preparing water-based quantum dot pigments according to one embodiment of the present application.

[0040] The following are the descriptions of the reference numerals:

[0041] 10. quantum dot pigment; 100. quantum dot; 200. first solvent; 300. resin; 103. quantum dot-resin composite. DETAILED DESCRIPTION

[0042] Typical embodiments that embody the features and advantages of the present invention will be described in detail in the following description. It should be understood that the present invention can have various changes in different embodiments without departing from the scope of the present invention, and the descriptions and illustrations therein are essentially used for illustration purposes rather than for limiting the present invention.

[0043] In addition, the terms "first" and "second" are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. Thus, the features defined as "first" and "second" may explicitly or implicitly include one or more of the features. In the description of this application, the meaning of "plurality" is two or more, unless otherwise clearly and specifically defined.

[0044] In the description of this application, it should be noted that, unless otherwise clearly specified and limited, the terms "installation", "setting", and "connection" should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection, or it can be an indirect connection through an intermediate medium, or it can be the internal communication of two components. For ordinary technicians in this field, the specific meanings of the above terms in this application can be understood according to specific circumstances.

[0045] Paint is a substance that can be applied to the surface of an object to form a solid film layer with protective, decorative or special properties. It is widely used in the fields of construction, industry, automobiles, homes, etc. According to its main functions and uses, it can be divided into decorative paints, protective paints and functional paints. The composition of paints usually includes film-forming substances, pigments, fillers, solvents and additives, so that the paint can have a variety of application scenarios. Among them, pigments can give the paint color and opacity, and also provide certain anti-corrosion and anti-ultraviolet functions. However, in some special applications, traditional pigments face challenges and limitations in color adjustment, and customized development of quantum dot pigments has important application value.

[0046] refer to Figure 1The present application provides a quantum dot pigment 10, which is in a liquid or semi-solid state. The quantum dot pigment 10 includes quantum dots 100 and a first organic solvent 200. The quantum dots 100 have different sizes and are uniformly dissolved and dispersed in the first organic solvent 200.

[0047] It should be noted here that the quantum dot 100 is not limited to any one or a combination of two or more of Se, CdS, CdTe, ZnO, ZnSe, ZnS, ZnTe, HgS, HgSe, HgTe, CdZnSe, InAs, InP, InN, GaN, InSb, InAsP, InGaAs, GaAs, GaP, GaSb, AlP, AlN, AlAs, AlSb, CdSeTe, ZnCdS, CdZnSeS, and perovskite quantum dots; The organic solvent 200 includes, but is not limited to, any one of petroleum ether, gasoline, octane, nonane, ethyl benzene, turpentine, heptane, hexane, carbon disulfide, xylene, toluene, propylene chloride, benzene, ethyl bromide, benzene bromide, dichloroethane, chloroform, isopropyl ether, nitromethane, butyl acetate, ethyl acetate, amyl acetate, ethyl ether, acetic acid, ethyl ester, n-pentane, n-butanol, phenol, methyl ethyl alcohol, tert-butanol, tetrahydrofuran, dioxane, methyl ethyl ketone, methyl isopropyl ketone, cyclohexanone, acetone, ethanol, acetonitrile, methanol, dimethylformamide, and water.

[0048] In one embodiment, the first organic solvent 200 is an organic solvent with a lipophilic group, such as n-hexane, petroleum ether, benzene, ether and other organic solvents. At this time, the ligand of the quantum dot 100 is lipophilic, and the quantum dot 100 can be evenly dispersed in the organic solvent with a lipophilic group, so that the quantum dot pigment is an oily quantum dot pigment. The user can add the oily quantum dot pigment to an oily coating or paint to mix and disperse to obtain a quantum dot oily coating.

[0049] In one embodiment, the first organic solvent 200 is an organic solvent with a hydrophilic group, such as methanol, ethanol, acetone and other organic solvents. After the quantum dots 100 are evenly dispersed in the hydrophilic organic solvent, the ligands obtained have hydrophilicity, so that the quantum dot pigment is a water-based quantum dot pigment. The user can add the water-based quantum dot pigment to the water-based paint for mixing and dispersion to obtain the quantum dot water-based paint.

[0050] In one embodiment, reference Figure 2, the quantum dot pigment 10 also includes a resin 300, the quantum dots 100 are uniformly dispersed in the resin to form a quantum dot-resin complex 103, and the quantum dot-resin complex 103 is dissolved in the first organic solvent 200. This further increases the stability of the quantum dot pigment 10 itself. It should be noted that in other embodiments, the quantum dot pigment 10 can also be directly added and dispersed into the coating, and at this time, the quantum dots 100 and the resin in the coating form a quantum dot-resin complex 103. Therefore, for the quantum dot pigment 10 of the present application, without considering the stability of the quantum dots 100 in the quantum dot pigment 10, whether the quantum dot pigment 10 includes the resin 300 is not limited. It should be noted that the resin 300 is a polymer compound, including two major categories: water-based resins and oily resins. Both oily resins and water-based resins can be used as the main dispersing components of the coating to form oily coatings and water-based coatings, respectively.

[0051] In the second aspect, the present application also provides a method for preparing quantum dot pigments. The quantum dot pigments 10 include oily quantum dot pigments and water-based quantum dot pigments. The oily quantum dot pigments are used in combination with oily paints and oil paints to achieve a colorful display of quantum dot paints. The water-based quantum dots are used in combination with water-based paints to achieve a colorful display of quantum dot pigments.

[0052] It should be noted that individual quantum dots are unstable and need to combine with ligands in organic solvents to form a stable quantum dot coordination structure. This combination process is called ligand modification of quantum dots.

[0053] refer to Figure 3 , a method for preparing oily quantum dot pigments, comprising the following steps:

[0054] S10, preparation of quantum dots;

[0055] S20, dissolving and dispersing the quantum dots in an alkane solvent, fully mixing to obtain a quantum dot solution, then adding an extraction solvent, and centrifuging to obtain oily quantum dots; wherein the alkane solvent carries a lipophilic alkyl ligand, and the alkyl ligand is coordinated and combined with the quantum dots to form oily quantum dots, that is, the oily quantum dots are quantum dot structures after the quantum dots are modified with ligands;

[0056] S30, dissolving and dispersing the oily quantum dots in a lipophilic organic solvent to obtain an oily quantum dot pigment.

[0057] In one embodiment, in step S30, the oily quantum dots need to be first dispersed in an oily resin to obtain a lipophilic quantum dot-resin complex, and then the lipophilic quantum dot-resin complex is dispersed and dissolved in a lipophilic organic solvent to obtain an oily quantum dot pigment. The quantum dot-resin complex structure greatly improves the stability of the quantum dots themselves. It should be understood that in other embodiments, if no other modification is required for the oily quantum dots, the quantum dot solution obtained in step S20 is lipophilic and can be directly added to oily coatings and paints as a pigment, and can also achieve quantum dot color development.

[0058] In one embodiment, in step S30, the lipophilic organic solvent is selected as n-hexane solvent. As a lipophilic organic solvent commonly used in experiments, n-hexane solvent can fully dissolve and disperse oily quantum dots.

[0059] refer to Figure 4 The preparation method of water-based quantum dot pigments requires modifying oily quantum dots into water-based quantum dots through ligand exchange, which includes the following steps:

[0060] S10, preparation of quantum dots;

[0061] S20, dissolving and dispersing the quantum dots in an alkane solvent, fully mixing to obtain a quantum dot stock solution, then adding an extraction solvent, and centrifuging to obtain oily quantum dots;

[0062] S30, dissolving the oily quantum dots and adding an organic solvent with a hydrophilic group, fully mixing to complete the ligand conversion, then adding an extraction solvent, and centrifuging to obtain water-based quantum dots;

[0063] S40, dissolving and dispersing the water-based quantum dots in a hydrophilic organic solvent to obtain a water-based quantum dot pigment.

[0064] Among them, the first organic solvent is any one including but not limited to petroleum ether, gasoline, octane, nonane, ethyl benzene, turpentine, heptane, hexane, carbon disulfide, xylene, toluene, propylene chloride, benzene, ethyl bromide, benzene bromide, dichloroethane, chloroform, isopropyl ether, nitromethane, butyl acetate, ethyl acetate, amyl acetate, ethyl ether, acetic acid, ethyl ester, n-pentane, n-butanol, phenol, methyl ethyl alcohol, tert-butanol, tetrahydrofuran, dioxane, methyl ethyl ketone, methyl isopropyl ketone, cyclohexanone, acetone, ethanol, acetonitrile, methanol, dimethylformamide, and water.

[0065] In one embodiment, in step S40, the water-based quantum dots need to be first dispersed in the water-based resin to obtain a hydrophilic quantum dot-resin complex, and then the hydrophilic quantum dot-resin complex is dispersed and dissolved in a hydrophilic organic solvent to obtain an oily quantum dot pigment. The quantum dot-resin complex structure greatly improves the stability of the quantum dots themselves.

[0066] In one embodiment, during the preparation of quantum dot pigments, steps S20 to S40 are all performed under yellow light conditions. This is because quantum dots are not very stable under natural light or white light during preparation, so try to avoid light during production to improve the stability of the quantum dot experiment.

[0067] Preferably, in the present application, the concentration of the quantum dots in the organic solvent with hydrophilic groups is controlled to be in the range of 0.1 to 500 mg / mL according to the size and composition of the quantum dots.

[0068] In one embodiment, the quantum dot stock solution is first centrifuged with acetone. The above operation removes the alkane solvent and excess oily ligands. During the centrifugation process, the unstable ligands will be separated from the quantum dots. In step S30, 1 ml of the oily quantum dot solution is mixed with 1 ml of 3-methylacrylic acid (MAP), and then slightly shaken and ultrasonicated for 1 hour. Add 3 times the volume of acetone and centrifuge to remove the upper liquid to obtain water-based quantum dots. Finally, the water-based quantum dots are added to 0.5 ml of dimethylformamide (DMF) solvent and ultrasonically dissolved and dispersed to obtain water-based quantum dot pigments. Among them, 3-methylacrylic acid contains hydrophilic thiol ligands. This embodiment converts the lipophilic alkyl ligands in the quantum dots into hydrophilic thiol ligands to achieve water-based modification of the quantum dots, and the water-based quantum dots have stronger stability.

[0069] It should be noted that the stability of quantum dots in solution is stronger than that in solid state, so the quantum dot pigments prepared by quantum dot modification need to be dissolved and dispersed in organic solvents for preservation.

[0070] In a third aspect, the present application provides a quantum dot coating, including a coating, a second organic solvent and a quantum dot pigment, wherein the coating is dissolved in the second organic solvent to form a coating solution, and the quantum dot pigment and the coating solution are uniformly mixed to form a quantum dot coating. Here, the quantum dot coating includes oily and water-based, specifically, the oily quantum dot pigment is mixed with the oily coating solution to form an oily quantum dot coating; the water-based quantum dot pigment is mixed with the water-based coating solution to form a water-based quantum dot coating.

[0071] Preferably, in the present application, the first organic solvent is the same as the second organic solvent, that is, the solvent in the quantum dot pigment and the solvent in the coating solution are the same solvent, so that the quantum dot pigment and the coating solution are mixed more evenly and fully, and the mixed quantum dot coating is more stable.

[0072] Preferably, in the present application, the concentration of quantum dots in the coating is 2 to 50 wt %.

[0073] In the present application, the source of the coating can be existing pure color or transparent coating purchased from the market, or can be prepared by the laboratory itself. The coating includes but is not limited to any one of natural resin coating, phenolic coating, alkyd coating, amino coating, nitro coating, epoxy coating, chlorinated rubber coating, acrylic coating, polyurethane coating, silicone resin coating, fluorocarbon resin coating, polysiloxane coating, and vinyl resin coating.

[0074] In the present application, the resin is used as the main component of the coating. The quantum dot pigment can be mixed and dispersed with the resin before being mixed with the coating solution to form a stable quantum dot-resin mixture. The quantum dot pigment can also be directly mixed with the coating solution. The quantum dots react with the resin in the coating to form a quantum dot-resin mixture. The quantum dot-resin mixture improves the stability of the quantum dots as pigments.

[0075] The fourth aspect

[0076] The present application also provides a quantum dot coating, which is a film material prepared by coating quantum dot coating on a substrate. The coating process is called a coating film forming process operation process. The coating film forming methods include but are not limited to brushing, rolling, spraying, dipping, spin coating, printing, and ultrasonic spraying. Here, the quantum dot coating can be used to adjust the thickness of the quantum dot coating by adjusting the process parameters such as the content of quantum dots in the quantum dot coating, coating speed, coating time, curing temperature, and curing time.

[0077] Pigments are related to both human visual characteristics and the objective radiation observed. Color is an important indicator for evaluating the quality of pigment products.

[0078] As an important type of nano-photoelectric material, quantum dots have attracted attention for their high luminous efficiency, adjustable spectral characteristics and solution preparation, and have shown broad application prospects in the fields of lighting display, detection imaging, and biomarkers. Quantum dots have adjustable size absorption and emission, and can achieve colorful color presentation through the control of the synthesis method. Based on the unique multi-color performance of quantum dots, the present invention combines them with coatings to give quantum dot coatings more excellent performance.

[0079] The present application provides a quantum dot pigment and a preparation method thereof, a quantum dot coating, and a quantum dot coating. The quantum dots are modified, dissolved and dispersed in an oily or aqueous organic solvent to obtain a quantum dot solution, and the obtained quantum dot solution is used as a pigment in coating materials such as coatings and paints. The quantum dot pigment of the present application can achieve colorful color display of pigments with the same chemical component: on the one hand, based on the size effect of quantum dots, the quantum dot growth process is controlled to prepare quantum dots of different sizes, and the color is controlled by the size of the quantum dots; on the other hand, the thickness of the quantum dot coating can be adjusted by controlling the coating film forming process, and the thickness of the quantum dot coating can also control the color. Traditional quantum dot pigments are achieved by combining natural or artificial pigments of various chemical components to achieve quantum dot color display, while the quantum dot pigment of the present application can adjust the color by adjusting the size of the quantum dots and the thickness of the quantum dot coating based on the size effect and optical properties of the quantum dots, so as to achieve colorful color display of the same chemical component.

[0080] Although the present invention has been described with reference to several typical embodiments, it should be understood that the terms used are illustrative and exemplary, rather than restrictive. Since the present invention can be embodied in a variety of forms without departing from the spirit or essence of the invention, it should be understood that the above embodiments are not limited to any of the foregoing details, but should be interpreted broadly within the spirit and scope defined by the appended claims, so all changes and modifications falling within the scope of the claims or their equivalents should be covered by the appended claims.

Claims

1. A quantum dot pigment, characterized in that: The quantum dot pigment includes quantum dots and a first organic solvent.

2. The quantum dot pigment according to claim 1, characterized in that The first organic solvent is an alkane solvent, the ligand of the quantum dot is lipophilic, and the quantum dot pigment is an oily quantum dot pigment.

3. The quantum dot pigment according to claim 1, characterized in that The first organic solvent is an amide solvent, the ligand of the quantum dot is hydrophilic, and the quantum dot pigment is a water-based quantum dot pigment.

4. The quantum dot pigment according to claim 1, characterized in that The quantum dot pigment further includes a resin, the quantum dots are uniformly dispersed in the resin to form a quantum dot-resin composite, and the quantum dot-resin composite is dissolved in the first organic solvent; And / or, the concentration of the quantum dots in the first organic solvent is 0.1-500 mg / mL.

5. A method for preparing a quantum dot pigment, characterized in that: The steps include: S10, preparation of quantum dots; S20, dissolving and dispersing the quantum dots in an alkane solvent, fully mixing, then adding an extraction solvent, and centrifuging to obtain oily quantum dots; S30, dissolving and dispersing the oily quantum dots in a lipophilic organic solvent to obtain an oily quantum dot pigment.

6. A method for preparing a quantum dot pigment, characterized in that: The steps include: S10, preparation of quantum dots; S20, dissolving and dispersing the quantum dots in an alkane solvent, fully mixing, then adding an extraction solvent, and centrifuging to obtain oily quantum dots; S30, dissolving the oily quantum dots and adding an organic solvent with a hydrophilic group, fully mixing to complete ligand conversion, then adding an extraction solvent, and centrifuging to obtain water-based quantum dots; S40, dissolving and dispersing the water-based quantum dots in a hydrophilic organic solvent to obtain a water-based quantum dot pigment.

7. The method for preparing quantum dot pigment according to claim 6, characterized in that: In step S40, it is necessary to first disperse the aqueous quantum dots in a resin to form a quantum dot-resin complex, and then disperse the quantum dot-resin complex in an organic solvent with a hydrophilic group; And / or, in step S40, the concentration of the quantum dots in the organic solvent with hydrophilic groups is controlled to be 0.1 to 500 mg / mL; And / or, steps S20 to S40 are all performed under yellow light conditions.

8. A quantum dot coating, characterized in that: include: A coating solution comprising a coating and a second organic solvent, wherein the coating is dissolved in the second organic solvent; as well as A quantum dot pigment as claimed in any one of claims 1 to 4 or a quantum dot pigment prepared by the method of any one of claims 5 to 7; Wherein, the coating solution and the quantum dot pigment are uniformly mixed.

9. The quantum dot coating according to claim 8, characterized in that: The concentration of the quantum dots in the coating solution is 2 to 50 wt %; And / or, the second organic solvent is the same as the first organic solvent.

10. A quantum dot coating, characterized in that: It comprises the quantum dot coating as described in claim 8 or 9, wherein the quantum dot coating is prepared by coating the quantum dot coating on a substrate.

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