WO2019000581A1 - 着色剂及其制备方法 - Google Patents

着色剂及其制备方法 Download PDF

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WO2019000581A1
WO2019000581A1 PCT/CN2017/096520 CN2017096520W WO2019000581A1 WO 2019000581 A1 WO2019000581 A1 WO 2019000581A1 CN 2017096520 W CN2017096520 W CN 2017096520W WO 2019000581 A1 WO2019000581 A1 WO 2019000581A1
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rare earth
alkali metal
phosphate
phosphorus
compound
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PCT/CN2017/096520
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English (en)
French (fr)
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李成宇
张洪杰
田磊
池建义
庞然
姜伟
王明
王滨
董开强
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中国科学院包头稀土研发中心
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Priority to US16/084,379 priority Critical patent/US11208561B2/en
Priority to EP17905906.8A priority patent/EP3447093B1/en
Publication of WO2019000581A1 publication Critical patent/WO2019000581A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/20—Compounds containing only rare earth metals as the metal element
    • C01F17/288—Sulfides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/06—Treatment with inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/62—L* (lightness axis)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/63—Optical properties, e.g. expressed in CIELAB-values a* (red-green axis)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/64—Optical properties, e.g. expressed in CIELAB-values b* (yellow-blue axis)

Definitions

  • the invention relates to a coloring agent and a preparation method thereof, in particular to a phosphorus-containing rare earth sulfide coloring agent and a preparation method thereof.
  • the invention also relates to the use of a phosphorus-containing compound.
  • Rare earth sulfides are bright, non-toxic, strong in hiding power and strongly absorb ultraviolet rays. They can replace the widely used organic red pigments and heavy metal pigments containing lead and cadmium, which are widely used in plastics, plastic paints, inks, leather and many other fields. .
  • the Beijing Research Institute of Nonferrous Metals has developed a two-stage process for the preparation of red pigment sulphide ruthenium, using ruthenium oxide, sulphur, sodium carbonate and hydrogen as raw materials.
  • the process does not use toxic gases such as hydrogen sulfide or carbon sulfide, and is easy to implement industrially.
  • Inner Mongolia University of Science and Technology prepares the rare earth sulfide precursor by reacting the rare earth salt solution with the sulfurizing reagent, and then passes through the dry sulfurized gas to vulcanize at less than 1000 ° C to obtain a rare earth sulfide pigment.
  • a ruthenium compound as a raw material, an alkali metal compound as an additive, sulfur as a vulcanizing agent, and activated carbon as an auxiliary agent to prepare a rare earth sulfide pigment at a high temperature.
  • Some methods for preparing rare earth sulfides are also disclosed in CN1201441A, CN1271332A, CN1426376A, and CN1087273C.
  • the rare earth sulfide obtained by the above method can be directly used as a pigment after being pulverized, but the vividness of the pigment is not good, and thus it is necessary to undergo a fluorine washing treatment process to improve color properties.
  • the fluorine washing process is more complicated and produces a large amount of industrial waste liquid; Lead to increased production costs and reduced production efficiency. Therefore, there is still a need for a rare earth sulfide coloring agent which can achieve a high degree of vividness without undergoing a fluorine washing treatment process. Also, a method for preparing a coloring agent is required, which does not require a fluorine washing treatment process, thereby Save production costs and increase production efficiency.
  • Chinese Patent Application No. 200710036985.3 discloses a method for synthesizing a rare earth oxysulfide luminescent material using an alkali metal sulfide, an alkali metal carbonate, an alkali metal phosphate and an alkali metal hydrogen phosphate.
  • One or more mixtures as a flux at a high temperature, the flux first reacts with elemental sulfur, an alkali metal sulfide or a mixture of the two to form an alkali metal polysulfide, and the resulting alkali metal polysulfide reacts with the rare earth compound.
  • the corresponding rare earth oxysulfide luminescent material is synthesized.
  • the above method uses an alkali metal phosphate and an alkali metal hydrogen phosphate as a flux to reduce the reaction temperature of the high-temperature solid phase reaction, but does not involve the use of an alkali metal phosphate or the like to enhance the rare earth sulfide colorant. Brightness.
  • rare earth sulphur oxide luminescent materials and rare earth sulphide colorants belong to different technical fields. Rare earth sulphur oxides and rare earth sulphide have different chemical structures and have completely different properties. They belong to different technical fields and usually do not emit light. The manufacturing technology of materials is applied to the manufacture of colorants. Further, the amount of the alkali metal phosphate and the alkali metal hydrogen phosphate as the flux is very small with respect to the rare earth element, and is negligible in the product.
  • Another object of the present invention is to provide a rare earth sulfide coloring agent, the vividness thereof Improved, but does not require a fluorine wash treatment process.
  • Still another object of the present invention is to provide a method for producing the above coloring agent, which is simple in process and omits the fluorine washing treatment step.
  • the present invention provides a use of a phosphorus-containing compound for improving the vividness of a rare earth sulfide coloring agent selected from the group consisting of alkali metal phosphates, alkali metal hydrogen phosphates, alkali metal dihydrogen phosphates, alkaline earth metals.
  • a rare earth sulfide coloring agent selected from the group consisting of alkali metal phosphates, alkali metal hydrogen phosphates, alkali metal dihydrogen phosphates, alkaline earth metals.
  • the rare earth sulfide colorant has the following chemical formula:
  • RE is selected from one or more of La, Ce, Pr, Nd, and Sm, and the ratio of y to x is 0.001 to 0.65.
  • the present invention also provides a rare earth sulfide colorant having the following chemical formula:
  • RE is selected from one or more of La, Ce, Pr, Nd, and Sm, and the ratio of y to x is 0.001 to 0.65.
  • RE is La, Ce, Pr or Nd
  • the ratio of y to x is from 0.01 to 0.55.
  • the chromaticity coordinates of the colorant are:
  • the present invention also provides a method for preparing the above coloring agent, comprising the steps of: mixing a rare earth compound, a sulfur source, a phosphorus-containing compound, and an alkali metal compound to obtain a mixture, and mixing the mixture
  • the coloring agent is obtained by reacting at 700 to 1500 ° C; wherein the phosphorus-containing compound is selected from the group consisting of alkali metal phosphates, alkali metal hydrogen phosphates, alkali metal dihydrogen phosphates, alkaline earth metal phosphates, and rare earth metals.
  • the rare earth compound is one or more selected from the group consisting of rare earth metal carbonates, rare earth metal oxides, rare earth metal oxalates, rare earth metal sulfates, and rare earth metal nitrates;
  • the sulfur source is selected from one or more of sulfur, sulfide or sulfate; and the alkali metal compound is selected from one or more of a carbonate, an oxide and a hydroxide of an alkali metal element.
  • the molar ratio of the alkali metal element in the alkali metal compound to the rare earth element in the rare earth compound is 0.06 to 0.30:1; the alkali metal element in the alkali metal compound and The molar ratio of the sulfur element in the sulfur source is 0.02 to 0.1:1; and the molar ratio of the alkali metal element in the alkali metal compound to the phosphorus element in the phosphorus-containing compound is 0.1 to 0.4:1.
  • the molar ratio of the rare earth element in the rare earth compound to the sulfur element in the sulfur source is 1:1.5 to 4, and the sulfur element in the sulfur source and the phosphorus
  • the molar ratio of the phosphorus element in the compound is from 0.9 to 16:1.
  • the mixture is reacted in the following atmosphere to obtain the colorant: hydrogen, hydrogen sulfide, carbon disulfide, carbon monoxide, nitrogen or air.
  • the invention adds the phosphorus-containing compound to the preparation process of the rare earth sulfide coloring agent, thereby improving the vividness of the coloring agent, and thus the coloring agent with high vividness can be obtained without the fluorine washing treatment process.
  • the preparation method of the present invention can reduce the production cost, omit the sewage treatment link, and improve the production efficiency.
  • Example 1 is an XRD diffraction pattern of Example 5.
  • Example 12 is an XRD diffraction pattern of Example 12.
  • the Lab color space is designed to be close to human vision.
  • the color space of the present invention is also referred to as color space and chromaticity coordinates.
  • L represents brightness
  • a and b represent dimensions of color opposition.
  • the L value is 0, the color is black, the L value is white when it is close to 100; the a value indicates the position of the color between red and green; and the b value indicates the position of the color between blue and yellow.
  • the present invention provides the use of a phosphorus-containing compound for improving the vividness of a rare earth sulfide colorant.
  • the phosphorus-containing compound is selected from the group consisting of alkali metal phosphates, alkali metal hydrogen phosphates, alkali metal dihydrogen phosphates, alkaline earth metal phosphates, rare earth metal phosphates, transition metal phosphates, ammonium phosphate salts, One or more of ammonium hydrogen phosphate, ammonium dihydrogen phosphate, aluminum phosphate, boron phosphate, and phosphorus pentoxide.
  • the phosphorus-containing compound is selected from the group consisting of alkali metal phosphates, alkali metal hydrogen phosphates, alkali metal dihydrogen phosphates, ammonium phosphate salts, ammonium hydrogen phosphate salts, ammonium dihydrogen phosphate salts or aluminum phosphate salts. More preferably, the phosphorus-containing compound is selected from the group consisting of alkali metal phosphates, alkali metal hydrogen phosphates, alkali metal dihydrogen phosphates, ammonium phosphate salts, ammonium hydrogen phosphate salts, and ammonium dihydrogen phosphate salts.
  • the phosphorus-containing compound is selected from the group consisting of alkali metal phosphates or ammonium phosphate salts.
  • the phosphorus-containing compound of the present invention include, but are not limited to, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, sodium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, potassium phosphate, potassium hydrogen phosphate, potassium dihydrogen phosphate, aluminum phosphate. , zinc phosphate, etc.
  • the phosphorus-containing compound of the present invention is ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, aluminum phosphate or zinc phosphate.
  • the rare earth sulfide colorant has the following chemical formula:
  • RE is selected from one or more of La, Ce, Pr, Nd, and Sm, and the ratio of y to x is 0.001 to 0.65.
  • RE is preferably La, Ce, Pr or Nd, and more preferably Ce.
  • the ratio of y to x is from 0.01 to 0.55.
  • the rare earth sulfide colorant include, but are not limited to, Ce 2-2x S 3-3x ⁇ 2y [CePO 4 ], La 2-2x S 3-3x ⁇ 2y [ LaPO 4 ], Pr 2-2x S 3- 3x ⁇ 2y [PrPO 4 ], Nd 2-2x S 3-3x ⁇ 2y [NdPO 4 ], Sm 2-2x S 3-3x ⁇ 2y [SmPO 4 ].
  • the ratio of y to x is from 0.001 to 0.65; preferably from 0.01 to 0.55.
  • the colorant of the present invention is a rare earth sulfide and has the following chemical formula:
  • RE is selected from one or more of La, Ce, Pr, Nd, and Sm, and the ratio of y to x is 0.001 to 0.65.
  • RE is preferably La, Ce, Pr, Nd or Sm, more preferably Ce.
  • the ratio of y to x is from 0.01 to 0.55.
  • the rare earth sulfide colorant may include Ce 2-2x S 3-3x ⁇ 2y [CePO 4 ], La 2-2x S 3-3x ⁇ 2y [ LaPO 4 ], Pr 2-2x S 3-3x 2y [PrPO 4 ], Nd 2-2x S 3-3x ⁇ 2y [NdPO 4 ] or Sm 2-2x S 3-3x ⁇ 2y [SmPO 4 ].
  • the ratio of y to x is from 0.001 to 0.65; preferably from 0.01 to 0.55.
  • the colorants of the present invention may be of different colors, such as red, green or yellow, depending on the rare earth element RE.
  • Ce 2-2x S 3-3x ⁇ 2y [CePO 4 ] displays red.
  • the chromaticity coordinates of the colorant of the present invention may be:
  • the chromaticity coordinates of the colorant of the present invention are:
  • the chromaticity coordinates of the colorant of the present invention are:
  • the method for producing a coloring agent of the present invention comprises the steps of: mixing a rare earth compound, a sulfur source, a phosphorus-containing compound, and an alkali metal compound to obtain a mixture, and reacting the mixture at 700 to 1500 ° C to obtain the coloring agent.
  • the above preparation method does not include a fluorine washing treatment process, thereby saving production costs, reducing industrial waste liquid, and shortening the process flow.
  • the order of mixing is not particularly limited. For example, a rare earth compound, a sulfur source, and a phosphorus-containing compound are uniformly mixed, and then an alkali metal compound is added as a flux, and uniformly mixed to obtain a mixture. For another example, a rare earth compound, a sulfur source, a phosphorus-containing compound, and an alkali metal compound are mixed together to obtain a mixture.
  • the phosphorus-containing compound is selected from the group consisting of alkali metal phosphates, alkali metal hydrogen phosphates, alkali metal dihydrogen phosphates, alkaline earth metal phosphates, rare earth metal phosphates, transition metal phosphates, phosphoric acid.
  • alkali metal phosphates alkali metal hydrogen phosphates, alkali metal dihydrogen phosphates, alkaline earth metal phosphates, rare earth metal phosphates, transition metal phosphates, phosphoric acid.
  • an ammonium salt, an ammonium hydrogen phosphate salt, an ammonium dihydrogen phosphate salt, an aluminum phosphate salt, a boron phosphate salt, and phosphorus pentoxide is selected from the group consisting of alkali metal phosphates, alkali metal hydrogen phosphates, alkali metal dihydrogen phosphates, alkaline earth metal phosphates, rare earth metal phosphates, transition metal phosphat
  • the phosphorus-containing compound is selected from the group consisting of alkali metal phosphates, alkali metal hydrogen phosphates, alkali metal dihydrogen phosphates, Ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate or aluminum phosphate. More preferably, the phosphorus-containing compound is selected from the group consisting of alkali metal phosphates, alkali metal hydrogen phosphates, alkali metal dihydrogen phosphates, ammonium phosphate salts, ammonium hydrogen phosphate salts, and ammonium dihydrogen phosphate salts.
  • the phosphorus-containing compound is selected from the group consisting of alkali metal phosphates or ammonium phosphate salts.
  • the phosphorus-containing compound of the present invention include, but are not limited to, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, sodium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, potassium phosphate, potassium hydrogen phosphate, potassium dihydrogen phosphate, aluminum phosphate. , zinc phosphate, etc.
  • the phosphorus-containing compound of the present invention is ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, aluminum phosphate or zinc phosphate.
  • the rare earth compound may be selected from one or more of a rare earth metal carbonate, a rare earth metal oxide, a rare earth metal oxalate, a rare earth metal sulfate, and a rare earth metal nitrate; It is a rare earth metal carbonate, a rare earth metal oxide or a rare earth metal oxalate; more preferably a rare earth metal carbonate or a rare earth metal oxide.
  • the rare earth compound is a cerium-containing compound selected from one or more of cerium carbonate, cerium oxide, cerium oxalate, cerium sulfate, cerium nitrate; preferably cerium oxide, cerium carbonate or Oxalic acid oxalate; more preferably cerium oxide or cerium carbonate.
  • the sulfur source may be selected from one or more of sulfur, sulfide or sulfate; preferably sulfur and sulfide; more preferably sulfur.
  • the alkali metal compound may be selected from one or more of a carbonate, an oxide, and a hydroxide of an alkali metal element.
  • the alkali metal may be lithium, sodium or potassium.
  • the alkali metal compound is preferably a carbonate; specific examples include sodium carbonate or potassium carbonate, preferably sodium carbonate.
  • the molar ratio of the alkali metal element in the alkali metal compound to the rare earth element in the rare earth compound may be 0.06 to 0.30:1; preferably 0.08 to 0.25:1, more preferably 0.1 to 0.2:1. Controlling the molar ratio of the alkali metal element to the rare earth element within the above range is advantageous for improving the vividness.
  • the molar ratio of the alkali metal element in the alkali metal compound to the sulfur element in the sulfur source may be 0.02 to 0.1:1; preferably 0.035 to 0.1:1, more preferably 0.04 ⁇ 0.08:1. Controlling the molar ratio of the alkali metal element to the sulfur element within the above range is advantageous for improving the vividness.
  • the molar ratio of the alkali metal element in the alkali metal compound to the phosphorus element in the phosphorus-containing compound may be from 0.1 to 0.4:1; preferably from 0.2 to 0.4:1, more preferably 0.3 to 0.4:1. Controlling the molar ratio of the alkali metal element to the phosphorus element in the above range is advantageous for improving the vividness.
  • the molar ratio of the rare earth element in the rare earth compound to the sulfur element in the sulfur source may be 1:1.5 to 4; preferably 1:2.0 to 3.9. Controlling the molar ratio of the rare earth element to the sulfur element to the above range is advantageous for improving the vividness.
  • the molar ratio of the sulfur element in the sulfur source to the phosphorus element in the phosphorus-containing compound is from 0.9 to 16:1; preferably from 3 to 13:1; more preferably from 5 to 10. :1. Controlling the molar ratio of the sulfur element to the phosphorus element in the above range is advantageous for improving the vividness.
  • a mixture obtained by mixing a rare earth compound, a sulfur source, a phosphorus-containing compound, and an alkali metal compound is placed in a reaction vessel for a high-temperature solid phase reaction.
  • the material of the reaction vessel may be a high temperature resistant material such as metal, ceramic, corundum or quartz.
  • the invention can adopt a graphite boat, a quartz tube, a crucible or the like for high-temperature solid phase reaction.
  • the mixture is reacted in an atmosphere to obtain the colorant: hydrogen, hydrogen sulfide, carbon disulfide, carbon monoxide, nitrogen or air.
  • the atmosphere is preferably hydrogen sulfide, carbon disulfide, carbon monoxide and hydrogen.
  • the reaction temperature of the present invention may be from 700 to 1500 ° C, preferably from 900 to 1300 ° C, more preferably from 1,000 to 1200 ° C. This is advantageous in obtaining a brighter coloring agent.
  • test methods of the following examples and comparative examples are as follows:
  • the Lab value was tested using a Konica Minolta CM-5 spectrophotometer.
  • the XRD was tested using a Brooke D8 Advance X-ray diffractometer.

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Abstract

本发明公开了一种稀土硫化物着色剂及其制备方法。本发明的稀土硫化物着色剂的化学式为RE2-2xS3-3x·2y[REPO4]，其中，RE选自La、Ce、Pr、Nd、Sm的一种或多种，y与x的比例为0.001～0.65。本发明还公开了一种含磷化合物用于提高稀土硫化物着色剂的鲜艳度的用途。

Description

着色剂及其制备方法 技术领域
本发明涉及一种着色剂及其制备方法，尤其是一种含磷的稀土硫化物着色剂及其制备方法。本发明还涉及一种含磷化合物的用途。
背景技术
随着人们环保意识的增强，许多国家出台相关法律严禁使用含重金属铅、镉、汞等有毒颜料。2016年，我国的工信部、科学技术部、环境保护部联合发布《国家鼓励的有毒有害原料(产品)替代品目录》，将稀土硫化物(例如硫化铈)作为替代品。
稀土硫化物颜色鲜艳、无毒性、遮盖力强、强烈吸收紫外线，可以取代目前大量使用的有机红色颜料和含铅、镉的重金属颜料，从而广泛应用于塑料、塑胶油漆、油墨、皮革等诸多领域。
北京有色金属研究总院开发出两段法制备红颜料硫化铈新工艺，以氧化铈、硫磺、碳酸钠及氢气等为原料。该工艺不使用硫化氢、硫化碳等有毒气体，易于产业化实施。内蒙古科技大学将稀土盐溶液与硫化试剂反应制备稀土硫化盐前躯体，然后通入干燥硫化气体，在低于1000℃下硫化获得稀土硫化物颜料。另外，还可以以铈的化合物为原料，碱金属化合物为添加剂，硫磺为硫化剂，活性炭为辅助剂，在高温下反应制备稀土硫化物颜料。CN1201441A、CN1271332A、CN1426376A和CN1087273C中也公开了一些稀土硫化物的制备方法。
一方面，上述方法获得的稀土硫化物经过粉碎后可以直接作为颜料使用，但是该颜料的鲜艳度不佳，因而需要经过氟洗处理工艺来提高颜色性能。氟洗处理工艺较为复杂，并产生大量工业废液；同时会 导致生产成本增加、降低生产效率。因此，目前仍然需要一种稀土硫化物着色剂，其不需要经过氟洗处理工艺就可以达到较高的鲜艳度；同时也需要一种着色剂的制备方法，其不需要氟洗处理工序，从而节约生产成本、提高生产效率。
另一方面，申请号为200710036985.3的中国专利申请公开了一种稀土硫氧化物发光材料的合成方法，采用碱金属硫化物、碱金属碳酸盐、碱金属磷酸盐和碱金属磷酸氢盐中的一种或多种的混合物作为助熔剂，在高温下助熔剂首先与单质硫、碱金属硫化物或两者的混合物反应生成碱金属多硫化物，生成的碱金属多硫化物与稀土化合物反应，合成相应的稀土氧硫化物发光材料。也就是说，上述方法中采用碱金属磷酸盐和碱金属磷酸氢盐作为助熔剂使用，从而降低高温固相反应的反应温度，但并未涉及采用碱金属磷酸盐等提高稀土硫化物着色剂的鲜艳度。此外，稀土硫氧化物发光材料与稀土硫化物着色剂属于不同的技术领域，稀土硫氧化物与稀土硫化物化学结构不同，并且具有完全不同的性质，属于不同的技术领域，通常不会将发光材料的制造技术应用于着色剂的制造。再有，作为助熔剂的碱金属磷酸盐和碱金属磷酸氢盐相对于稀土元素的用量非常少，在产物中可以忽略不计。
综上，目前尚没有含磷的稀土硫化物着色剂的报道，其不需要经过氟洗处理工艺就可以达到较高的鲜艳度；也没有采用含磷化合物提高稀土硫化物着色剂鲜艳度的报道。
发明内容
本发明的一个目的在于提供一种含磷化合物的用途，其可以提高稀土硫化物着色剂的鲜艳度。
本发明的另一个目的在于提供一种稀土硫化物着色剂，其鲜艳度 得到改善，但不需要氟洗处理工序。
本发明的再一个目的在于提供上述着色剂的制备方法，其工艺简单，省略氟洗处理工序。
本发明提供一种含磷化合物用于提高稀土硫化物着色剂的鲜艳度的用途，所述的含磷化合物选自碱金属磷酸盐、碱金属磷酸氢盐、碱金属磷酸二氢盐、碱土金属磷酸盐、稀土金属磷酸盐、过渡金属磷酸盐、磷酸铵盐、磷酸氢铵盐、磷酸二氢铵盐、磷酸铝盐、磷酸硼盐、五氧化二磷中的一种或多种。
根据本发明的用途，优选地，所述稀土硫化物着色剂具有如下化学式：
RE2-2xS3-3x·2y[REPO4]
其中，RE选自La、Ce、Pr、Nd、Sm的一种或多种，y与x的比例为0.001～0.65。
本发明还提供一种稀土硫化物着色剂，所述稀土硫化物着色剂具有如下化学式：
RE2-2xS3-3x·2y[REPO4]
其中，RE选自La、Ce、Pr、Nd、Sm的一种或多种，y与x的比例为0.001～0.65。
根据本发明的着色剂，优选地，RE为La、Ce、Pr或Nd，y与x的比例为0.01～0.55。
根据本发明的着色剂，优选地，所述着色剂的色度坐标为：
(1)L＝55±5、a＝58±5和b＝40±5；
(2)L＝80±5、a＝-20±5和b＝40±5；或
(3)L＝85±5、a＝5±2和b＝85±5。
本发明也提供上述着色剂的制备方法，包括如下步骤：将稀土化合物、硫源、含磷化合物和碱金属化合物混合得到混合物，将该混合 物在700～1500℃下反应，得到所述着色剂；其中，所述的含磷化合物选自碱金属磷酸盐、碱金属磷酸氢盐、碱金属磷酸二氢盐、碱土金属磷酸盐、稀土金属磷酸盐、过渡金属磷酸盐、磷酸铵盐、磷酸氢铵盐、磷酸二氢铵盐、磷酸铝盐、磷酸硼、五氧化二磷盐中的一种或多种；所述的制备方法不包括氟洗处理工序。
根据本发明的制备方法，优选地，所述稀土化合物选自稀土金属碳酸盐、稀土金属氧化物、稀土金属草酸盐、稀土金属硫酸盐、稀土金属硝酸盐中的一种或多种；所述硫源选自硫磺、硫化物或硫酸盐的一种或多种；所述碱金属化合物选自碱金属元素的碳酸盐、氧化物、氢氧化物中的一种或多种。
根据本发明的制备方法，优选地，所述碱金属化合物中的碱金属元素与所述稀土化合物中的稀土元素的摩尔比为0.06～0.30:1；所述碱金属化合物中的碱金属元素与所述硫源中的硫元素的摩尔比为0.02～0.1:1；所述碱金属化合物中的碱金属元素与所述含磷化合物中的磷元素的摩尔比为0.1～0.4:1。
根据本发明的制备方法，优选地，所述稀土化合物中的稀土元素与所述硫源中的硫元素的摩尔比为1:1.5～4，所述硫源中的硫元素与所述含磷化合物中的磷元素的摩尔比为0.9～16:1。
根据本发明的制备方法，优选地，将该混合物在以下气氛中反应得到所述着色剂：氢气、硫化氢、二硫化碳、一氧化碳、氮气或空气。
本发明将含磷化合物加入稀土硫化物着色剂的制备过程，从而提高了着色剂的鲜艳度，因而不需要氟洗处理工序即可获得鲜艳度较高的着色剂。此外，本发明的制备方法可以降低生产成本，省略污水处理环节，并提高生产效率。
附图说明
图1为实施例5的XRD衍射图。
图2为实施例12的XRD衍射图。
具体实施方式
下面结合具体实施例对本发明作进一步的说明，但本发明的保护范围并不限于此。Lab颜色空间被设计用来接近人类视觉。本发明的色彩空间也称之为颜色空间、色度坐标。在Lab色彩空间中，L表示亮度，a和b表示颜色对立的维度。L值为0时，色彩为黑色，L值接近100时为白色；a值表示色彩在红色和绿色之间的位置；b值表示色彩在蓝色和黄色之间的位置。
<用途>
本发明提供一种含磷化合物的用途，其用于提高稀土硫化物着色剂的鲜艳度。在本发明中，所述的含磷化合物选自碱金属磷酸盐、碱金属磷酸氢盐、碱金属磷酸二氢盐、碱土金属磷酸盐、稀土金属磷酸盐、过渡金属磷酸盐、磷酸铵盐、磷酸氢铵盐、磷酸二氢铵盐、磷酸铝盐、磷酸硼盐、五氧化二磷中的一种或多种。作为优选，所述的含磷化合物选自碱金属磷酸盐、碱金属磷酸氢盐、碱金属磷酸二氢盐、磷酸铵盐、磷酸氢铵盐、磷酸二氢铵盐或磷酸铝盐。作为更优选，所述的含磷化合物选自碱金属磷酸盐、碱金属磷酸氢盐、碱金属磷酸二氢盐、磷酸铵盐、磷酸氢铵盐、磷酸二氢铵盐。最优选地，所述的含磷化合物选自碱金属磷酸盐或磷酸铵盐。本发明的含磷化合物的实例包括但不限于磷酸铵、磷酸氢铵、磷酸二氢铵、磷酸钠、磷酸氢钠、磷酸二氢钠、磷酸钾、磷酸氢钾、磷酸二氢钾、磷酸铝、磷酸锌等。 作为优选，本发明的含磷化合物为磷酸铵、磷酸氢铵、磷酸二氢铵、磷酸铝或磷酸锌。
在本发明中，所述稀土硫化物着色剂具有如下化学式：
RE2-2xS3-3x·2y[REPO4]
其中，RE选自La、Ce、Pr、Nd、Sm的一种或多种，y与x的比例为0.001～0.65。
在本发明中，RE优选为La、Ce、Pr或Nd，更优选为Ce。在本发明中，优选地，y与x的比例为0.01～0.55。所述稀土硫化物着色剂的实例包括但不限于Ce2-2xS3-3x·2y[CePO4]、La2-2xS3-3x·2y[LaPO4]、Pr2-2xS3-3x·2y[PrPO4]、Nd2-2xS3-3x·2y[NdPO4]、Sm2-2xS3-3x·2y[SmPO4]。其中，y与x的比例为0.001～0.65；优选地，0.01～0.55。
<着色剂>
本发明的着色剂为稀土硫化物，并具有如下化学式：
RE2-2xS3-3x·2y[REPO4]
其中，RE选自La、Ce、Pr、Nd、Sm的一种或多种，y与x的比例为0.001～0.65。
在本发明中，RE优选为La、Ce、Pr、Nd或Sm，更优选为Ce。在本发明中，优选地，y与x的比例为0.01～0.55。
在本发明中，稀土硫化物着色剂可以包括Ce2-2xS3-3x·2y[CePO4]、La2-2xS3-3x·2y[LaPO4]、Pr2-2xS3-3x·2y[PrPO4]、Nd2-2xS3-3x·2y[NdPO4]或Sm2-2xS3-3x·2y[SmPO4]。其中，y与x的比例为0.001～0.65；优选地，0.01～0.55。
本发明的着色剂可以为不同颜色，例如红色、绿色或黄色，根据稀土元素RE而定。例如，Ce2-2xS3-3x·2y[CePO4]显示红色。为了获得更好的鲜艳度，本发明的着色剂的色度坐标可以为：
(1)L＝55±5、a＝58±5和b＝40±5；
(2)L＝80±5、a＝-20±5和b＝40±5；或
(3)L＝85±5、a＝5±2和b＝85±5。
作为优选，本发明的着色剂的色度坐标为：
(1)L＝55±3、a＝58±3和b＝40±3；
(2)L＝80±3、a＝-20±3和b＝40±3；或
(3)L＝85±3、a＝5±1和b＝85±3。
作为更优选，本发明的着色剂的色度坐标为：
(1)L＝55±1、a＝58±1和b＝40±1；
(2)L＝80±1、a＝-20±1和b＝40±1；或
(3)L＝85±1、a＝5±0.5和b＝85±1。
<着色剂的制备方法>
本发明的着色剂的制备方法包括如下步骤：将稀土化合物、硫源、含磷化合物和碱金属化合物混合得到混合物，将该混合物在700～1500℃下反应，得到所述着色剂。上述制备方法不包括氟洗处理工序，因而可以节约生产成本，减少工业废液、缩短工艺流程。混合的顺序并没有特别限定。例如，将稀土化合物、硫源和含磷化合物混合均匀，然后加入碱金属化合物作为助熔剂，混合均匀得到混合物。又如，将稀土化合物、硫源、含磷化合物和碱金属化合物一起混合均匀得到混合物。
在本发明的制备方法中，所述的含磷化合物选自碱金属磷酸盐、碱金属磷酸氢盐、碱金属磷酸二氢盐、碱土金属磷酸盐、稀土金属磷酸盐、过渡金属磷酸盐、磷酸铵盐、磷酸氢铵盐、磷酸二氢铵盐、磷酸铝盐、磷酸硼盐、五氧化二磷中的一种或多种。作为优选，所述的含磷化合物选自碱金属磷酸盐、碱金属磷酸氢盐、碱金属磷酸二氢盐、 磷酸铵盐、磷酸氢铵盐、磷酸二氢铵盐或磷酸铝盐。作为更优选，所述的含磷化合物选自碱金属磷酸盐、碱金属磷酸氢盐、碱金属磷酸二氢盐、磷酸铵盐、磷酸氢铵盐、磷酸二氢铵盐。最优选地，所述的含磷化合物选自碱金属磷酸盐或磷酸铵盐。本发明的含磷化合物的实例包括但不限于磷酸铵、磷酸氢铵、磷酸二氢铵、磷酸钠、磷酸氢钠、磷酸二氢钠、磷酸钾、磷酸氢钾、磷酸二氢钾、磷酸铝、磷酸锌等。作为优选，本发明的含磷化合物为磷酸铵、磷酸氢铵、磷酸二氢铵、磷酸铝或磷酸锌。
在本发明的制备方法中，所述稀土化合物可以选自稀土金属碳酸盐、稀土金属氧化物、稀土金属草酸盐、稀土金属硫酸盐、稀土金属硝酸盐中的一种或多种；优选为稀土金属碳酸盐、稀土金属氧化物或稀土金属草酸盐；更优选为稀土金属碳酸盐或稀土金属氧化物。根据本发明的一个实施方式，所述稀土化合物为含铈化合物，其选自碳酸铈、氧化铈、草酸铈、硫酸铈、硝酸铈中的一种或多种；优选为氧化铈、碳酸铈或草酸铈；更优选为氧化铈或碳酸铈。
在本发明的制备方法中，所述硫源可以选自硫磺、硫化物或硫酸盐的一种或多种；优选为硫磺和硫化物；更优选为硫磺。
在本发明的制备方法中，所述碱金属化合物可以选自碱金属元素的碳酸盐、氧化物、氢氧化物中的一种或多种。所述碱金属可以为锂、钠或钾。所述碱金属化合物优选为碳酸盐；具体的实例包括碳酸钠或碳酸钾，优选为碳酸钠。
在本发明的制备方法中，所述碱金属化合物中的碱金属元素与所述稀土化合物中的稀土元素的摩尔比为可以为0.06～0.30:1；优选为0.08～0.25:1，更优选为0.1～0.2:1。将碱金属元素与稀土元素的摩尔比控制在上述范围，有利于改善鲜艳度。
在本发明的制备方法中，所述碱金属化合物中的碱金属元素与所述硫源中的硫元素的摩尔比可以为0.02～0.1:1；优选为0.035～0.1:1，更优选为0.04～0.08:1。将碱金属元素与硫元素的摩尔比控制在上述范围，有利于改善鲜艳度。
在本发明的制备方法中，所述碱金属化合物中的碱金属元素与所述含磷化合物中的磷元素的摩尔比可以为0.1～0.4:1；优选为0.2～0.4:1，更优选为0.3～0.4:1。将碱金属元素与磷元素的摩尔比控制在上述范围，有利于改善鲜艳度。
在本发明的制备方法中，所述稀土化合物中的稀土元素与所述硫源中的硫元素的摩尔比可以为1:1.5～4；优选为1:2.0～3.9。将稀土元素与硫元素的摩尔比控制在上述范围，有利于改善鲜艳度。
在本发明的制备方法中，所述硫源中的硫元素与所述含磷化合物中的磷元素的摩尔比为0.9～16:1；优选为3～13:1；更优选为5～10:1。将硫元素与磷元素的摩尔比控制在上述范围，有利于改善鲜艳度。
将稀土化合物、硫源、含磷化合物和碱金属化合物混合得到的混合物置于反应容器进行高温固相反应。反应容器的材质可以为金属、陶瓷、刚玉、石英等耐高温材料。本发明可以采用石墨舟、石英管、坩埚等容器进行高温固相反应。
在本发明的制备方法中，将该混合物在如下气氛中反应得到所述着色剂：氢气、硫化氢、二硫化碳、一氧化碳、氮气或空气。所述气氛优选为硫化氢、二硫化碳、一氧化碳和氢气。本发明的反应温度可以为700～1500℃，优选为900～1300℃，更优选为1000～1200℃。这样有利于获得鲜艳度更好的着色剂。
以下实施例和对比例的测试方法说明如下：
Lab值采用利用柯尼卡美能达公司的CM-5分光测色计进行测试。
XRD采用德国布鲁克公司D8Advance X射线衍射仪进行测试。
实施例1
将0.75摩尔升华硫，0.15摩尔碳酸铈，0.0095摩尔无水碳酸钠和0.063摩尔磷酸铵混合，在1000℃反应3小时。将所述反应产物研磨、水洗、烘干，得到着色剂Ce0.3S0.45·0.063[CePO4]。色度坐标为(L*＝55，a*＝58，b*＝40)。
实施例2
将0.5摩尔升华硫，0.15摩尔氧化铈，0.01125摩尔无水碳酸钠和0.0675摩尔磷酸二氢铵混合，在1000℃反应3小时。将所述反应产物研磨、水洗、烘干，得到着色剂Ce0.3S0.45·0.0675[CePO4]。色度坐标为(L*＝55，a*＝58，b*＝40)。
实施例3
将0.75摩尔升华硫，0.125摩尔草酸铈，0.01625摩尔无水碳酸钠和0.088摩尔磷酸氢二铵混合，在800℃反应3小时。将所述反应产物研磨、水洗、烘干，得到着色剂Ce0.25S0.375·0.088[CePO4]。色度坐标为(L*＝55，a*＝58，b*＝40)。
实施例4
将0.5摩尔升华硫，0.075摩尔碳酸铈，0.0135摩尔无水碳酸钠和0.083摩尔磷酸锌混合，在900℃反应3小时。将所述反应产物研磨、水洗、烘干，得到着色剂Ce0.15S0.225·0.083[CePO4]。色度坐标为 (L*＝55，a*＝58，b*＝40)。
实施例5
将0.75摩尔升华硫，0.125摩尔碳酸铈，0.02摩尔无水碳酸钠和0.1摩尔磷酸铝混合，在1000℃反应3小时。将所述反应产物研磨、水洗、烘干，得到着色剂Ce0.25S0.375·0.1[CePO4]。色度坐标为(L*＝55，a*＝58，b*＝40)。
实施例6
将0.5摩尔升华硫，0.085摩尔碳酸铈，0.01摩尔无水碳酸钠和0.054摩尔磷酸铝混合，在1000℃反应3小时。将所述反应产物研磨、水洗、烘干，得到着色剂Ce0.17S0.255·0.054[CePO4]。色度坐标为(L*＝55，a*＝58，b*＝40)。
实施例7
将0.75摩尔升华硫，0.13摩尔碳酸铈，0.015摩尔无水碳酸钠和0.075摩尔磷酸铝混合，在1000℃反应3小时。将所述反应产物研磨、水洗、烘干，得到着色剂Ce0.26S0.39·0.075[CePO4]。色度坐标为(L*＝55，a*＝58，b*＝40)。
实施例8
将0.75摩尔升华硫，0.15摩尔碳酸镧，0.0095摩尔无水碳酸钠和0.063摩尔磷酸铵混合，在1000℃反应3小时。将所述反应产物研磨、水洗、烘干，得到着色剂La0.3S0.45·0.063[LaPO4]。色度坐标为(L*＝80，a*＝-20，b*＝40)。
实施例9
将0.5摩尔升华硫，0.15摩尔氧化镧，0.01125摩尔无水碳酸钠和0.0675摩尔磷酸二氢铵混合，在1000℃反应3小时。将所述反应产物研磨、水洗、烘干，得到着色剂La0.3S0.45·0.0675[LaPO4]。着色剂的色度坐标为(L*＝80，a*＝-20，b*＝40)。
实施例10
将0.75摩尔升华硫，0.125摩尔草酸镧，0.01625摩尔无水碳酸钠和0.088摩尔磷酸氢二铵混合，在800℃反应3小时。将所述反应产物研磨、水洗、烘干，得到着色剂La0.25S0.375·0.088[LaPO4]。色度坐标为(L*＝80，a*＝-20，b*＝40)。
实施例11
将0.5摩尔升华硫，0.075摩尔碳酸镧，0.0135摩尔无水碳酸钠和0.083摩尔磷酸锌混合，在900℃反应3小时。将所述反应产物研磨、水洗、烘干，得到着色剂La0.15S0.225·0.083[LaPO4]。色度坐标为(L*＝80，a*＝-20，b*＝40)。
实施例12
将0.75摩尔升华硫，0.125摩尔碳酸镧，0.02摩尔无水碳酸钠和0.1摩尔磷酸铝混合，在1000℃反应3小时。将所述反应产物研磨、水洗、烘干，得到着色剂La0.25S0.375·0.1[LaPO4]。色度坐标为(L*＝80，a*＝-20，b*＝40)。
实施例13
将0.5摩尔升华硫，0.085摩尔碳酸镧，0.01摩尔无水碳酸钠和 0.054摩尔磷酸铝混合，在1000℃，反应3小时。将所述反应产物研磨、水洗、烘干，得到着色剂La0.17S0.255·0.054[LaPO4]。色度坐标为(L*＝80，a*＝-20，b*＝40)。
实施例14
将0.75摩尔升华硫，0.13摩尔碳酸镧，0.015摩尔无水碳酸钠和0.075摩尔磷酸铝混合，在1000℃反应3小时。将所述反应产物研磨、水洗、烘干，得到着色剂La0.26S0.39·0.075[LaPO4]。色度坐标为(L*＝80，a*＝-20，b*＝40)。
实施例15
将0.75摩尔升华硫，0.15摩尔碳酸钐，0.0095摩尔无水碳酸钠和0.063摩尔磷酸铵混合，在1000℃反应3小时。将所述反应产物研磨、水洗、烘干，得到着色剂Sm0.3S0.45·0.063[Sm PO4]。色度坐标为(L*＝85，a*＝5，b*＝85)。
实施例16
将0.5摩尔升华硫，0.15摩尔氧化钐，0.01125摩尔无水碳酸钠和0.0675摩尔磷酸二氢铵混合，在1000℃反应3小时。将所述反应产物研磨、水洗、烘干，得到着色剂Sm0.3S0.45·0.0675[SmPO4]。色度坐标为(L*＝85，a*＝5，b*＝85)。
实施例17
将0.75摩尔升华硫，0.125摩尔草酸钐，0.01625摩尔无水碳酸钠和0.088摩尔磷酸氢二铵混合，在800℃反应3小时。将所述反应产物研磨、水洗、烘干，得到着色剂Sm0.25S0.375·0.088[SmPO4]。色度坐 标为(L*＝85，a*＝5，b*＝85)。
实施例18
将0.5摩尔升华硫，0.075摩尔碳酸钐，0.0135摩尔无水碳酸钠和0.083摩尔磷酸锌混合，在900℃反应3小时。将所述反应产物研磨、水洗、烘干，得到着色剂Sm0.15S0.225·0.083[SmPO4]。色度坐标为(L*＝85，a*＝5，b*＝85)。
实施例19
将0.75摩尔升华硫，0.125摩尔碳酸钐，0.02摩尔无水碳酸钠和0.1摩尔磷酸铝混合，在1000℃反应3小时。将所述反应产物研磨、水洗、烘干，得到着色剂Sm0.25S0.375·0.1[SmPO4]。色度坐标为(L*＝85，a*＝5，b*＝85)。
实施例20
将0.75摩尔升华硫，0.13摩尔碳酸钐，0.015摩尔无水碳酸钠，0.075摩尔磷酸铝混合，在1000℃反应3小时。将所述反应产物研磨、水洗、烘干，得到着色剂Sm0.26S0.39·0.075[SmPO4]。色度坐标为(L*＝85，a*＝5，b*＝85)。
实施例21
将0.5摩尔升华硫，0.085摩尔碳酸钐，0.01摩尔无水碳酸钠，0.054摩尔磷酸铝混合，在1000℃反应3小时。将所述反应产物研磨、水洗、烘干，得到着色剂Sm0.17S0.255·0.054[SmPO4]。色度坐标为(L*＝85，a*＝5，b*＝85)。
实施例22
将0.75摩尔升华硫，0.13摩尔碳酸铈，0.015摩尔无水碳酸钠，0.0375摩尔五氧化二磷混合，在1000℃反应3小时。将所述反应产物研磨、水洗、烘干，得到着色剂Ce0.26S0.39·0.075[CePO4]。色度坐标为(L*＝55，a*＝58，b*＝40)。
比较例1
将0.75摩尔升华硫，0.15摩尔碳酸铈和0.0095摩尔无水碳酸钠混合，在1000℃反应3小时。将所述反应产物研磨、水洗、烘干，得到着色剂Ce2S3。色度坐标为(L*＝49，a*＝50，b*＝44)。
本发明并不限于上述实施方式，在不背离本发明的实质内容的情况下，本领域技术人员可以想到的任何变形、改进、替换均落入本发明的范围。

Claims (10)

  1. 一种含磷化合物用于提高稀土硫化物着色剂的鲜艳度的用途，其特征在于，所述的含磷化合物选自碱金属磷酸盐、碱金属磷酸氢盐、碱金属磷酸二氢盐、碱土金属磷酸盐、稀土金属磷酸盐、过渡金属磷酸盐、磷酸铵盐、磷酸氢铵盐、磷酸二氢铵盐、磷酸铝盐、磷酸硼盐、五氧化二磷中的一种或多种。
  2. 根据权利要求1所述的用途，所述稀土硫化物着色剂具有如下化学式：
    RE2-2xS3-3x·2y[REPO4]
    其中，RE选自La、Ce、Pr、Nd、Sm的一种或多种，y与x的比例为0.001～0.65。
  3. 一种稀土硫化物着色剂，其特征在于，所述稀土硫化物着色剂具有如下化学式：
    RE2-2xS3-3x·2y[REPO4]
    其中，RE选自La、Ce、Pr、Nd、Sm的一种或多种，y与x的比例为0.001～0.65。
  4. 根据权利要求3所述的着色剂，其特征在于，RE为La、Ce、Pr或Nd，y与x的比例为0.01～0.55。
  5. 根据权利要求3所述的着色剂，其特征在于，所述着色剂的色度坐标为：
    (1)L＝55±5、a＝58±5和b＝40±5；
    (2)L＝80±5、a＝-20±5和b＝40±5；或
    (3)L＝85±5、a＝5±2和b＝85±5。
  6. 根据权利要求3～5任一项所述的着色剂的制备方法，其特征在于，包括如下步骤：将稀土化合物、硫源、含磷化合物和碱金属化合物混合得到混合物，将该混合物在700～1500℃下反应，得到所述 着色剂；其中，所述的含磷化合物选自碱金属磷酸盐、碱金属磷酸氢盐、碱金属磷酸二氢盐、碱土金属磷酸盐、稀土金属磷酸盐、过渡金属磷酸盐、磷酸铵盐、磷酸氢铵盐、磷酸二氢铵盐、磷酸铝盐、磷酸硼盐、五氧化二磷中的一种或多种；并且所述的制备方法不包括氟洗处理工序。
  7. 根据权利要求6所述的制备方法，其特征在于，所述稀土化合物选自稀土金属碳酸盐、稀土金属氧化物、稀土金属草酸盐、稀土金属硫酸盐、稀土金属硝酸盐中的一种或多种；所述硫源选自硫磺、硫化物或硫酸盐的一种或多种；所述碱金属化合物选自碱金属元素的碳酸盐、氧化物、氢氧化物中的一种或多种。
  8. 根据权利要求6所述的制备方法，其特征在于，所述碱金属化合物中的碱金属元素与所述稀土化合物中的稀土元素的摩尔比为0.06～0.30:1；所述碱金属化合物中的碱金属元素与所述硫源中的硫元素的摩尔比为0.02～0.1:1；所述碱金属化合物中的碱金属元素与所述含磷化合物中的磷元素的摩尔比为0.1～0.4:1。
  9. 根据权利要求6所述的制备方法，其特征在于，所述稀土化合物中的稀土元素与所述硫源中的硫元素的摩尔比为1:1.5～4，所述硫源中的硫元素与所述含磷化合物中的磷元素的摩尔比为0.9～16:1。
  10. 根据权利要求6所述的制备方法，其特征在于，将该混合物在以下气氛中反应得到所述着色剂：氢气、硫化氢、二硫化碳、一氧化碳、氮气或空气。
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