Ion absorption type nitride coloring pigment

Abstract

The invention belongs to the technical field of tinting pigments and preparation thereof, and particularly relates to an ion absorption type nitride tinting pigment, the composition general formula of the ion absorption type nitride tinting pigment is aAX. [mM3N2.yREN [delta] 1 / 3]. N [(1-x) Si3N4.xDN [delta] 2 / 3]. BC, the ion absorption type nitride tinting pigment is obtained by calcining for 1-50 hours in an inert or reducing atmosphere at the temperature of 1300-1800 DEG C, the obtained pigment can realize continuous coloring in an orange red visible light region under sunlight. The ion absorption type inorganic nitride coloring pigment is non-toxic, has strong absorption in a blue-green light region and a wide absorption band, can realize continuous coloring in an orange-red visible light region, and overcomes the defects of weak light absorption, extremely poor coloring performance and unstable color generation of the functional luminous pigment. The pigment has the advantages of bright red color, stable physical and chemical properties, environmental friendliness in preparation and use processes and the like, and accords with an ideal coloring pigment.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of colored pigments and its preparation, and particularly relates to an ion-absorbing nitride colored pigment. BACKGROUND

[0002] Pigments can be classified into colored pigments, functional pigments, white pigments, etc. Colored pigments can impart color to objects, and their performance mainly depends on color (hue, lightness, and saturation) and color rendering (color strength and hiding power). Functional pigments refer to pigments with specific functional properties (such as luminescent pigments, pearlescent pigments, anti-rust pigments, magnetic pigments, conductive pigments, heat-resistant pigments, etc.), and the core requirement is to exert specific functional effects in the materials or products to which they are applied through their chemical composition, crystal structure, or physical properties, while the coloring effect is only auxiliary, or even completely lacks coloring ability. For example, luminescent pigments can store energy after light exposure and emit light in the dark (luminescent pigments), or emit fluorescence under specific conditions (such as ultraviolet light) (fluorescent pigments), thereby being applied in weak light illumination indication or anti-counterfeiting fields.

[0003] Colored pigments achieve coloring through selective absorption and scattering (reflection) of visible light: for example, when the absorption wavelength extends to >530 nm, the color evolves to red, i.e., red pigments absorb green and yellow light and reflect red light. The currently widely used traditional inorganic colored red pigments still have bottlenecks that need to be solved: 1) most of them contain toxic elements, such as molybdenum chromium red (PbCr2O4 and PbMoO4), realgar (α-As4S4), red lead (Pb3O4), cinnabar (HgS), cadmium red (CdS 1-x Se x Coating a layer of SiO2 / ZrSiO4 on the outer surface can reduce its toxicity and improve the use temperature, but still cannot avoid environmental pollution and harm to living organisms during preparation and use. 2) Iron red pigments (Fe2O3) are non-toxic and inexpensive, but the color rendering is dark, making it difficult to meet the diversified color requirements. 3) New developed low-toxicity alternative warm-toned pigments, such as rare earth sulfides (such as γ-Ce2S3) red pigments, have a relatively serious environmental pollution during production, and the stability needs to be improved; while Ca 1-x La x Ta(O, N)3 orange-red pigments have good stability and wide color rendering range, but due to the element Ta, they are expensive and have poor practicality. The color development of these colored pigments is related to the band gap absorption of the substrate itself, and their advantage is high color rendering efficiency based on intrinsic absorption. Colored pigments require the band gap absorption limit to be located in the visible light region, and there are very few such narrow-band inorganic colored pigments, and it is extremely difficult to find new narrow-band materials. Therefore, it is urgent to develop inorganic red pigments that are non-toxic to the environment and living organisms and have pure color development.

[0004] On the contrary, most of the inorganic materials belong to wide band gap materials with band gap absorption limit in the ultraviolet region, and there are many kinds. The body color is white, which cannot be directly used for coloring pigments. At this time, specific ions can be doped in wide band gap materials to realize coloring of wide band gap materials by using the ion absorption of visible light. For example, photoluminescence materials emit fluorescence (usually visible light) of a specific color by absorbing specific wavelength (usually ultraviolet light) incident light. Among them, wide excitation band luminescent materials, such as long afterglow materials and luminescent materials for white light LED, have an absorption limit that can be extended to the blue-green light region and color, such as: 1) alkaline earth sulfide long afterglow luminescent materials, such as (Ca, Sr) S: Eu, Ln, the absorption limit can reach 560 nm, as a kind of effect red fluorescent pigment, has been applied to the weak light illumination indicating field, but the moisture resistance of (Ca, Sr) S is very poor, and it cannot be applied to humid indoor and outdoor environments. 2) Alkaline earth silicon nitride white light LED and long afterglow luminescent materials, such as Sr2Si5N8: Eu, CaAlSiN3: Eu, the absorption limit can reach 600 nm, but the coloring performance is very weak. In theory, these wide excitation band luminescent materials can meet the requirements of coloring pigments, but their visible light absorption and reflection ability is particularly poor, which is two orders of magnitude weaker than the above-mentioned narrow band gap coloring pigments, and the coloring performance is extremely poor. Secondly, the use conditions of luminescent materials are usually strong excitation, such as the excitation density of LED lighting can reach 2000 kW / m 2 ; while the use conditions of pigments are conventional light or sunlight, and the maximum excitation density does not exceed 1 kW / m 2 . In addition, due to the existence of strong luminescence, the radiation transition luminescence is superimposed on the reflected light, which seriously interferes with the coloration. The color and coloration fluctuate greatly with different irradiation environments, which cannot meet the color stability requirements of coloring pigments. When measuring the coloration data of these luminescent materials using a conventional spectrometer, accurate data is often not obtained. Therefore, these luminescent materials can be used as functional luminescent pigments, such as long afterglow luminescent toys, anti-counterfeiting inks, etc., which use the luminescent effect, rather than as coloring pigments, because their coloring power, hiding power and other coloration properties are poor and unstable. SUMMARY

[0005] In view of the shortcomings of the prior art, the present application provides an ion absorption type inorganic nitride coloring pigment with performance comparable to that of narrow band gap coloring pigments, and overcomes the three shortcomings of the above-mentioned functional luminescent pigments. Red coloring is achieved under visible light irradiation. The pigment has the advantages of good coloring effect, stable chemical properties, etc.

[0006] Technical scheme of the present application:

[0007] An ion absorption type nitride coloring pigment, the general formula of which is:

[0008] aAX·[mM3N2·yREN δ1 / 3]·n[(1-x)Si3N4·xDN δ2 / 3 ]·bC

[0009] Where A is Li + Na + K + NH4 + One or more of the following; M is Mg 2+ Ca 2+ 、Sr 2+ Ba 2+ Zn 2+ Mn 2+ One or more of them; X is a halogen F - Cl - ,Br - One or more of the following; RE is a colorant or a mixture of a colorant and an auxiliary colorant, wherein the colorant is Eu. 2+ Yb 2+ Ce 3+ One or more of the following, with Sm as the auxiliary colorant. 3+ 、Nd 3+ One or two of them; D is Li + Al 3+ B 3+ Fe 3+ Ti 4+ One or more of the following elements are used: δ1 is the valence state of element RE, δ2 is the valence state of element D, and a, b, m, n, x, and y are mole fractions, where a = 0.01-0.2; the initial raw materials are added in the form of oxides or nitrides; b is equal to the molar ratio of element C to element O in the initial raw materials, i.e., b = 0.80-2.0, 3m+y = 0.7-5.2, n = 0.25-4.2, x = 0.01-1.0, and y = 0.01-1.5. Calcination at 1300-1800 ℃ in an inert or reducing atmosphere for 1-50 h yields ion-absorbing nitride coloring pigments. The resulting pigments can achieve continuous coloring in the orange-red visible light region under sunlight.

[0010] The initial raw material C source is added directly by mixing in, and the preferred C source is organic sugars of C5-C7, melamine (C3H6N6), 5-aminotetrazole (C2H4N4) and other organic compounds.

[0011] In the above general formula, the preferred components are as follows:

[0012] M is Ca 2+ 、Sr 2+ Ba 2+ One or more of the following conditions must be met: 0.8 ≤ 3m + y ≤ 1.2, 0.25 ≤ n ≤ 0.4, 0 ≤ x ≤ 0.2, and D = Al.3+ .

[0013] M is Mg 2+ Ca 2+ 、Sr 2+ Ba 2+ One or more of the following conditions must be met: 3.8 ≤ 3m + y ≤ 4.2, 0.28 ≤ n ≤ 0.38, 0 ≤ x ≤ 0.2, and D = Al. 3+ .

[0014] M is Ca 2+ 、Sr 2+ And its combinations, 0.8≤3m+y≤1.21, 1.1≤n≤1.30, 0.50≤x≤0.85 and D=Al 3 + .

[0015] M is Ca 2+ 、Sr 2+ Ba 2+ One or more of the following conditions must be met: 1.8 ≤ 3m + y ≤ 2.2, 1.45 ≤ n ≤ 1.90, 0 ≤ x ≤ 0.2, and D = Al. 3+ .

[0016] M is Mg 2+ Ca 2+ 、Sr 2+ One or more of the following conditions must be met: 2.8 ≤ 3m + y ≤ 3.2, 1.8 ≤ n ≤ 2.2, 0.8 ≤ x ≤ 1.2, and D = Al. 3+ .

[0017] M is Mg 2+ Ca 2+ 、Sr 2+ One or more of the following conditions must be met: 0.8 ≤ 3m + y ≤ 1.2, 2.2 ≤ n ≤ 2.5, 0.35 ≤ x ≤ 0.5, and D = Al. 3+ .

[0018] M is Mg 2+ Ca 2+ 、Sr 2+ One or more of the following conditions must be met: 3.8 ≤ 3m + y ≤ 4.2, 2.5 ≤ n ≤ 2.8, 0.6 ≤ x ≤ 0.9, and D = 1 / 2Al. 3+ + 1 / 2Li + .

[0019] M is Mg 2+ Ca 2+ 、Sr 2+ One or more of the following conditions must be met: 4.8 ≤ 3m + y ≤ 5.2, 2.5 ≤ n ≤ 2.8, 0.6 ≤ x ≤ 0.9, and D = Al. 3+ .

[0020] M is Ca 2+ 、Sr 2+ One or more of the following conditions must be met: 0.8 ≤ 3m + y ≤ 1.2, 3.8 ≤ n ≤ 4.2, 0.9 ≤ x ≤ 1.1, and D = 3 / 4Al. 3+ + 1 / 4Li + .

[0021] The beneficial effects of this invention are as follows: This ion-absorbing inorganic nitride coloring pigment is non-toxic, exhibits strong absorption in the blue-green light region with a wide absorption band, and can achieve continuous coloring in the orange-red visible light region. It also overcomes the shortcomings of the aforementioned functional luminescent pigments, such as weak light absorption, extremely poor coloring performance, and unstable color. This pigment displays a bright red color, has stable physicochemical properties, and is environmentally friendly during preparation and use, thus possessing many advantages that make it an ideal coloring pigment. Attached Figure Description

[0022] Figure 1 This is the reflectance spectrum of Example 2;

[0023] Figure 2 This is the reflectance spectrum of Example 6;

[0024] Figure 3 This is the reflectance spectrum of Example 7;

[0025] Figure 4 This is the reflectance spectrum of Example 8;

[0026] Figure 5 This is the reflectance spectrum of Example 9;

[0027] Figure 6 This is the reflectance spectrum of Example 10;

[0028] Figure 7 This is the reflectance spectrum of Example 11;

[0029] Figure 8 This is the reflectance spectrum of Example 12. Detailed Implementation

[0030] The following specific embodiments illustrate the nitride coloring pigments of the present invention with different compositions and their optical properties.

[0031] Comparative Example 1: Commercial CaAlSiN3:Eu red phosphor for LEDs.

[0032] Example 1: NH4F (98%), Ca3N2 (98%), Si3N4 (98%), Eu2O3 (99%), Fe2O3 (98%), and C powder were used as initial raw materials. The C powder was added directly, and the C / O molar ratio was 1.2. The raw materials were weighed according to the table below, ground thoroughly for 30 min under an inert atmosphere, placed in a corundum tube, and then placed in a resistance furnace. The furnace was filled with N2 gas, and the sample was heated to 1650 °C at a rate of 10 °C / min, held for 4 h, and then cooled to room temperature. After grinding, the target product was obtained. The performance indicators are compared with those of Comparative Example 1, as shown in the table below. The color measurement conditions for all examples of this invention were kept consistent, and the performance of the obtained pigments is shown in the table below.

[0033] Using a similar method, C powder was added at a C / O molar ratio of 1.2, and the proportions of other elements are shown in the table below, to obtain Examples 2 through 27.

[0034] The above embodiments employ a solid-state reaction method for preparation. The initial raw materials can be halides, oxides, sulfides, hydrides, carbides, nitrides, or complex salts containing the elements mentioned in the technical solution, such as carbonates, oxalates, nitrates, acetates, and sulfates. The calcination temperature is between 1300-1800 °C, adjusted according to the amount of material, particle size, and reactivity. For example, in Example 1, if the initial raw materials are Ca(NO3)2, tetraethyl orthosilicate (TEOS), Eu(NO3)3, ammonia, and the organic carbon source glucose, the precursor can be prepared via a sol-gel method, and the corresponding calcination temperature can be reduced to 1300 °C. The calcination time is between 1-50 h, adjusted according to the amount of material and the reactivity of the initial raw materials; a shorter calcination time is required when the amount of material is small and the initial raw materials have high reactivity.

[0035] In the above embodiments, halides are the most effective choice for component AX, typically fluorides and chlorides, while bromides and iodides are more expensive. Sulfides and nitrides also show good results, especially nitrides, which do not introduce impurities and result in a very pure phase, but their stability is poor, increasing the difficulty of preparation, requiring inert gas protection, and are also more expensive. Component aAX (a=0.01-0.2) acts as a co-solvent, lowering the reaction temperature by 10-100 °C, and can also make the pigment color more vibrant, further improving pigment performance (absorbance, hiding power, tinting strength) by 7-23%. The optimal addition amount a is between 0.01-0.2, and the specific optimal addition amount needs to be adjusted according to the initial raw material particle size, reactivity, and reaction temperature. When the initial raw material particle size is coarse, the reactivity is low, and the reaction temperature is high, the a value approaches 0.2. Conversely, the a value approaches 0.01.

[0036] In the above embodiments, component M can be selected from oxides (such as CaO) or carbonates (such as CaCO3), hydrides (such as CaH2), carbides (such as CaC2), nitrides (such as Ca3N2), or carbon-containing complexes (such as CaCN2), or its metal powder (such as Ca powder) of the corresponding elements, which has the best overall performance (coloring effect and cost). 2+ 、Sr 2+ and Ba 2+ It is the element with the best overall performance (coloring effect and cost) and can be used as a matrix component; moreover, the components M can be substituted for each other, which can greatly adjust the absorption edge. If Ca3N2 is replaced with Sr3N2, using the same method as in Example 1, Example 2 can be obtained. The properties of the obtained pigment are shown in the table below, and its reflectance spectrum is shown in... Figure 1 Compared to Example 1, its color is significantly more warm-toned. If Ca3N2 is replaced with Ba3N2, and the same method as in Example 1 is used, Example 3 can be obtained; the properties of the resulting pigment are shown in the table below. Compared to Examples 1 and 2, its color is significantly more cool-toned. Based on Examples 1-3, the M element in Mg... 2+ Ca 2+ 、Sr 2+ Ba 2+ Combinations and transformations between them. For example, Ca 2+ +Sr 2+ 、Sr 2+ +Ba 2+ Therefore, the color can be arbitrarily changed between Examples 1-3. Due to the significant difference in ionic radii, Ba... 2+ +Ca 2+ The combination of these elements makes it difficult to obtain a pure phase; the color development is noticeably biased towards cool tones, and the color regularity is weak. In Examples 1-3, a small amount of Mg... 2+ (<10 mol%) Ca substitution 2+ 、Sr 2+ Ba 2+ This can increase the purity of red color development by 5-10%. Due to its small ionic radius, Zn... 2+ It cannot be used independently as a matrix material, but a small amount of Zn 2+ (<10 mol%) Ca substitution 2+ 、Sr 2+ Ba 2+ This can improve color rendering by 7-13%. Because Zn 2+ It is easily volatilized under inert and reducing atmospheres, and needs to be added after the reduction calcination process, followed by a second oxidation calcination at a low temperature (<800 °C). Mg 2+ and Ca 2+ 、Sr 2+ Ba 2+ When used together, they can form a series of pigment components, such as Mg.2+ +Ca 2+ Mg 2+ +Sr 2+ Mg 2+ +Ba 2+ Example 6 is Mg 2+ +Ba 2+ The combination, its reflectance spectrum is shown in Figure 2 Mn 2+ ionic radius and Mg 2+ Zn 2+ It is comparable and can replace Mg 2+ Zn 2+ The ion is suitable for all systems in Examples 1-27. Its addition amount, not exceeding y / 3, can significantly enhance absorbance by 14-23%, reducing the amount of colorant required. Mn 2+ Adding too much will cause the red pigment to appear darker and less vibrant.

[0037] For component M, if a small amount of M is selected as a halide, used alone or in combination with AX at a concentration not exceeding 5%, it can act as a co-solvent due to its low melting point, such as SrF2, or NaF+MgF2, ZnF2, CaF2, and BaF2, resulting in a purer phase and better performance. The 3m+y value has a significant impact on the pigment's coloring and tinting properties, and also affects the calcination temperature and particle size. A higher 3m+y value results in a warmer pigment hue, with an optimal value between 0.7 and 5.3. Within this range, the pigment phase composition is usually not pure, but all exhibit good color rendering properties. It should be noted that even with 3m+y values ​​outside this range, good color rendering properties are still achieved, but due to the presence of more impurities, it may lead to a waste of some initial raw materials from an economic perspective.

[0038] In the above embodiments, trivalent REs in the RE component are best selected from oxides (RE2O3) for overall performance (coloring effect and cost), while divalent REs are preferably selected from sulfides (such as EuS), although trivalent REs can also be used, which are then reduced during the preparation process (Example 1). Due to their low melting point, halides such as fluorides or chlorides can also be used, which can significantly reduce the calcination temperature. Directly adding nitrides can simplify the preparation process and largely adjust the color tone towards a warmer hue, but nitrides themselves are expensive, which will significantly increase the cost. For the same matrix, the colorant can be changed to Yb. 2+ Ce 3+ As in Examples 7-9, its color is similar to that of the colorant Eu. 2+ The differences are shown in the comparison of their reflectance spectra. Figure 3 -5. Colorant Ce 3+ The color shift is subtle, leaning towards a cooler tone. Figure 3 ), colorant Yb 2+The coloration of Eu 2+ Similar in color, leaning towards warm tones, but with slightly less light absorption than Eu. 2+ ( Figures 4-5 Co-doping with colorants can significantly improve absorbance by 13-35%, such as Ce. 3+ +Eu 2+ Yb 2+ +Eu 2+ Ce 3+ +Yb 2+ However, this will increase costs. Auxiliary colorant Sm 3+ 、Nd 3+ It will significantly quench, thereby eliminating color fluctuations in the obtained pigment under different lighting conditions and enhancing the application performance of the pigment. Its addition amount should not exceed y / 3. The effects of various component parameters, such as a, m, n, x, and y, on the pigment color follow similar patterns to those in Examples 1-11, such as for yREN... δ1 / 3 Generally speaking, the larger the y value, the warmer the hue. See Examples 10-12 for details, and the reflection spectrum comparison is shown below. Figures 6-8 The optimized value is between 0.1 and 1.5. When m=0, the y value reaches its maximum, which can exceed the optimized value of 1.5, and the color tends to be warm, but the preparation difficulty and cost will increase.

[0039] In the above embodiments, metallic Si, oxide (SiO2), or nitride (such as Si3N4) are selected as the component Si, offering the best overall performance (coloring effect and cost). Directly using nitrides simplifies the preparation process and significantly adjusts the color towards a warmer tone, but increases costs. Directly using metallic Si powder also simplifies the preparation process, but it is more expensive. The n value also affects the pigment calcination temperature and the pigment's hue. The warmer the n value, the higher the calcination temperature and the warmer the hue. The optimal n value is between 0.25 and 4.2, and the best optimal value depends on the combination with the m value. Within this optimal range, the pigment phase composition is usually not pure, and all phases exhibit good color rendering properties. It should be noted that even with n values ​​outside this range, good color rendering properties are still achieved, but due to the presence of more impurities, it may result in some waste of initial raw materials from an economic perspective.

[0040] Component Si can be partially or completely replaced by element D to form a solid solution, thereby improving the pigment's color development or promoting calcination. Adding a small amount of Li... + (Equivalent to the value of a), it mainly acts as a co-solvent, suitable for all systems in Examples 1-27, and can replace Si when added in large quantities. 4+ It becomes part of the matrix (Examples 19-21). B 3+ Can replace Al 3+ This causes a blue shift in the spectrum, thereby adjusting the pigment's color rendering to lean towards cooler tones, making it suitable for all pigments containing Al.3+ In this system, the nitridation of boron is relatively difficult, increasing the difficulty and cost of preparation. Ti 4+ and Fe 3+ It is a variable valence element, and some valence states have strong absorption in the visible light region, which can significantly enhance the light absorption of pigments by 9-15%, reduce the amount of colorant added, and is suitable for all systems in Examples 1-27. Ti 4+ and Fe 3+ High amounts of Ti will also cause the red pigment to appear darker and less vibrant. 4+ and Fe 3+ As an auxiliary additive, it is usually not added alone, and the amount added does not exceed 50% of the D or Si elements.

[0041] The final nitride content after calcination significantly affects the performance of the resulting pigment. O causes a blue shift in the pigment's spectrum; higher O content results in a color bias towards orange-yellow-green, exhibiting excellent color rendering but with a cooler tone. Carbon (C) can reduce and eliminate O. The amount of C added depends on the purity and type of the raw materials and atmosphere. The parameter b depends on the initial C / O ratio of the raw materials, the particle size, and the reactivity. Its optimized value is b = C / O = 0.80-2.0. When the raw material particle size is small and the reactivity is high, the b value approaches 0.80. Conversely, the b value approaches 2.0.

[0042] Using a method similar to that used in Examples 1-27, the effects of other parameters not listed in Examples 1-27 on color, absorbance, and tinting strength can also be obtained. When A=Rb + or Cs + When, with A=K + Similar results were obtained, but Rb + and Cs + The price is relatively high. Performance is better when used in combination A, such as A=Li. + and NH4 + The combination of these factors can result in a more uniform product particle size, and while maintaining the color, the calcination temperature can be appropriately reduced by 25-50 ℃. When M contains a portion of Be... 2+ or Cd 2+ While these elements may not affect the performance of the sample, they may cause difficulties in application due to environmental protection requirements.

[0043] The data and results for each embodiment are shown in Table 1 below:

[0044] Table 1

[0045]

[0046]

[0047]

[0048]

[0049]

[0050]

[0051]

Claims

1. An ion-absorbing nitride coloring pigment, characterized in that, The general formula for the ion-absorbing nitride coloring pigment is: aAX·[mM3N2·yREN δ1 / 3 ]·n[(1-x)Si3N4·xDN δ2 / 3 ]·bC Where A is Li + Na + K + NH4 + One or more of the following; M is Mg 2+ Ca 2+ 、Sr 2+ Ba 2+ Zn 2+ Mn 2+ One or more of them; X is a halogen F - Cl - ,Br - One or more of the following; RE is a colorant or a mixture of a colorant and an auxiliary colorant, wherein the colorant is Eu. 2+ Yb 2+ Ce 3+ One or more of the following, with Sm as the auxiliary colorant. 3+ 、Nd 3+ One or two of them; D is Li + Al 3+ B 3+ Fe 3+ Ti 4+ One or more of the following: δ1 is the valence state of element RE, δ2 is the valence state of element D, and a, b, m, n, x, y are mole fractions, a = 0.01-0.2; the substances in the initial raw materials are added in the form of oxides or nitrides; b is equal to the molar ratio of element C to element O in the initial raw materials, i.e., b = 0.80-2.0, 3m+y = 0.7-5.2, n = 0.25-4.2, x = 0.01-1.0, y = 0.01-1.5; calcined at 1300-1800 ℃ in an inert or reducing atmosphere for 1-50 h, ion-absorbing nitride coloring pigments are obtained, and the obtained pigments can achieve continuous coloring in the orange-red visible light region under sunlight.

2. The ion-absorbing nitride coloring pigment according to claim 1, characterized in that, The C source in the initial raw materials is added directly by mixing. The C source is one or more of C5-C7 organic sugars, melamine, and 5-aminotetrazole.

3. The ion-absorbing nitride coloring pigment according to claim 1, characterized in that, M is Ca 2+ 、Sr 2+ Ba 2+ One or more of the following conditions must be met: 0.8 ≤ 3m + y ≤ 1.2, 0.25 ≤ n ≤ 0.4, 0 ≤ x ≤ 0.2, and D = Al. 3+ .

4. The ion-absorbing nitride coloring pigment according to claim 1, characterized in that, M is Mg 2+ Ca 2+ 、Sr 2+ Ba 2+ One or more of the following conditions must be met: 3.8 ≤ 3m + y ≤ 4.2, 0.28 ≤ n ≤ 0.38, 0 ≤ x ≤ 0.2, and D = Al. 3+ .

5. The ion-absorbing nitride coloring pigment according to claim 1, characterized in that, M is Ca 2+ 、Sr 2+ And its combinations, 0.8≤3m+y≤1.21, 1.1≤n≤1.30, 0.50≤x≤0.85 and D=Al 3+ .

6. The ion-absorbing nitride coloring pigment according to claim 1, characterized in that, M is Ca 2+ 、Sr 2+ Ba 2+ One or more of the following conditions must be met: 1.8 ≤ 3m + y ≤ 2.2, 1.45 ≤ n ≤ 1.90, 0 ≤ x ≤ 0.2, and D = Al. 3+ .

7. The ion-absorbing nitride coloring pigment according to claim 1, characterized in that, M is Mg 2+ Ca 2+ 、Sr 2+ One or more of the following conditions must be met: 2.8 ≤ 3m + y ≤ 3.2, 1.8 ≤ n ≤ 2.2, 0.8 ≤ x ≤ 1.2, and D = Al. 3+ .

8. The ion-absorbing nitride coloring pigment according to claim 1, characterized in that, M is Mg 2+ Ca 2+ 、Sr 2+ One or more of the following conditions must be met: 0.8 ≤ 3m + y ≤ 1.2, 2.2 ≤ n ≤ 2.5, 0.35 ≤ x ≤ 0.5, and D = Al. 3+ .

9. The ion-absorbing nitride coloring pigment according to claim 1, characterized in that, M is Mg 2+ Ca 2+ 、Sr 2+ One or more of the following conditions must be met: 3.8 ≤ 3m + y ≤ 4.2, 2.5 ≤ n ≤ 2.8, 0.6 ≤ x ≤ 0.9, and D = 1 / 2Al. 3+ + 1 / 2Li + .

10. The ion-absorbing nitride coloring pigment according to claim 1, characterized in that, M is Mg 2+ Ca 2+ 、Sr 2+ One or more of the following conditions must be met: 4.8 ≤ 3m + y ≤ 5.2, 2.5 ≤ n ≤ 2.8, 0.6 ≤ x ≤ 0.9, and D = Al. 3+ .

11. The ion-absorbing nitride coloring pigment according to claim 1, characterized in that, M is Ca 2+ 、Sr 2+ One or more of the following conditions must be met: 0.8 ≤ 3m + y ≤ 1.2, 3.8 ≤ n ≤ 4.2, 0.9 ≤ x ≤ 1.1, and D = 3 / 4Al. 3+ + 1 / 4Li + .

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