WO2020001010A1

WO2020001010A1 - Pigment simultaneously having high brightness, color purity and coverage effect and preparation method therefor

Info

Publication number: WO2020001010A1
Application number: PCT/CN2019/072566
Authority: WO
Inventors: 林一中; 王振兴
Original assignee: 林一中
Priority date: 2018-06-29
Filing date: 2019-01-21
Publication date: 2020-01-02
Also published as: CN110183875B; CN110183875A; CN108752977A

Abstract

The present invention relates to a pigment simultaneously having high brightness, high color purity and high coverage effect. The pigment comprises a core material and an outer cladding layer. The core material has a structure of 1-20 layers, and comprises an air layer, and/or one of the following three layers: a dielectric layer, a reflective layer, and a multilayer structure composed of the dielectric layer and one layer of the reflective layer. The total thickness of the core material is 20-1000 nm. The single layer thickness of the dielectric layer is 50-300 nm. The single layer thickness of the reflective layer is 20-100 nm. The total thickness of the core material and the single layer thickness of the dielectric layer or the reflective layer deviate by no more than 1% or 5 nm of the average of the total thickness and the corresponding layer thickness. One to six layers of the outer cladding layer are comprised, the total thickness of the outer cladding layer is 20-1000 nm, and the thickness of each cladding layer is 10-300 nm. The pigment of the present invention can be used in coatings, inks, cosmetics, and make-up products.

Description

Pigment with high brightness, color purity and covering effect at the same time and preparation method thereof

Technical field

The present invention relates to a pigment, and more particularly, to a pigment having excellent brightness, color purity, and hiding effect, and a preparation method and application thereof.

Background technique

Pearlescent pigments have a variety of colors, which can meet the application needs of various industries. With the further expansion of the scope of use and the further expansion of the use of occasions, more stringent requirements have been imposed on pearlescent pigments. For ordinary pearlescent pigments, the general brightness and hiding power are two contradictory properties. If the powder has a good hiding power, the general brightness is poor, and vice versa. Therefore, the requirements for both good hiding and brightness are proposed. However, because ordinary pearlescent pigments use a ground sheet material as the substrate and then cover the gas phase or liquid phase, the two properties cannot be taken into account.

The materials obtained by the physical vapor deposition (PVD) method to obtain various optical effects have been widely used in many industries. The Optically Variable (OVP) effect pigments obtained using the PVD method are also widely used in securities, coins and other occasions where high-level anti-counterfeiting is required. For example, in China ’s RMB 100 and RMB 50 optical variable anti-counterfeiting technology, this technology is used, and its structure has 5 symmetrical structures: semi-absorbing layer / dielectric layer / reflective layer / dielectric layer / semi-absorbing layer [Related patent US4779898, US5059245, ZL02816899.2], because of the existence of its absorbing layer, the powder has a very good hiding power; in order to obtain better color effects, generally more layers can be used, such as Chinese patent 201510632169.3, in order to obtain pure The red optical discoloration anti-counterfeiting pigment adopts a structure of 7 + 2 (n) layers. The general structure has a central reflection layer, a first dielectric layer, a first semi-absorbing layer, a second dielectric layer, a second semi-absorbing layer ... The structure can further eliminate the noise interference and obtain a more pure red. For pigments prepared solely by the PVD process, the process determines the existence of few free matter, even if the powder particles are small, the brightness of the pigment will not be significantly reduced, and the pigment layers have a higher level of flatness, color purity, and brightness. it is good. However, the pigment is prepared by PVD process and then pulverized, so that the pigment generally has a bare metal layer, and the reflective layer or semi-absorbing layer may be affected by air, water, acid, alkali or sulfide. However, the brightness is reduced during storage or use. In particular, the use of pigments containing an aluminum layer in an aqueous system may affect the use of the pigment.

According to the principle of interference pigments, the greater the difference in refractive index between adjacent layers, the better the color effect and the higher the color purity. Air is now considered to be the lowest refractive index material in the known materials, so the introduction of an air layer into the layer structure will improve the effect of the pigment. However, for pigments prepared by PVD, the layers in the pigment are arranged in parallel and contact each other, and it is impossible to introduce an air layer into the structure to obtain a special effect. Furthermore, the pigments mentioned in the aforementioned patents generally have a reflective layer, a dielectric layer, and a semi-absorptive layer, and there is no concern about wet-chemical coating with only the reflective layer and / or the dielectric layer as the substrate. Because the surface of the substrate obtained by the PVD method can be more flat, if the material prepared by PVD is used as the substrate and then wet chemical coating is performed by a specific process, a richer color effect pigment or special effect can be obtained, such as higher Color purity, better hiding power, higher brightness, etc.

For mica-based pearlescent pigments, because ground mica is used as a raw material, the steps on the surface will cause light scattering, and the fine-grained substrate will scatter light more obviously. In order to obtain better hiding power, light scattering generally needs to be improved. Therefore, materials with smaller particle diameters are generally selected, but their color purity and flicker effect will be greatly discounted due to light scattering. For a substrate with a large particle size, its cover will be poor. In order to achieve the purpose of covering and brightness at the same time, it is generally necessary to add a high absorption rate or high reflection layer to the material to improve it. For example, an aluminum sheet is used as a substrate, and a silica protective aluminum layer is coated thereon, and then a high refractive index iron oxide is coated thereon to obtain a pigment having a strong hiding power under a condition of a large particle size. . For pearlescent pigments prepared from glass substrates, because the glass substrate has better transparency than mica substrates, and there are no steps, the color purity of the pigments is higher, but because the thickness distribution of the glass substrate is relatively Wide, affecting the color purity and the production of special color effects. However, the thickness of the substrate prepared by the PVD method can be strictly controlled, and the thickness control of the substrate prepared by the ordinary coating method is more concentrated, and the color effect that cannot be obtained by the ordinary thickness distribution substrate can be obtained.

As for the refractive index, vacuum or air is the smallest. If an air layer with a low refractive index can be introduced into the pigment, a more excellent color effect can also be obtained. However, for the existing PVD preparation process, there is no condition for introducing an air layer structure into it. And the air layer (hollow layer) obtained through special treatment can improve the color effect. The patent disclosed in US patent US5611851 uses phosphoric acid or the like to treat pearlescent pigments, removes part of the mica substrate, and obtains pigments with a partially hollow structure, which changes the color effect to a certain extent. However, due to unevenness such as steps inherent in the substrate obtained by natural mica grinding, the excellent effect of replacing mica with air cannot be fully reflected, which affects the display and display of special color effects.

Summary of the invention

In view of the defects in the prior art, the object of the present invention is to provide a pigment that can simultaneously have the effects of high brightness, high color purity, and high hiding power. The pigment includes a core material and an outer coating layer.

The core material has a 1-20 layer structure, including an air layer, and / or one of the following three:

A dielectric layer, a reflective layer, and a multilayer structure composed of a dielectric layer and a reflective layer,

The total thickness of the core material is 20-1000 nm,

A single layer thickness of the dielectric layer is 50-300 nm, a single layer thickness of the reflective layer is 20-100 nm, and

The deviation between the total thickness of the core material and the thickness of a single layer of the dielectric layer or the reflective layer does not exceed 1% or 5 nm of the average of the total thickness and the thickness of the corresponding layer,

The outer cladding layer is 1-6 layers, the total thickness of the outer cladding layer is 20-1000 nm, and the thickness of each cladding layer is 10-300 nm.

The material of the reflective layer in the present invention may be selected from one or more of metals, metal oxides, non-metals, and non-metal oxides having high reflectivity;

The material of the dielectric layer in the present invention may be selected from one of a metal oxide, a metal fluoride, a metal sulfide, a non-metal oxide, a non-metal fluoride, and a non-metal sulfide with a refractive index lower than 1.8. Or more.

The material of the outer coating layer in the present invention may be selected from metal oxides, metal hydroxides, non-metal oxides, non-metal hydroxides, metal low oxides, metal fluorides, metal halides, and metal sulfur. One or more of a metal element, a metal sulfide, a metal nitride, a metal oxynitride, and a metal carbide, and at least one of the materials in the cladding layer has an emissivity higher than 1.6.

In a more preferred embodiment of the present invention, the thickness of each dielectric layer is 80-250 nm.

In a preferred embodiment of the present invention, the material constituting the dielectric layer is selected from the group consisting of SiO ₂ , MgF ₂ , Al ₂ O ₃ , AlF ₃ , Na AlF ₆ , BaF ₂ , NdF ₃ , CaF ₃ , LiF, and ZnS. One or more of them.

In a more preferred embodiment of the present invention, the material constituting the dielectric layer is selected from SiO ₂ and / or Al ₂ O ₃ .

In a preferred embodiment of the present invention, the material of the reflective layer is selected from one or more of aluminum, silver, copper, gold, titanium, tantalum, niobium, chromium, and nickel.

In a preferred embodiment of the present invention, the material constituting the outer cladding layer is selected from TiO ₂ , Fe ₂ O ₃ , TiFe ₂ O ₅ , Fe ₃ O ₄ , BiOCl, Cr ₂ O ₃ , ZrO ₂ , ZnO , SnO ₂ , CoO, Co ₃ O ₄ , VO ₂ , V ₂ O ₃ , iron titanate, Ti ₂ O ₃ , bismuth vanadate, cobalt aluminate, SiO ₂ , Al ₂ O ₃ , Al (OH) ₃ , One or more of MgF ₂ , B ₂ O ₃ , and ZnS.

In a more preferred embodiment of the present invention, the core material has a 3-9 layer structure. In another more preferred embodiment of the present invention, the core material includes 3-9 dielectric layers. In another more preferred embodiment of the present invention, the core material includes 3-9 reflective layers. In another more preferred embodiment of the invention, the core material comprises a layer of air. In another more preferred embodiment of the present invention, the core material includes a dielectric layer. In another more preferred embodiment of the present invention, the core material includes a reflective layer.

In another more preferred embodiment of the present invention, the core material has a 3-9 layer structure including an air layer and a dielectric layer, and the air layer and the dielectric layer are alternately distributed. In another more preferred embodiment of the present invention, the core material has a three-layer structure and includes one layer of air and two layers of silica, and the air layer is located between the two layers of silica.

In another more preferred embodiment of the present invention, the core material has a 3, 5, 7, or 9-layer structure, including 2, 4, 6, or 8 dielectric layers and a reflective layer, and the 2, 4 , 6 or 8 dielectric layers are symmetrically arranged with the reflective layer as the center.

In another more preferred embodiment of the present invention, the core material has a 3-9 layer structure including an air layer and a reflective layer, and the air layer and the reflective layer are alternately distributed.

Another object of the present invention is to provide a method for preparing a pigment that simultaneously has the effects of high brightness, high color purity, and high hiding power. The method includes the following steps:

(1) Provide super smooth polished stainless steel backing or glass as backing;

(2) A PVD method is used to deposit a peelable release layer on the substrate, and then a PVD method is used to deposit 1-20 dielectric layers, 1-20 reflective layers, or 2-19 dielectric layers and one A multilayer structure composed of reflective layers, and then depositing a peelable isolation layer, so as to deposit the peelable isolation layer and the 1-20 dielectric layer, 1-20 reflective layer, or 2 The multi-layer structure consisting of -19 dielectric layers and a reflective layer is a cycle, and the cycle is repeated 2-50 times;

(3) using a release agent to remove the peelable release layer in the material obtained in step (2), and then washing and classifying to obtain a core material precursor having a predetermined particle size distribution;

(4) Dispersing the core material precursor obtained in step (3) in water or ethanol to prepare a slurry, adding a coating solution, performing wet chemical coating, and sequentially coating 1-6 outer coatings,

Among them, after the coating of each layer of coating is completed, the coating of the next layer of coating can be continued by adjusting the coating conditions, or it can be re-dispersed in a solvent to prepare a slurry after filtering and washing. Cladding

(5) After the coating is completed, filtering, washing and drying are performed to obtain pigments with simultaneously high brightness, high color purity and high hiding power.

In a preferred embodiment of the present invention, the material constituting the reflective layer is selected from one or more of aluminum, silver, copper, gold, titanium, tantalum, niobium, chromium, and nickel.

In a preferred embodiment of the present invention, the material layer constituting the outer coating is selected from TiO ₂ , Fe ₂ O ₃ , TiFe ₂ O ₅ , Fe ₃ O ₄ , BiOCl, Cr ₂ O ₃ , ZrO ₂ , ZnO , SnO ₂ , CoO, Co ₃ O ₄ , VO ₂ , V ₂ O ₃ , iron titanate, Ti ₂ O ₃ , bismuth vanadate, cobalt aluminate, SiO ₂ , Al ₂ O ₃ , Al (OH) ₃ , One or more of MgF ₂ , B ₂ O ₃ , and ZnS.

In a preferred embodiment of the present invention, step (5) may further include a step of calcining after drying.

In a preferred embodiment of the present invention, the thickness of each dielectric layer in step (1) is 50-300 nm, and the thickness of each reflective layer is 20-100 nm. The total thickness of the core material and the thickness of the single layer are different. Not more than 1% or 5nm of the average of the total thickness and the thickness of the corresponding layer, and the multilayer is 2-20 layers;

In a preferred embodiment of the present invention, step (2) is to deposit a peelable release layer on the substrate using a PVD method, and then deposit 1-20 dielectric layers using a PVD method, and then deposit a layer of The isolation layer is peeled off, so that the deposition of the peelable isolation layer and the 1-20 dielectric layer is a cycle, and the cycle is repeated 2-50 times. In another preferred embodiment of the present invention, step (2) is to deposit a peelable release layer on the substrate using a PVD method, then deposit 1-20 reflective layers using a PVD method, and then deposit a layer of The isolation layer is peeled off, so that the deposition of the peelable isolation layer and the 1-20 reflection layer is a cycle, and the cycle is repeated 2-50 times. In another preferred embodiment of the present invention, step (2) is to deposit a peelable release layer on the substrate using a PVD method, and then to deposit 2-19 dielectric layers and a reflective layer using the PVD method. A multi-layer structure composed of a layer, and then a layer of peelable isolation layer is deposited. In this way, a multilayer structure composed of the layer of peelable isolation layer and the 2-19 layer dielectric layer and a reflective layer is deposited as a cycle. Repeat this cycle 2-50 times.

In a preferred embodiment of the present invention, the dielectric layer and / or the reflective layer deposited in step (2) may be dissolved and removed in the wet chemical coating of step (4).

In a more preferred embodiment of the present invention, the material of the dielectric layer in step (2) is zinc sulfide, and the zinc sulfide dielectric layer is dissolved and removed during the coating process in step (5), and is in the core of the final product. Material is replaced by air.

In another more preferred embodiment of the present invention, the material of the reflective layer in the step (2) is a metal aluminum layer, and the metal aluminum reflective layer is dissolved and removed during the coating process of the step (5) to form a core in the final product. Material is replaced by air.

The invention also provides the use of pigments with high brightness, high color purity, and high hiding power effects in coatings, inks, cosmetics, and makeup.

The pigment with high brightness, high color purity and high hiding power effect can be used in coatings, inks, cosmetics, and make-up. It is particularly suitable for the occasions where high coverage and high brightness are required at the same time. -90%.

Compared with the prior art, the present invention has the following beneficial effects:

The existing separate high-refractive oxide layer can also produce interference effects, but because the layer thickness is too thin, the mechanical light strength is poor, and it is easily broken during use and loses the pigment value. However, as far as Ben Fangming is concerned, because the core material precursor prepared by the PVD method or the core material in the final product also plays the role of substrate support, so that the pigment's mechanical stability is maintained while maintaining the pigment effect, making the product With the use of pigment properties.

The structure of the pigment of the present invention, in particular, the pigment containing the air layer core material obtained by the PVD method according to the prior art cannot be obtained. In products using mica or the like as a base material, the hollow effect of the base material or the like is not sufficient. expression.

The pigment of the invention has excellent effects of high brightness, high color purity and high hiding power.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic structural diagram of a pigment including a core material composed of a single dielectric layer or a reflective layer and a single outer coating layer. Among them, 1 indicates a core material, and 2 indicates an outer cladding layer.

FIG. 2 is a schematic structural diagram of a pigment including a three-layered core material and a single-layer outer coating layer. Among them, 1-1, 1-2, and 1-3 represent the three layers of the core material, and 2 represents the outer cladding layer.

FIG. 3 is a schematic structural diagram of a pigment including a three-layered core material and a single-layer outer coating layer. Among them, 1-1, 1-2, and 1-3 represent the three layers of the core material, 1-2 can be a dielectric layer or a reflective layer, or an air layer, and 2-1 and 2-2 represent two outer layers. Coating.

detailed description

In view of the defects existing in the existing pigments, the inventors have improved the existing pigment preparation methods through intensive research, and obtained a pigment with high brightness, high color purity, and high hiding power. The present invention has been completed on this basis.

The core material of the pigment having high brightness, high color purity, and high hiding power effect is obtained by the PVD method, and can be a single-layer dielectric layer or a reflective layer, or a multilayer dielectric layer or a reflective layer. It can also be a multilayer dielectric layer and a reflective layer. For multiple layers, it may be an odd layer or an even layer; these layers may have a symmetrical structure or an asymmetric structure, and preferably have a symmetrical structure. For example, when the core material is a multilayer dielectric layer and a reflective layer, it is preferable that the number of dielectric layers is an odd number, and it is more preferable that the dielectric layer is symmetrically disposed with the reflective layer as the center. For example, the number of layers of the core material is three, which includes one center layer and two side layers. The center layer is generally a reflective layer, and the side layer is generally a dielectric layer.

The material of the reflective layer of the present invention may be selected from one or more of metals, metal oxides, non-metals, and non-metal oxides having high reflectance and low transmittance. For example, one or a combination of aluminum, silver, copper, gold, titanium, tantalum, niobium, chromium, and nickel.

The material of the dielectric layer of the present invention may be selected from one or more of metal oxides, metal fluorides, metal sulfides, non-metal oxides, non-metal fluorides, and non-metal sulfides having a refractive index lower than 1.8. Species. For example, SiO ₂ , MgF ₂ , Al ₂ O ₃ , AlF ₃ , Na AlF ₆ , BaF ₂ , NdF3, CaF ₃ , LiF.

In the present invention, an ultra-smooth polished stainless steel substrate or glass is selected as the substrate substrate, and physical vapor deposition (PVD) is used (one of the three methods described above, such as resistance evaporation, electron beam evaporation, and sputtering deposition) can be used. (Combination) a peelable release layer is prepared on the backing, and then a reflective layer and / or a dielectric layer is deposited on the peelable release layer according to the design (the reflective layer and / or the dielectric layer deposited according to the design may be a single layer, Double layer, or multiple layers), after the designed reflective layer and / or dielectric layer is completely deposited, a peelable barrier layer is deposited again to deposit a peelable barrier layer and a reflective layer and / or a dielectric The layer is a cycle, and the cycle is repeated 1-50 times, preferably 5-30 times, to ensure that the equipment capacity is maximized, the power consumption of the equipment is reduced, and the production efficiency is increased under the condition of one installation of vacuum. And ensure that the coating is relatively flat, dense and complete. After completing the deposition by this method, multiple peelable isolation layers and multiple reflective layers and / or dielectric layers (or a single peelable isolation layer and a single reflective layer and / or dielectric) can be formed on a rigid substrate. Layer) of a periodic composite structure. The rigid substrate carrying the periodic composite structure is subjected to a release process using a specific release solvent. The peelable release layer will be dissolved in the release agent, the reflective layer and / or the dielectric. The composition of the layer will be peeled off the rigid substrate, and the multilayered structural units formed by multiple reflective layers and / or dielectric layers will also be separated, and then they will be collected for rinsing, filtering, pulverizing, and grading. A core material precursor was obtained.

For the core material precursor prepared by the above method, the reflective layer and / or the dielectric layer between the two peelable isolation layers may be a single layer, such as a single layer of silicon dioxide, aluminum oxide, calcium fluoride, fluorine Magnesium, zinc sulfide, etc. can also be multi-layered, such as having a side layer / middle layer / side layer structure, and further side layers are silica, alumina, calcium fluoride, magnesium fluoride, etc. The layer is metal aluminum, titanium, copper, copper, zinc, gold, or a co-deposition thereof, or magnesium fluoride, zinc sulfide, etc. The requirements for the side layer and the middle layer are not fluoride and / or sulfide. It may also have a more layer structure, and the number of layers may be an odd number layer or an even number layer.

For the deposition of a reflective layer and / or a dielectric layer of a specific structure, different mold release procedures can obtain different structural core material precursors when the release process is performed. Therefore, different treatment methods are adopted according to the situation: 1) If the middle layer of the core layer of the precursor of the core material is a layer containing zinc sulfide, and the side layer is a structure of silica or trialumina, if it can react with zinc sulfide, If dilute hydrochloric acid is removed as the release agent, after removing both the peelable barrier layer and zinc sulfide, it is possible to obtain a smooth and flat single-layer silicon dioxide or trichloride core material. If it is treated with a release agent that can remove the peelable barrier layer without affecting the zinc sulfide layer, an alternating distribution of a multilayer structure of silica or alumina and zinc sulfide can be obtained; 2) such as a core material precursor The multilayered structure containing fluoride (such as magnesium fluoride) and silicon dioxide in the deposited layer; if a release agent that can only remove the peelable release layer is used, a multilayer structure containing fluoride can be obtained; The above-treated samples are then treated with an acid, or when a release agent is used to remove the peelable barrier layer and fluoride at the same time during the release treatment, it is possible to obtain a roughened silica layer. Subsequent coating can obtain pigments with good hiding power.

The obtained material is used as a core material precursor for subsequent coating. The material of the outer cladding layer may be selected from metal oxides, metal hydroxides, non-metal oxides, non-metal hydroxides, metal low oxides, metal fluorides, metal halides, metal chalcogenides, metals One or more of sulfide, metal nitride, metal oxynitride, and metal carbide, and the material of at least one of the cladding layers has an emissivity higher than 1.6. For example, TiO ₂ , Fe ₂ O ₃ , TiFe ₂ O ₅ , Fe ₃ O ₄ , BiOCl, Cr ₂ O ₃ , ZrO ₂ , ZnO, SnO ₂ , CoO, Co ₃ O ₄ , VO ₂ , V ₂ O ₃ , One or more of iron titanate, Ti ₂ O ₃ , bismuth vanadate, cobalt aluminate, SiO ₂ , Al ₂ O ₃ , Al (OH) ₃ , MgF ₂ , B ₂ O ₃ , ZnS. The subsequent coating is preferably a wet chemical coating. The coated layers can be coated in organic solvent systems and / or water systems to obtain pigments with different structures and effects according to the conditions of different core material precursors and outer coating layers. In particular, the structure of the core material precursor containing the sulfide layer and / or fluoride can be obtained according to the subsequent wet chemical coating method, and the structure containing the sulfide layer or fluoride, or the sulfide or fluoride layer is replaced by the air layer. Of pigments. For example, a core material precursor containing a zinc sulfide layer is coated with a silica layer of a certain thickness in a subsequent wet chemical method, and then hydrochloric acid is added to adjust the pH of the system to acidic dissolution to remove the zinc sulfide. In the final product, the zinc sulfide layer Replaced by air.

The core material precursor containing metal aluminum is coated with a certain thickness of silicon dioxide layer by subsequent wet chemical methods, and then hydrochloric acid is added to adjust the pH of the system to acidic dissolution to remove aluminum, and the aluminum layer is replaced by air in the final product.

In the case of core material precursors containing materials such as silica, alumina, etc., because the material prepared by the PVD method is particularly flat and the thickness distribution is very concentrated, it is used as the base material for the outer coating. During coating, effects that cannot be obtained with ordinary substrates can be obtained. Therefore, in order to achieve the desired specific color effect for the pigments of this formula, the thickness and coating requirements are stricter than ordinary substrates. The same color effect is not a general basis for mica, etc. Wood thickness distribution pigment can achieve. For example, a silicon dioxide material with a thickness of 150 nm (thickness deviation less than 1.5 nm) prepared by the PVD method of the present invention can be coated with titanium dioxide (about 50 nm) or ferric oxide (about 40 nm) in a single layer, and the color can be obtained. Very good concentration of optical color-changing pigments, and can still have very good color purity and color-changing effect even when the particle size is very fine. Compared with the pigment prepared by the silica substrate prepared by the Merck tape method, the substrate prepared by the PVD method can have better flatness and a narrower thickness distribution, and can obtain more excellent Pigment properties. No noise appears. For a silica substrate with a thickness of 80 nm (with a thickness deviation of 1 nm), a very pure red color can be obtained by coating a layer of iron oxide with a thickness of 80 nm on the silica substrate, and there is no noise at all.

For core material precursors composed of multiple reflective layers and / or dielectric layers, different coating methods can be used to obtain pigments with different effects according to different layer structures. For example, when the core layer of the core material precursor is silver, because it has very good acid and alkali resistance, it can be directly used to coat various metal and non-metal oxides or hydroxides to obtain good color purity, Brightness and hiding pigment.

For a core material precursor using zinc sulfide as an intermediate symmetrical layer, such as a core material precursor composed of silicon dioxide, zinc sulfide, and silicon dioxide in sequence, if a silicon dioxide layer is first coated under alkaline conditions, After that, the pH of the system is adjusted to be acidic, zinc sulfide is removed, and then high-refractive metal and / or non-metal oxides and / or hydroxides are coated under certain conditions. Leveling, the intermediate layer becomes an air layer in the final pigment, which further increases the refractive index difference and enhances the effect of the pigment, and because of the outer silica layer, maintains the mechanical stability of the entire pigment.

For a core material precursor using fluoride as an intermediate layer, firstly coat silica under alkaline conditions, and then adjust the pH value to acidic so that the fluoride is removed, and because of the generation of hydrogen fluoride, the The layer is slightly corroded, which further improves the hiding power of the powder. Then, under certain conditions, high refractive index metal or non-metal oxides or hydroxides are coated to obtain products with good brightness, high hiding power and color purity.

For a core material precursor containing an aluminum layer, the first choice is to coat a protective layer of silica with a certain thickness in an organic solvent system, and then coat the oxide or hydroxide with a refractive index exceeding 1.6. Pigments that retain the structure of the aluminum layer can be obtained, giving the pigments very high brightness and hiding power.

In the present invention, the wet chemical coating can be performed by using generally existing existing process conditions. According to the specific situation, after the end of one layer of coating, the conditions can be directly adjusted for the next layer of coating, or the feed liquid can be processed, washed, and filtered before being put back into the reaction kettle for coating.

In a preferred embodiment, the core material precursor is coated with silica in an organic solvent system to obtain an acid-resistant substrate, and then a color paste is used to obtain a colored pigment.

For the thickness of the obtained core material as the base material, it is explained that, for ordinary mica powder or glass powder obtained by grinding, it has a wide particle size distribution and thickness distribution, because its thickness is a wider distribution. The overall effect of the thickness of the substrate on the color is that the color purity is poor but no obvious noise appears. Therefore, the thickness distribution of the mica substrate does not significantly affect the interference color of the final product. The color is mainly caused by the substrate. The refractive index of the cladding layer and the thickness of the cladding layer are determined. For the core material obtained using the PVD method of the present invention, because the surface is very flat, when the wet chemical method is used to deposit the coating thereon, the reflection and refraction effects of the core material on light will be exhibited. The uneven thickness distribution will cause different interference colors in the substrates of different thicknesses, which will cause "noise" phenomenon, which will be more serious than the noise caused by different thicknesses of mica. The thickness distribution of the substrate obtained by the PVD method is generally narrower than that of glass. However, because the flatness of the substrate is very high, the difference in the color of the overall powder due to the difference in thickness will be very obvious. Therefore, for the core material precursor of the present invention, the total thickness and the thickness of each layer are required to be very high. Generally, the deviation is not required to exceed 1% or 5 nm of the thickness. This is also a range that can be controlled by the PVD method. This range guarantees that the color effect of the obtained pigment will not appear mottled, especially at the angle of front view.

The "peelable release layer" in this article refers to the precipitation layer that can be removed by using a release agent during subsequent processing, which causes the substrate to be separated from the dielectric layer or the reflective layer after removal, and is used to form 1-20 of the core material. Layers of dielectric layers, 1-20 layers of reflective layers, or layers of 2-19 layers of dielectric layers and a layer of reflective layers are separated from each other to form a free core material. The peelable release layer is generally selected from organic solvent-soluble or water-soluble coatings, for example, a soluble polymer such as acrylic resin, or sodium chloride. The corresponding release agent is an organic solvent that can dissolve it, such as acetone or Acetone solution or water. When a sulfide is used as the material of the dielectric layer, it can also be used as a peelable release layer, and an acid substance that can dissolve the sulfide can be used as a release agent. For example, zinc sulfide can also be used as a peelable barrier layer in the present invention, and hydrochloric acid is used as a release agent.

In the present invention, the "core material precursor" is a precursor of the core material of the final pigment. The pigment of this method is an outer coating layer obtained by first preparing a core material precursor by a physical vapor deposition (PVD) method and then performing wet chemical coating. In the subsequent wet chemical coating conditions, some dielectric or reflective layers in the core material precursor may or may not be removed. Therefore, the structure of the core material may be different from that of the core material precursor. May be the same.

In the present invention, a metal or non-metal or two or more oxides having a high reflectance means a metal or non-metal or two or more oxides having a reflectance higher than 50%.

In the present invention, the "low-priced metal oxide" means an oxide having a metal valence state lower than the highest valence state of the metal.

This method uses the combination of PVD method and wet coating, which has the advantages of flatness and high effect of the substrate. The cost of effect pigments prepared by pure PVD method can be lower, and the pigment structure that can not be obtained by pure PVD method can be obtained. In addition, the pigment is completely coated. There is no cross section that easily reacts and destroys the properties and color effects of the pigment. It is more stable and has a wider range of use. Compared with the wet coating method using ordinary substrates, it has more Flat, especially narrower thickness distribution substrates can achieve better color results.

The present invention will be further described below with reference to specific embodiments. The specific embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and operation process are given. It should be understood that these examples are only used to illustrate the present invention and not to limit the scope of the present invention. The experimental methods without specific conditions in the following examples are generally performed under normal conditions. Unless otherwise stated, percentages and parts are by weight.

Example 1

The core material of the pigment of this embodiment is a single layer of silica, and the outer coating layer is titanium dioxide.

Use vacuum sputtering technology to deposit a layer of zinc sulfide of about 10nm on the backing glass plate, and then deposit silicon dioxide until it reaches 170nm, then deposit zinc sulfide of about 10nm, and then continue to deposit silicon dioxide at 170nm. Repeat the above process, repeating 10 cycles, the total thickness reached about 2um. The material was then immersed in hydrochloric acid (concentration 35%) for about 30 minutes, and zinc sulfide was removed to obtain a silica sheet with a very high surface flatness and a thickness of 170 nm. After subsequent washing and classification, a particle size distribution of 20 was obtained. -100um core material precursor, used as the substrate for subsequent coating, with a thickness of 170 ± 2nm.

Then 40g of this core material precursor was dispersed in 1L of water, heated to 78 ° C, and then the pH of the system was adjusted to about 2.0 with dilute hydrochloric acid. A titanium tetrachloride aqueous solution (concentration: 2mol / L) was added dropwise, and sodium hydroxide was added at the same time. The solution is used to maintain the stability of the pH of the system. When the thickness of the coating reaches about 50nm, the feeding is stopped, and the pH of the system is slowly raised to about 6.0, and then filtered, dried at 100 ° C, and calcined at 500 ° C to obtain a gold-red discoloration effect Pigment with very excellent brightness. Compared with the chameleon pigments currently obtained by grinding the mica substrate, the pigments have higher color purity and almost no noise, and pigments with more obvious color changing effects.

In the pigment, the core material precursor has the same structure as the core material after covering the outer coating layer.

Example 2

The core material of the pigment of this embodiment is a single-layered silica, and a mixed coating layer of an outer coating layer of titanium dioxide and ferric oxide.

A vacuum sputtering technique is used to deposit an organic peelable isolation layer of about 10 nm on a base glass plate, followed by deposition of silicon dioxide until it reaches 80 nm, and then deposit an organic peelable isolation layer of about 10 nm, and then continue to deposit two The silicon oxide is 80nm, the above process is repeated repeatedly, and the cycle is repeated 20 times, and the total thickness reaches about 2um. The material was then immersed in a mold release agent to remove the peelable barrier layer to obtain a silica sheet with extremely high surface flatness and a thickness of 80 nm. After subsequent washing and classification treatment, a core material with a particle size distribution of 10-60um was obtained. The precursor is used as a substrate for subsequent wet chemical coating, and its thickness is 80 ± 4 nm.

Then 40g of this substrate was dispersed in 1L of water, heated to 78 ° C, the pH of the system was adjusted to about 3.0 with hydrochloric acid, 0.7mol / L ferric chloride and 2.2mol / L titanium tetrachloride mixed solution were added, and ammonia water was added at the same time. In order to maintain the stability of the pH of the system, the feeding was stopped when the coating thickness reached 80 nm, and the pH of the system was slowly raised to about 6.0, and then filtered. After drying at 110 ° C and calcining at 800 ° C, a pigment with a golden effect is obtained, which has very excellent brightness. Compared with the silica substrate produced by the coating method, it has a more pure hue and no noise.

The core material precursor in the pigment has the same structure as the core material after the outer coating layer is coated.

Example 3

The core material of the pigment of this embodiment is a single layer of aluminum oxide, and the outer coating layer is iron oxide.

A vacuum sputtering technique is used to deposit an organic peelable isolation layer of about 10 nm on the backing glass plate, and then deposit aluminum oxide to 100 nm, and then deposit a peelable isolation layer of about 10 nm, and then continue to deposit Aluminium trioxide is 100nm, repeat the above process repeatedly, repeat 20 cycles, the total thickness reaches about 2um. The material was then immersed in an organic release agent to remove the peelable barrier layer to obtain alumina with a very high surface flatness and a thickness of 100 nm. After subsequent washing and classification, a core with a particle size distribution of 40-80um was obtained The material precursor, as a substrate for subsequent wet chemical coating, has a thickness of 100 ± 1.5 nm.

Then 40g of this substrate was dispersed in 1L of water, heated to 78 ° C, the pH of the system was adjusted to about 3.0 with hydrochloric acid, 1.0mol / L ferric chloride aqueous solution was added, and ammonia water was added to maintain the pH stability of the system. When the thickness reaches 100nm, stop feeding, and slowly increase the pH of the system to about 6.0, then filter, dry at 110 ° C, and calcined at 500 ° C to obtain a pigment with a red effect, which has very excellent brightness. Compared with the pigment prepared by the molten salt method for the alumina substrate, the substrate has a very uniform thickness, a very flat surface, color purity, and brightness.

Example 4

The core material of the pigment of this embodiment is two silica layers and an air layer located between the two silica layers, and the outer covering layer is silica and ferric oxide.

A vacuum sputtering technology is used to deposit an organic peelable isolation layer of about 10 nm on a backing glass plate, followed by a 40 nm silicon dioxide layer, then a 20 nm zinc sulfide layer, and then a 40 nm silicon dioxide layer is further deposited. After that, a 10-nm organic peelable isolation layer was deposited, and the above process was repeated repeatedly, repeating 20 cycles, and the total thickness reached about 2um. The material was then immersed in an organic release agent, and the peelable release layer was removed to obtain a silica / zinc sulfide / silica three-layer substrate with extremely high surface flatness and a thickness of 40/20 / 40nm, respectively. Subsequent washing and classification treatments yield a core material precursor with a particle size distribution of 10-40um. As a subsequent wet chemically coated substrate, its thickness is 100nm ± 2nm.

Then 40g of this substrate was dispersed in 1L of water, heated to 78 ° C, the pH value of the system was adjusted to about 8.5 with sodium hydroxide solution, and a 1mol / L sodium silicate aqueous solution was added, while dilute hydrochloric acid was added to maintain the stability of the pH of the system. When the thickness of the coating layer reaches about 40nm, stop feeding, and slowly reduce the pH of the system to about 1.0, and raise the temperature to 90 ° C. Stir the reaction sufficiently to make the zinc sulfide completely react, then filter, wash thoroughly, and then powder Put it back into the reactor, disperse it in 1L of water, heat to 78 ° C, adjust the pH to 3.0 with hydrochloric acid, add a 1mol / L ferric chloride solution, and maintain the pH of the system by adding sodium hydroxide. The coating thickness is 80nm, and the golden pigment with higher color purity can be obtained after drying at 100 ℃. Because the pigment has a hollow layer in the middle, the color has a higher color purity. The core material precursor in this pigment is different from the core material structure in the pigment coated with the outer coating layer, because during the wet chemical coating process of the pigment, the zinc sulfide layer in the core material A thin layer of silica was removed by adding hydrochloric acid, which was replaced by air in the final pigment.

Example 5

The core material of the pigment of this embodiment is two silicon dioxide layers and a silver layer located between the two silicon dioxide layers, and the outer coating layer is titanium dioxide.

A vacuum sputtering technique is used to deposit an organic peelable isolation layer of about 10 nm on the backing glass plate, and then deposit silicon dioxide until it reaches about 60 nm, then deposit 20 nm silver, and then continue to deposit silicon dioxide at 60 nm. After that, a 10-nm isolation layer was deposited, and the above process was repeated repeatedly, repeating 20 cycles, and the total thickness reached about 2um. The material was then immersed in an organic mold release agent to remove the peelable release layer to obtain a silica / silver / silica three-layer substrate with extremely high surface flatness and a thickness of 60/20 / 60nm, respectively. The core material precursor with a particle size distribution of 10-40um was obtained by washing and classification treatment. As a subsequent wet chemical coating substrate, its thickness was 100nm ± 4nm.

Then 40g of the above substrate was dispersed in 1L of water, heated to 78 ° C, the pH of the system was adjusted to about 2.0 with dilute hydrochloric acid, 2mol / L titanium tetrachloride aqueous solution was added, and sodium hydroxide was added to maintain the stability of the pH of the system When the thickness of the coating layer reaches about 10nm, the feeding is stopped, and the pH of the system is slowly reduced to about 6.0, and then filtered, washed thoroughly, and dried at 100 ° C to obtain a pigment with high brightness.

Example 6

The core material of the pigment of this embodiment is two silica layers and an aluminum layer located between the two silica layers, and the outer cladding layer is silica and ferric oxide.

A vacuum sputtering technique is used to deposit an organic peelable release layer of about 10 nm on the backing glass plate, followed by deposition of silicon dioxide until it reaches 60 nm, then 20 nm of aluminum, and then deposition of silicon dioxide at 60 nm. Deposit a 10nm organic peelable release layer, repeat the above process repeatedly, repeat 20 cycles, the total thickness reaches about 2um, and then immerse the material in the release agent, remove the peelable release layer, and obtain a very high surface flatness and thickness. A silica / aluminum / silica three-layer substrate with a thickness of 60/20 / 60nm, respectively. After subsequent washing and classification, a core material precursor with a particle size distribution of 10-50um is obtained as a subsequent wet chemical coating. The thickness of the substrate used is 140nm ± 2nm.

Then 40 g of this substrate was dispersed in 1 L of ethanol, heated to 40 ° C, and a 1 mol / L ethyl orthosilicate ethanol solution was added, and 2 g of a mixed solution of water and ammonia water (NH ₃ concentration 10%) was added. The thickness of the coating on the substrate reaches about 60nm, and then it is filtered, washed, and the powder is re-dispersed in water, heated to 70 ° C, and the pH of the system is adjusted to about 3.0 with hydrochloric acid, and 1mol / L is an aqueous solution of ferric chloride, and the pH of the system is maintained by using 30% ammonia water. After the thickness of the coated iron oxide reaches 50 nm, it is filtered, fully washed, dried at 100 ° C, and calcined at 400 ° C to obtain a golden powder with very good hiding power. body.

In the pigment, the core material precursor has the same structure as that of the core material after covering the outer coating layer.

Example 7

The core material of the pigment of this embodiment is composed of silicon dioxide, zinc sulfide, silicon dioxide, zinc sulfide, and silicon dioxide in this order, and the outer coating layer is silicon dioxide, aluminum hydroxide, and carbon black.

Using a vacuum sputtering technique, an organic peelable release layer of about 10 nm is deposited on a backing glass plate, followed by 100 nm silicon dioxide, 20 nm zinc sulfide, and then 100 nm silicon dioxide. Then deposit 20nm thick zinc sulfide, and then deposit 100nm silicon dioxide; then deposit an organic peelable isolation layer, repeat the above process again, and repeat 7 cycles, the total thickness reaches about 2um. The material was then immersed in an organic mold release agent to remove the peelable release layer to obtain silica / zinc sulfide / silica / sulfide with extremely high surface flatness and thicknesses of 100/20/100/20 / 100nm respectively. The zinc / silica five-layer substrate was subjected to subsequent washing and classification processes to obtain a core material precursor with a particle size distribution of 10-100um. As a substrate for subsequent wet chemical deposition, its thickness was 340nm ± 4nm.

Then, 40 g of this core material precursor was dispersed in 1 L of ethanol, heated to 40 ° C, 1.5 mol / L of ethyl orthosilicate solution in ethanol was added, and 2 g of a mixed solution of water and ammonia water (NH ₃ concentration 15%) was added. After the thickness of the coating of the core material reaches about 70 nm, the silica is filtered, washed, and the powder is re-dispersed in water, heated to 40 ° C, and the pH of the system is adjusted to about 6.5, and 1 mol is added. / L aluminum chloride aqueous solution, carbon black slurry (containing 1 g of carbon black) was added, filtered, washed thoroughly, and dried at 100 ° C. to obtain a carbon black colored powder.

Example 8

The core material of the pigment of this embodiment is a single-layer air layer, and the outer cladding layer is a silicon dioxide layer and an iron trioxide layer.

A vacuum sputtering technique is used to deposit an organic peelable release layer of about 20nm on the backing glass plate, and then deposit a zinc sulfide layer of 150nm (deposit an organic peelable release layer of about 20nm, and then deposit 150nm zinc sulfide For one cycle), repeat the above process 12 times, the total thickness reached about 2um. The material was then immersed in an organic mold release agent to remove the peelable barrier layer to obtain a zinc sulfide sheet with a very high surface flatness and a thickness of 150 nm. After subsequent washing and classification, a core material with a particle size distribution of 10-60um was obtained. The precursor, as a substrate for subsequent coating, has a thickness of 150 ± 2 nm.

Then, 40 g of this core material precursor was dispersed in 1 L of ethanol, heated to 40 ° C, 1.5 mol / L of ethyl orthosilicate solution in ethanol was added, and 2 g of a mixed solution of water and ammonia water (NH ₃ concentration 15%) was added. After the coating thickness of the core material reaches about 50 nm, the silica is filtered, washed, and the powder is re-dispersed in water, and the pH of the system is slowly reduced to about 1.0, and the temperature is increased to At 90 ° C, stir the reaction thoroughly to make the zinc sulfide completely react, and then filter and wash thoroughly. Put the powder back into the reactor, disperse in 1L of water, heat to 78 ° C, adjust the pH to 3.0 with hydrochloric acid, and add 1mol / L. Ferric chloride solution, and by adding sodium hydroxide to maintain the pH of the system, the thickness of ferric oxide is about 80nm. A pigment having a red effect is obtained. Compared with the red pigment obtained by grinding the mica substrate now, because of the introduction of the air layer, the color purity is higher and the brightness is higher.

In the pigment, the structure of the core material precursor is inconsistent with that of the core material after covering the outer coating layer.

The basic principles and main features of the present invention and the advantages of the present invention have been shown and described above. Those skilled in the art should understand that the present invention is not limited by the foregoing embodiments. What is described in the above embodiments and the description is only to explain the principle of the present invention. The present invention will also have the following without departing from the spirit and scope of the present invention. Various changes and improvements fall within the scope of the claimed invention. The scope of protection of the invention is defined by the appended claims and their equivalents.

Claims

A pigment having both high brightness, high color purity, and high hiding power effects. The pigment includes a core material and an outer coating layer, and is characterized in that:

The core material has a 1-20 layer structure, including an air layer, and / or one of the following three:

A dielectric layer, a reflective layer, and a multilayer structure composed of one or more dielectric layers and a reflective layer,

The total thickness of the core material is 20-1000 nm,

A single layer thickness of the dielectric layer is 50-300 nm, a single layer thickness of the reflective layer is 20-100 nm, and

The deviation between the total thickness of the core material and the thickness of a single layer of the dielectric layer or the reflective layer does not exceed 1% or 5 nm of the average of the total thickness and the thickness of the corresponding layer,

The outer cladding layer is 1-6 layers, the total thickness of the outer cladding layer is 20-1000 nm, and the thickness of each cladding layer is 10-300 nm.
Pigment according to claim 1, characterized in that the material constituting the dielectric layer is selected from SiO 2, MgF 2, Al 2 O 3, AlF 3, Na AlF 6, BaF 2, NdF 3, CaF 3, One or more of LiF and ZnS.
The pigment according to claim 1, wherein a material constituting the reflective layer is selected from one or more of aluminum, silver, copper, gold, titanium, tantalum, niobium, chromium, and nickel.
The pigment according to claim 1, wherein the material constituting the outer coating layer is selected from the group consisting of TiO 2 , Fe 2 O 3 , TiFe 2 O 5 , Fe 3 O 4 , BiOCl, Cr 2 O 3 , and ZrO. 2 , ZnO, SnO 2 , CoO, Co 3 O 4 , VO 2 , V 2 O 3 , iron titanate, Ti 2 O 3 , bismuth vanadate, cobalt aluminate, SiO 2 , Al 2 O 3 , Al (OH ) 3 , one or more of MgF 2 , B 2 O 3 , and ZnS.
The pigment according to any one of claims 1-4, wherein the core material has a 3-9 layer structure including an air layer and a dielectric layer, and the air layer and the dielectric layer are alternately distributed .
The pigment according to claim 5, wherein the core material has a three-layer structure and includes one layer of air and two layers of silica, and the air layer is located between the two layers of silica.
The pigment according to claim 1-4, wherein the core material comprises only one air layer.
The pigment according to any one of claims 1 to 4, wherein the core material has a 3, 5, 7, or 9-layer structure, including 2, 4, 6, or 8 dielectric layers and a reflective layer The two, four, six, or eight dielectric layers are symmetrically disposed with the reflective layer as a center.
A method for preparing a pigment having both high brightness, high color purity, and high hiding power effects, which is characterized in that the method includes the following steps:

(1) Provide super smooth polished stainless steel backing or glass as backing;

(2) A PVD method is used to deposit a peelable release layer on the substrate, and then a PVD method is used to deposit 1-20 dielectric layers, 1-20 reflective layers, or 2-19 dielectric layers and one A multilayer structure consisting of reflective layers, and a peelable isolation layer is deposited, so that a peelable isolation layer and 1-20 dielectric layers, 1-20 reflective layers, or 2-19 dielectric layers are deposited. The multilayer structure consisting of a layer and a reflective layer is a cycle, and the cycle is repeated 1-50 times;

(3) using a release agent to remove the peelable release layer in the material obtained in step (2), and then washing and classifying to obtain a core material precursor having a predetermined particle size distribution;

(4) dispersing the core material precursor obtained in step (3) in water and / or ethanol to prepare a slurry, adding a coating solution, performing wet chemical coating, and sequentially coating 1-6 layers of coating;

Among them, after the coating of each layer of coating is completed, the coating of the next layer of coating can be continued by adjusting the coating conditions, or it can be re-dispersed in a solvent to prepare a slurry after filtering and washing. Covering

(5) After the coating is completed, filtering, washing and drying are performed to obtain pigments with simultaneously high brightness, high color purity and high hiding power.
The method according to claim 9, wherein step (5) further comprises a step of calcining after drying.
The manufacturing method according to claim 9 or 10, wherein one of the 1-20 layer dielectric layer or the 2-19 layer dielectric layer in step (2) is in Eventually the pigment disappears and forms an air layer.
The method according to claim 9 or 10, wherein the material constituting the dielectric layer is selected from the group consisting of SiO 2 , MgF 2 , Al 2 O 3 , AlF 3 , Na AlF 6 , BaF 2 , NdF 3 , One or more of CaF 3 , LiF, and ZnS.
The method according to claim 9 or 10, wherein the material constituting the reflective layer is selected from one or more of aluminum, silver, copper, gold, titanium, tantalum, niobium, chromium, and nickel.
The method according to claim 9 or 10, characterized in that the material constituting the outer coating layer is selected from the group consisting of TiO 2 , Fe 2 O 3 , TiFe 2 O 5 , Fe 3 O 4 , BiOCl, Cr 2 O 3 , ZrO 2 , ZnO, SnO 2 , CoO, Co 3 O 4 , VO 2 , V 2 O 3 , iron titanate, Ti 2 O 3 , bismuth vanadate, cobalt aluminate, SiO 2 , Al 2 O 3 , One or more of Al (OH) 3 , MgF 2 , B 2 O 3 , and ZnS.
The pigment having high brightness, high color purity and high hiding power effect according to any one of claims 1 to 8 or the high brightness, high color purity and high hiding power effect prepared by the preparation method according to any one of claims 9 to 14 Of pigments in coatings, inks, cosmetics, and makeup.