EP4299827A1 - Composé particulaire et procédé de formation d'un composé particulaire - Google Patents

Composé particulaire et procédé de formation d'un composé particulaire Download PDF

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Publication number
EP4299827A1
EP4299827A1 EP22382613.2A EP22382613A EP4299827A1 EP 4299827 A1 EP4299827 A1 EP 4299827A1 EP 22382613 A EP22382613 A EP 22382613A EP 4299827 A1 EP4299827 A1 EP 4299827A1
Authority
EP
European Patent Office
Prior art keywords
sepiolite
compound
particles
inorganic pigment
pigment
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP22382613.2A
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German (de)
English (en)
Inventor
Manel SUBIRATS COSTA
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Horizon Research Lab SL
Original Assignee
Horizon Research Lab SL
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Horizon Research Lab SL filed Critical Horizon Research Lab SL
Priority to EP22382613.2A priority Critical patent/EP4299827A1/fr
Priority to PCT/IB2023/056608 priority patent/WO2024003726A1/fr
Publication of EP4299827A1 publication Critical patent/EP4299827A1/fr
Pending legal-status Critical Current

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
    • D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/0076—Dyeing with mineral dye
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/673—Inorganic compounds
    • D06P1/67383—Inorganic compounds containing silicon
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/58—Material containing hydroxyl groups
    • D06P3/60—Natural or regenerated cellulose

Definitions

  • the present disclosure concerns a compound, particularly a particulate compound which is suitable for coloring substrates, preferably substrates comprising cellulose fibers.
  • a preferred application of the compound is dyeing textiles.
  • the present disclosure concerns a solution or dispersion comprising said compound, and methods for manufacturing, i.e. preparing, said compound, solution or dispersion.
  • the present disclosure concerns the use of said compound or solution or dispersion for coloring substrates, and particularly concerns a method for dyeing textiles using said compound.
  • the present disclosure concerns a textile dyed using said method for dying textiles.
  • the present invention provides a compound which comprises components which can be found in nature.
  • the compound can be made and used with methods which are not complex nor difficult to implement.
  • the use of the compound for dyeing textiles does not require the consumption of large quantities of water, and hence the present invention is particularly useful and beneficial to the textile industry which always requires improvements aimed at being environmentally friendly and safe to the industry's workers, to the users of textiles, and to the society as a whole.
  • a first aspect of the present invention concerns a particulate compound, the compound comprising sepiolite and an inorganic pigment.
  • Sepiolite is a natural clay.
  • the inorganic pigment is or comprises a mineral.
  • the compound according to the first aspect of the invention is particulate i.e. the compound comprises or consists of particles. Said particles, may comprise particles of sepiolite and/or the (inorganic) pigment, but preferably at least some, or more preferably all, of the compound's particles comprise both sepiolite and pigment, and most preferably in the particles which comprise both sepiolite and pigment, at least some of the pigment is bonded to the sepiolite.
  • said compound may comprise, or may be described as. a sepiolite-pigment complex.
  • a sepiolite-pigment complex preferably at least some, and more preferably all, of the inorganic pigment is bonded to the sepiolite.
  • the sepiolite's structure may provide for channels in which the pigment can diffuse and attach to the sepiolite.
  • the pigment may attach on the surface of the sepiolite.
  • at least some, and preferably all, of the inorganic pigment may be on a surface or inside channels of the sepiolite.
  • the particles of the compound if the latter is dispersed or dissolved in a liquid may change in size and/or shape.
  • the particulate nature of the compound renders the latter suitable for being processed in the form of aqueous solutions or dispersion, for use for the coloring substrates, particularly textiles.
  • the compound works exceptionally well for coloring or dyeing substrates.
  • the sepiolite may act as a carrier of the pigment for the delivery of the latter to a substrate that may require coloring or dyeing.
  • the compound is particularly effective for high quality coloring or dyeing of substrates which comprise cellulose fibers, e.g. textiles comprising cotton.
  • the sepiolite may have a particularly affinity and attach to cellulose fibers for delivering the pigment at said fibers.
  • the compound consists of the sepiolite and the inorganic pigment. Hence, the use of artificial and/or toxic chemicals may be avoided, to the benefit of the environment.
  • a concentration of the inorganic pigment in the compound is of between 10% and 90% by weight, and preferably is of between 30% and 70%, and more preferably is of between 40% and 60%, and most preferably is about 50%.
  • the concentration of the pigment may be varied according to the aforementioned values and value ranges, so that advantageously the color of the pigment is controlled, for thereby controlling the change in the color that may be imparted on a substrate treated with the compound.
  • the pigment concentration may be controlled for optimizing the morphology and homogeneity of the particulate compound. If the pigment concentration is very small, e.g. is less that 10%, the compound may not be capable for efficiently coloring a substrate, and if the pigment concentration is very high, e.g. is more than 90%, then a substrate colored with the compound may be uneven.
  • a compound with 50% (by weight) pigment has been found to advantageously be homogeneous and particularly easy to use for dyeing textiles which comprise cotton.
  • the compound comprises particles of a size of less than 15 ⁇ m.
  • Said particles may be particles of sepiolite, pigment and/or a mixture (or complex) of sepiolite and pigment. Having particles of sizes less than 15 ⁇ m aids towards the compound being homogenous and processable in solution, e.g. for the compound being suitable for being adequately dissolved or dispersed in water.
  • Said "size” may preferably be understood as a diameter of the particle. In particular, the size may be the size, e.g.
  • the compound comprises particles of a size of between 100 nm and 15 ⁇ m or of between 100 nm and 1 ⁇ m.
  • said inorganic pigment comprises an iron oxide, a transition metal oxide, a spinel, a silicate or a mixture thereof.
  • These are minerals found in nature, and of sufficient natural abundance.
  • the aforementioned types of minerals, as well as others, may provide colors which are highly desired for coloring substrates of interest, particularly for dyeing textiles.
  • the compound is for coloring a substrate, particularly for dyeing textiles.
  • another aspect of the present invention concerns a solution or dispersion, comprising a particulate compound which is according to any of the previous claims.
  • said solution or dispersion is aqueous, meaning that the particulate compound is dissolved or dispersed in water.
  • Another aspect of the invention concerns a method for forming a particulate compound, the method comprising: mixing particles of sepiolite with particles of an inorganic pigment, thereby forming a particulate mixture, wherein the inorganic pigment is or comprises a mineral; and heating under vacuum the particulate mixture at a temperature of up to about 300°C. Said heating can provoke the breaking of the particles into smaller ones, and can provoke or accelerate the formation of bonds between the inorganic pigment and the sepiolite, as well as provoke or accelerate the possible diffusion of the pigment in channels of the sepiolite. It is noted that at temperatures higher than 300°C there may occur reactions which may be detrimental to the (intended) color or structure of the compound.
  • a contemplated effect of the heating is also the potential formation of sepiolite-pigment complexes which may have distinct morphology (e.g. particles size and/or shape) and solubility properties (e.g. solubility or dispersibility in water) compared to particles which have not being heated.
  • an effect of said heating is the formation of a compound with advantageously good morphological and physicochemical properties for the applications intended, and especially for coloring textiles.
  • the vacuum used during heating the particulate mixture aids towards dehydrating the sepiolite and/or the pigment. Said vacuum may advantageously also prevent the bonding of the sepiolite with other materials such as for example compounds being present in the air and containing hydrogen, nitrogen, oxygen or carbon. It is estimated that the removal of water molecules from the sepiolite surface, and particularly from the channels in the sepiolite structure, advantageously promotes the mixing and possible reaction of the pigment with the sepiolite.
  • the method before mixing the particles of the sepiolite with the particles of the inorganic pigment, the method further comprises drying the particles of the sepiolite. More preferably said drying is done by heating under vacuum the particles of the sepiolite at a temperature of about 130°C for 30 minutes.
  • Preferred embodiments of said method also comprise micronizing the sepiolite and/or the inorganic pigment for forming, respectively, said particles of the sepiolite and said particles of the inorganic pigment, preferably the micronizing done using a micronized mill.
  • at least some, preferably most or all, of the particles of the sepiolite and/or the particles of the inorganic pigment have a size of 10 ⁇ m or less. It has been observed that sepiolite and pigment particles of size of 10 ⁇ m or less, advantageously mix well and result to the formation of a particulate compound with good homogeneity and solubility or dispersibility in water. The use of a commercially available industrial scale micronizer mill has been found to particularly be suitable for obtaining the aforementioned advantageous particles sizes, at industrially relevant quantities.
  • the steps of mixing and heating are done in a reactor which comprises a mixer and a vessel in which said mixing and heating takes place, and wherein: the particles of the sepiolite and the particles of the inorganic pigment are loaded in the vessel by suction (i.e. the force of vacuum); in said vessel the sepiolite and the inorganic pigment are mixed by means of the mixer; and said vessel is heated, thereby gradually heating the particulate mixture at the temperature of up to about 300°C.
  • the mixture remains, i.e. is maintained, at said temperature for a period of about 30 minutes.
  • the proportion by weight between the inorganic pigment and the sepiolite in the particulate mixture is of between 10/90 and 90/10, preferably of between 30/70 and 70/30, more preferably of between 40/60 and 60/40, and most preferably is about 50/50.
  • Another aspect of the invention concerns a method for dyeing textiles, the method comprising: wetting a textile with an aqueous solution of a compound which comprises sepiolite and an inorganic pigment, and wherein said inorganic pigment is or comprises a mineral; the textile remaining wet (i.e. wet and dyed) for a period of time; washing the textile; and drying the textile.
  • the aforementioned method step of "the textile remaining wet for a period of time” can also be interpreted as meaning “permitting or allowing the textile to remain wet for a period of time”.
  • the step wherein the textile remains wet during said period of time may also be called “maturing" step.
  • the textile is a fabric and is processed using rollers.
  • Other known machinery systems or components may also be used for implementing the present invention's method for dyeing textiles.
  • the compound in the solution is particulate, because said compound may be dissolved sufficiently so that it is difficult or practically impossible to resolve any particles of said compound in the solution.
  • the compound when not dissolved, or when isolated/extracted from the solution may be particulate, when dissolved (i.e. in the solution) may not be particulate, or may comprise particles which are very small and difficult to measure/resolve.
  • the compound is also particulate in an aqueous solution or dispersion of said compound.
  • the step of wetting the textile with the aqueous solution comprises: spraying or showering the aqueous solution on the textile; and passing the wet textile between two or more cylinders which squeeze the fabric. Said spraying or showering can yield a uniform wetting of the textile and a uniform distribution of the compound on the textile.
  • the amount of aqueous solution that is applied on the textile e.g. by controlling said amount, as a function of a speed via which the textile moves in a processing line, the amounts of the compound and of the pigment deposited on the textile per unit surface or unit volume of the material, can be controlled.
  • the amounts of the compound and of the pigment deposited on the textile per unit surface or unit volume of the material may also be controlled by a pressure applied on the textile by the aforementioned optionally used two or more cylinders.
  • the solution used for wetting the compound is at a temperature below 50°C, and more preferably at a temperature of between 20°C and 50°C, most preferably of about 30°C.
  • the solution does not need to be heated because the compound may dissolve and dye effectively the textile, even when the solution used it is at or close to room temperature.
  • the textile after passing between the two or more cylinders has a wet pickup value of between 30% and 90%, preferably of between 50% and 70%, more preferably of between 60 and 70%.
  • a wet pickup value of 70% means that 70 kg of aqueous solution is retained (absorbed) by a textile which when it is dry (before absorbing the solution) weights 100 kg. It is contemplated that in many cases (but not all) when the pickup value is less than 30%, then the pigment molecules may not diffuse or migrate sufficiently into the textile, and hence the textile may not be dyed as desired.
  • the textile comprises cellulose fibers, and preferably comprises cotton.
  • the compound works very well on textiles, e.g. on fabrics, comprising or consisting of cotton.
  • the method further comprises: rolling the textile on a cylinder thereby forming a roll; and rotating said roll during the period of time at which the textile remains wet.
  • rotating said roll is done at a constant speed. An effect of rotating the roll in the previous two embodiments, is that gravity does not produce downward color migration.
  • the method further comprises wrapping the roll in a plastic or polymer film.
  • An advantageous effect of said wrapping is to prevent evaporation on the outer layers or on the sides of the fabric roll (cylinder) so that color migration is homogeneous and controlled during the said period of time which may also be called “maturing" time.
  • said period of time is more than 30 minutes, preferably is of between 30 minutes and 48 hours, more preferably is of between 1 hour and 24 hours, most preferably is about 24 hours. If the time is too short, e.g. less than 30 minutes, then disadvantageously there may not be formed sufficiently strong bonds between the pigment or the pigment-sepiolite compound and the textile. If the time is too long, e.g. more than 48 hours, then the overall process may disadvantageously be slow and costly. A maturing time of 24 hours has been found to work exceptionally well for dyeing textiles, particularly fabrics comprising or consisting of cotton.
  • the compound consists of particles of the sepiolite and the inorganic pigment.
  • the sepiolite and inorganic pigment form complexes.
  • Said complexes, and more generally the material that results from the possible bonding between the sepiolite and the pigment, may advantageously exhibit good solubility or dispersibility in water.
  • a concentration of the compound in the aqueous solution is of between 10 and 30 gr/L.
  • a concentration within the concentration range may advantageously contribute to the delivery of a sufficient amount of compound, and hence pigment, on the textile.
  • a quantity of the aqueous solution used for wetting the textile is of between 0.5 liters and 2 liters, preferably about 1 liter, for every kilogram of the textile.
  • drying the textile is done in at least one heat setting oven.
  • said drying is done in a plurality of sequentially arranged heat setting ovens through which the textile passes.
  • drying the textile particularly comprises: a first heating step which comprises heating the fabric at first temperature, and maintaining the fabric at said first temperature for a duration of time during which the fabric is not completely dry; and a second heating step which comprises heating the fabric at a second temperature which is higher than the first temperature, for completely drying the fabric.
  • a first heating step which comprises heating the fabric at first temperature, and maintaining the fabric at said first temperature for a duration of time during which the fabric is not completely dry
  • a second heating step which comprises heating the fabric at a second temperature which is higher than the first temperature, for completely drying the fabric.
  • Said “two sides effect” refers to the case where the two faces of the same fabric are left with a different intensity due to “vertical migration” across the fabric, from its underside to its top side (a migration of color through the "thickness" of the fabric, which could happen especially in cases where the fabric runs horizontally) during an unoptimized drying process.
  • drying the textile is done using an oven configured to heat the fabric under an atmosphere which is free of condensed vapor, and the oven is also configured to avoid the formation and falling on the textile of water droplets inside the oven, and more preferably the first heating step is done under an atmospheric humidity of about 10% and with the first temperature being about 55°C.
  • the method for drying textiles may further comprise additional textile processing or finishing steps. Therefore, in a preferred embodiment of the method, after drying the textile, the method further comprises softening the textile and drying it again.
  • Another aspect of the invention concerns a textile dyed using the invention's method for dyeing textiles.
  • Said textile preferably is a fabric.
  • a textile dyed according to the aforementioned textile dyeing method may comprise at least traces of sepiolite or of a sepiolite-pigment compound or complex.
  • a preferred embodiment of a particulate compound according to the invention comprises sepiolite and an inorganic pigment, wherein the inorganic pigment is or comprises a mineral.
  • a preferred embodiment of a method for forming a particulate compound according to an aspect of the invention comprises the steps of:
  • a particularly preferred embodiment of a method for forming a particulate compound according to an aspect of the invention comprises the steps of:
  • Step 101a may be a part of the aforementioned step 101. Also steps 102a and 102b may be a part of the aforementioned step 102. In alternative embodiment, the particles of sepiolite are first loaded in the reactor, and then step 100b is done.
  • the compound formation process may be aided by the breaking of certain covalent bonds inside (and around) the sepiolite, which may in turn promote the bonding of the pigment to the sepiolite.
  • the raw materials used for making the compound are micronized for reducing the particle diameter. Pulverizing solid raw materials to the nanometer level may be very expensive and slow. Because of this, a reasonable and practical option is aiming for obtaining particles the size of which is 10 microns ( ⁇ m) or smaller. With particles of such sizes, advantageously the efficiency of the compound formation process is good.
  • the sepiolite and the pigment are micronized to about 10 microns.
  • segmentation of pigment clusters may take place, which can promote the diffusion of pigment molecules or clusters within channels of the sepiolite.
  • the micronized product, before used, may be stored in a hopper.
  • the pigment and sepiolite particles used for making the compound were prepared using a micronizer which works at a rate of 30 kg/h and with a fineness of 10 ⁇ m.
  • Said micronizer is a grinding facility and classified with a high-performance filter type Jet for the control of emissions into the atmosphere.
  • the system used has a paddle classifier and a grinding plate with pins or hammers, both turning at different revolutions to obtain the desired granulometric curve.
  • the grinding chamber is protected with a liner that, due to its shape and arrangement, favors the grinding of the product.
  • the entire mill/motor assembly is mounted on a metal base.
  • the raw materials are mixed in a reactor at high temperature and under vacuum.
  • the reactor allows:
  • the sepiolite in the reactor before mixing the sepiolite with pigment, the sepiolite is pre-heated so that it is, at least partially, activated. Hence, in said non-limiting example, there following happens:
  • the reactor used in the above non-limiting example comprises a helical vertical mixer which has the following specifications:
  • a preferred embodiment of the method for dyeing textiles comprises the steps of:
  • there textile is a fabric, and there are the following features:
  • a textile dyed according to the aforementioned method of an aspect of the invention may comprise at least traces of the sepiolite and/or of the sepiolite-pigment compound used for the dyeing process. It is further contemplated that at least traces on the textile, may be detected by electron microscopy or a different experimental technique.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Coloring (AREA)
EP22382613.2A 2022-06-29 2022-06-29 Composé particulaire et procédé de formation d'un composé particulaire Pending EP4299827A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP22382613.2A EP4299827A1 (fr) 2022-06-29 2022-06-29 Composé particulaire et procédé de formation d'un composé particulaire
PCT/IB2023/056608 WO2024003726A1 (fr) 2022-06-29 2023-06-27 Composé particulaire et procédé de formation d'un composé particulaire

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP22382613.2A EP4299827A1 (fr) 2022-06-29 2022-06-29 Composé particulaire et procédé de formation d'un composé particulaire

Publications (1)

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EP4299827A1 true EP4299827A1 (fr) 2024-01-03

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EP22382613.2A Pending EP4299827A1 (fr) 2022-06-29 2022-06-29 Composé particulaire et procédé de formation d'un composé particulaire

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EP (1) EP4299827A1 (fr)
WO (1) WO2024003726A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080044582A1 (en) * 2006-08-17 2008-02-21 Yosuke Kitagawa Aqueous textile printing composition and continuous textile printing method of aqueous textile printing composition
US8123850B2 (en) * 2008-03-10 2012-02-28 Mayan Pigments, Inc. Environmentally-friendly near infrared reflecting hybrid pigments
CN105199435A (zh) * 2015-10-15 2015-12-30 中国科学院兰州化学物理研究所 一种钴蓝/黏土矿物杂化颜料的制备方法
CN106278031A (zh) * 2016-08-11 2017-01-04 北京南极海新材料股份有限公司 一种滚涂型硅藻泥环保内墙粉体材料及其制备方法
CN107083696A (zh) * 2017-06-13 2017-08-22 杭州牛墨科技有限公司 一种环保布艺染料及其制备方法

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Publication number Priority date Publication date Assignee Title
GB9400574D0 (en) * 1994-01-13 1994-03-09 Unilever Plc Synthetic zeolite pigments
JP4486206B2 (ja) * 2000-02-25 2010-06-23 レンゴー株式会社 触媒物質含有機能材およびその製造方法

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US20080044582A1 (en) * 2006-08-17 2008-02-21 Yosuke Kitagawa Aqueous textile printing composition and continuous textile printing method of aqueous textile printing composition
US8123850B2 (en) * 2008-03-10 2012-02-28 Mayan Pigments, Inc. Environmentally-friendly near infrared reflecting hybrid pigments
CN105199435A (zh) * 2015-10-15 2015-12-30 中国科学院兰州化学物理研究所 一种钴蓝/黏土矿物杂化颜料的制备方法
CN106278031A (zh) * 2016-08-11 2017-01-04 北京南极海新材料股份有限公司 一种滚涂型硅藻泥环保内墙粉体材料及其制备方法
CN107083696A (zh) * 2017-06-13 2017-08-22 杭州牛墨科技有限公司 一种环保布艺染料及其制备方法

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Title
CHEN HUIWEN ET AL: "A new method to prepare 'Maya red' pigment from sepiolite and Basic red 46", APPLIED CLAY SCIENCE, vol. 174, 27 March 2019 (2019-03-27), pages 38 - 46, XP085668006, ISSN: 0169-1317, DOI: 10.1016/J.CLAY.2019.03.023 *

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