• 专利附录
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    • 专利摘要:
    The present invention relates to a method for producing a bismuth-based pigment with improved resistance to alkaline conditions, the method comprising: i) obtaining a dried bismuth-based pigment; ii) encapsulation of the bismuth-based pigment by a chelating agent; iii) final processing of the encapsulated pigment; and v) drying the pigment. In addition, the present invention is directed to a bismuth-based pigment encapsulated by a low chelating agent.
    公开号:BE1025298B1
    申请号:E2017/5674
    申请日:2017-09-22
    公开日:2019-01-17
    发明作者:Zeki Acar；Vincent Devreux；Greta Verspaille；Jurgen D'haeveloose；Emmanuelle Clabaux
    申请人:Cappelle Pigments Nv；
    IPC主号:
    专利说明:

    CAPPELLE PIGMENTS nv, Kortrijkstraat 153, 8930 MENEN Belgium;
    represented by
    VAN DAELE Maarten, Mechelsesteenweg 32, bus 103, 2018, ANTWERP;
    a Belgian invention patent with a duration of 20 years granted, subject to payment of the annual fees as referred to in Article XI.48, § 1 of the Economic Law Code, for: Method of producing a bismuth-based pigment with an improved resistance to alkaline conditions.
    INVENTOR (S):
    ACAR Zeki, Kortrijkstraat 153, 8930, MENEN;
    DEVREUX Vincent, Kortrijkstraat 153, 8930, MENEN;
    VERSPAILLE Greta, Kortrijkstraat 153, 8930, MENEN;
    D'HAEVELOOSE Jurgen, Kortrijkstraat 153, 8930, MENEN;
    CLABAUX Emmanuelle, Kortrijkstraat 153, 8930, MENEN;
    PRIORITY :
    09/09/2016 EP 16190051.9;
    DIVISION:
    Split from basic application:
    Submission date of the basic application:
    Article 2. - This patent is granted without prior research into the patentability of the invention, without guarantee of the merit of the invention or of the accuracy of its description and at the risk of the applicant (s).
    Brussels, 17/01/2019,
    With special authorization:
    BE2017 / 5674
    Process for producing a bismuth-based pigment with improved resistance to alkaline conditions
    FIELD OF THE INVENTION
    The present invention relates to a method for producing bismuth-based pigments, and more specifically to a method for producing bismuth-based pigments with improved resistance to alkaline conditions. In addition, the invention relates to a bismuth-based pigment with improved resistance to alkaline conditions.
    BACKGROUND OF THE INVENTION
    Paint is any liquid, soluble, or mastic composition that, after being applied to a substrate in the form of a thin layer, is converted into a solid film. It is most commonly used for protecting, coloring and / or providing texture to objects. It mainly comprises pigments, binders and liquid. Pigments are finely ground particles or powders, dispersed in paints, which provide coloristic properties to the paint.
    Depending on the application area, in particular for façade applications that have been exposed
    BE2017 / 5674 in extreme weather conditions such as rain, sunlight, heat and cold, the pigment used in paint must be carefully selected and is extremely important. The paint, generally comprising a high pigment volume concentration, when applied to chemically active substrates, such as concrete, results in a porous paint film over the surface of the substrate. Due to such a porous nature of the paint film, oxygen and other gases from the air or soluble salts of concrete can penetrate through it, which, together with the UV radiation and moisture, leads to degradation of the pigments with premature degradation of the pigment result.
    In addition, the substrates cure after a period of time and produce hydrates such as calcium hydroxide which makes the environment alkaline, with a pH value generally of 12 to 13. Such an alkaline environment affects the pigments, especially organic pigments. Therefore, inorganic pigments are recommended for use in façade applications. However, most inorganic pigments contain a heavy metal such as cobalt or chromium.
    Today, due to environmental awareness, pigments become cadmium, lead and chromium
    BE2017 / 5674 contain more and more considered to be harmful from an ecological and toxicological point of view. Therefore, alternative pigments, generally without toxicological disadvantages, such as mainly bismuth-based pigments, were tested for their coloristic properties.
    These bismuth-based pigments offer, in addition to being non-toxic, not only the desired coloristic properties, but also very good resistance to weather parameters such as light and heat, together with resistance to most chemical substances. However, these bismuth-based pigments are particularly unstable in alkaline media with a pH in the range of about 8 to 13. Such poor resistance of the pigments can lead to partial or even complete discoloration of the pigment and therefore also of the coating. This poor resistance of the bismuth-based pigments to the alkaline media limits the purpose of their use in water-based paints or surface coatings such as silicate coatings and patches. Accordingly, there is a need for improved resistance to alkaline conditions of bismuth-based pigment so that it can be used in the paint industry.
    BE2017 / 5674
    There became already improve from the circumstances of the like them too baptize with c
    resistive agents such as great effort for the alkaline bismuth-based pigments, alkaline earth metal, zinc, aluminum or phosphate.
    US3946134 discloses a method for improving the chemical stability of an inorganic pigment based on solid particle substrate by encapsulating each particle with a continuous layer of aluminum phosphate complex.
    US5123965 relates to a process for stabilizing treatment with of BiVa pigment by said pigment a metal phosphate selected from the group consisting of calcium, magnesium, aluminum, zirconium and titanium orthophosphates.
    However, the method results in a change of the coloristic properties as well as the rheological properties in a water-based system by the phosphate derivatives, which is generally not preferred.
    method for improving properties such as color strength, color intensity as well as gloss of coloring obtained in a bismuth vanadate pigment by coating it with
    BE2017 / 5674 polyvinyl alcohol. However, the method does not provide resistance to alkaline conditions that is required
    are for it coating system with high pH for the architectural coatings. US6423131 a coating for the bismuth vanadate based on calcium fluoride,
    bismuth oxyfluoride or lantanide fluoride. Such a coating is intended to improve the chemical resistance properties of the bismuth vanadate. However, it does not increase its resistance properties in alkaline media to a desired level.
    Other references revealed different types of coatings for bismuth vanadate pigments to improve their properties. For example: US4063956, for example, discloses coating a bismuth vanadate pigment with a layer of metal oxide hydrate followed by a second dense layer of amorphous silicon dioxide.
    In another example it reveals
    US4115141 a method for stabilizing bismuth vanadate by coating it with silicon dioxide or aluminum phosphate. US4455174 describes first coating a bismuth vanadate pigment with zirconium dioxide and then with silicon dioxide. EP271813
    BE2017 / 5674 fluoride metal oxide coatings based on silicon dioxide, magnesium silicate and magnesium fluoride mixed with a wax layer.
    Although all of these disclosed methods provided higher chemical resistance along with other improvements in bismuth-based pigment properties, none of them was very effective in increasing the resistance of bismuth-based pigments in alkaline media to a desired level, more specifically in the highly alkaline architectural coatings.
    EP2584010 seeks to provide improved bismuth-based pigment coatings for the alkaline media describing a double-layer coating of the pigment based on silica and organo-functionalized silane. Despite a clear improvement, this method does not provide the necessary level of resistance to alkaline conditions as desired for highly alkaline architectural coatings.
    In some other recognized attempts, various pigments were mixed together with the bismuth vanadate in order to take advantage of the good coloristic properties of the bismuth vanadate pigments and the poor resistance to
    BE2017 / 5674 improve alkaline conditions through very strong pigments in alkaline media. Such an example is disclosed in WO2014055555, which discloses a dye comprising a mixture of pigments.
    The pigments have a similar coloration but a different resistance to corrosion.
    The mixing ratio is selected to optimize the corrosion resistance to color brightness and / or acid corrosion resistance to alkali corrosion resistance of the dye. However, this method is not preferred because it drastically reduces the coloristic properties of the bismuth vanadate pigment.
    Accordingly, there is a need in the art for a method for improving the chemical resistance properties, more specifically the resistance to alkaline media, of the bismuth-based conditions by the action of cations present in pigments while maintaining their excellent coloristic properties.
    Summary of the invention
    The present invention was made in view of the above problems and discloses a method for producing bismuth-based pigment with improved resistance to alkaline
    BE2017 / 5674 to block a coating formulation. The method comprises slurrying a dried pigment obtained from an in situ pigment synthesis process. The method further comprises introducing a chelating agent into the slurry of the pigment thereby encapsulating the bismuth-based pigment. The pigment is then dried and processed to obtain the bismuth-based pigment with desirable resistance properties to alkaline conditions.
    In general, the dried pigment is slurried again by adding an amount of solvent to the dried pigment in a predetermined temperature range and stirring the dispersion for a predetermined period of time.
    Re-slurrying is prepared by adding RO water and stirring in one
    temperature range between 35 ° C and 45 ° C during a period of time in the area from 5 0 minutes until 70 minutes.The method includes optional further it
    adding an antifoam additive and a silica derivative to improve the powder properties of the dried pigment, such as its
    BE2017 / 5674 possibility of free flowing, non-dusting behavior and non-stickiness during the drying process.
    The method may further include the addition of one or more organic compounds in the pigment slurry to obtain an organic layer around the pigment that limits the interaction of the pigment with the cations.
    The process may also include the addition of one or more inorganic compounds and / or a silane in the pigment slurry.
    In another aspect of the present
    invention is an alternative method for it produce of bismuth based pigment with a improved resistance to alkaline conditions revealed in which a pigment is made into a slurry
    by means of a solution based on chelating agent.
    In yet another aspect, the present invention discloses a method for producing bismuth-based pigment with improved resistance to alkaline conditions, wherein the chelating agent is prepared in situ via a polymerization reaction by means of sodium vinyl sulfonate, sodium styryl sulfonate and / or
    BE2017 / 5674 acrylic acid polymers, preferably in combination with non-ionic monomers such as typically epoxide, organized modified siloxane and ethylene glycol monomers.
    In yet another aspect, the present invention discloses a bismuth-based pigment with an improved resistance to alkaline conditions that offers vivid colors and a high color strength to complex inorganic colored pigments.
    The details of one or more embodiments are shown in the accompanying drawings and description below.
    Other aspects, features and advantages of the subject matter disclosed herein become apparent from the description, the drawings, and the claims.
    Brief description of the drawings
    Other objects, features and advantages of the invention become apparent from the following description when read with reference to the accompanying drawings. In the drawings, in which the same reference numbers indicate corresponding parts across the various displays:
    FIG. 1 is a flowchart illustrating a method for producing an op
    BE2017 / 5674 bismuth based pigment with improved resistance to alkaline conditions according to an embodiment of the present invention.
    FIG. 2 is a flow chart illustrating a method for producing a bismuth-based pigment with improved resistance to alkaline conditions according to another embodiment of the present invention.
    FIG. 3 is a flow chart illustrating a method for producing a bismuth-based pigment with improved resistance to alkaline conditions according to yet another
    embodiment of the present invention. FIG. 4 a table That alkaline stability of a pigment in 25% K 2 CO 3 after 24 hours displays immersion time. FIG. 5 a table That alkaline stability of a pigment in 10% NaOH after 24 hours displays immersion time. FIG. 6 a table That alkaline stability of a pigment in 10% KOH after 24 hours displays immersion time. FIG. 7 a table that one
    comparison between alkaline stability of
    BE2017 / 5674 a pigment in 25% K2CO3, a pigment in 10% NaOH and a pigment in 10% KOH after a 24-hour immersion time Detailed description of the preferred embodiments
    Reference is now made in detail to the preferred embodiment of the present invention, examples of which are illustrated in the accompanying drawings. Aspects, advantages, and / or other features of the exemplary embodiment of the disclosure become apparent in view of the following detailed description, which discloses various non-limiting embodiments of the invention. For the sake of clarity, specific terminology is used in the description of characterizing embodiments. However, the embodiments are not intended to be limited to this specific terminology.
    It must be stated that each specific part includes all technical equivalents that work in a similar way to a
    Available in similar objective.
    In the following detailed description, various specific details are included to provide a thorough understanding of the invention. However, it is obvious to anyone who is skilled in it
    BE2017 / 5674 that the invention can be practiced without these specific details. In other cases, methods, procedures and / or components were not described in detail in order not to obscure the invention.
    Bismuth-based pigments, such as bismuth vanadate used in resistance and based pigments, are becoming the coating industry and offer good coloristic properties. One major disadvantage of use, however, is their conditions, a low resistance to alkaline property of bismuth-based pigments required in certain water-based coating formulations such as silicate coatings. This limited resistance to alkaline conditions of these pigments leads to partial or even complete discoloration of the pigment and therefore also of the coating. This is because the chemical structure of Bi (bismuth) based pigments is changed when exposed to a highly alkaline environment due to the presence of a high concentration of ions such as Na +, K +, Ca + 2, Zn2 +, Ba2 + etc. the bismutiones are replaced in order to form other vanadate salts, which leads to the discoloration.
    BE2017 / 5674
    This limitation can be seen by performing alkaline resistance test of coated plates immersed in alkaline aqueous solutions (NaOH - KOH), leading to partial discoloration of the plates, and the more discoloration, the less resistant the pigment is against alkaline media. As a result, there is a need to improve the resistance to alkaline conditions of the pigment for architectural coatings.
    The present invention provides a method for producing bismuth-based pigment with improved resistance to alkaline conditions by in situ treating the resulting bismuth-based pigments with chelating agents such as EDTA (ethylenediamine tetraacetate), alkyl glycoside, polymers and / or copolymers that have a chelating effect due to the presence of carboxylic acid or sulphonic acid functions. These chelating agents block the action of the ions present in the coating formulation, thereby improving alkaline stability while preventing discoloration of Bi-based pigments. In addition, chelating agents that have been modified with organic
    BE2017 / 5674 groups in some embodiments of the present invention are used to form an organic layer around the pigment that prevents the interaction of the ions with the BiVa (bismuth vanadate) molecule and / or the crystal lattice of bismuth vanadate. In some embodiments, these chelating agents can be prepared in situ via a polymerization, typically by means of sodium vinyl sulfonate, sodium styryl sulfonate and / or acrylic acid polymers, preferably in combination with non-ionic monomers. The pigments produced by this method provide vivid colors and have a high color strength compared to complex inorganic colored pigments (CICP).
    The general process for the preparation of bismuth-based pigments is as follows:
    There turn into very pure solutions from commodities used from which it pigment is going to be knocked down, followed through heat treatment and
    stabilization.
    The pigment is then separated and purified.
    The purified product is dried and optionally calcined to obtain bismuth-based pigments.
    BE2017 / 5674
    Various embodiments of the invention describe the coating of these bismuth-based pigments with chelating agents.
    Embodiment 1:
    In an embodiment of the present invention, a method 100 is discussed as illustrated in FIG. 1 for coating the bismuth-based pigments with chelating agents. The method 100 begins at step 102 and proceeds to step 104, where a dried and optionally calcined bismuth based pigment is obtained from an in-situ pigment preparation process. In step 106 the dried pigment obtained is again slurried. The slurry of the pigment is prepared by adding an amount of solvent to the dried pigment in a predetermined temperature range and then stirring it to form a homogeneous aqueous dispersion. In one example, the re-slurry is prepared by adding water, preferably reverse osmosis water followed by stirring in a temperature range between 10 C and 100 C, preferably between 35 C and 45 C for a period of time in the range between 30 minutes and 120 minutes, preferably minutes to 70 minutes. In other examples it is possible
    BE2017 / 5674 pigment can be re-slurried in any solvent including, but not limited to, tap water, river water, reverse osmosis water, glycol-based esters, and the like. The method 100 then proceeds to step 108, where the bismuth-based pigment is encapsulated by the addition of a chelating agent in the slurry obtained in step 106. The encapsulation step is generally responsible for improving the resistance to alkaline conditions of the pigment. Once the pigment is encapsulated, the process 100 proceeds to step 110 where the encapsulated pigment is again separated and purified for its final processing followed by drying and packaging of the pigment in step 112.
    Preferred chelating agents used in embodiment 1 may be glycosides and polyglycoside derivatives.
    Embodiment 2:
    FIG. 2 illustrates an alternative method
    200 for coating the bismuth-based pigments with chelating agents wherein the chelating agent is prepared via an in-situ polymerization. The method 200 starts with step 204, in which one is dried on bismuth
    BE2017 / 5674 based pigment is obtained and proceeds to step 206 where the chelating agent is polymerized. The polymerization step comprises adding an amount of a reactive ion-active monomer followed by a polymerization initiator to the pigment slurry and stirring the dispersion in a temperature range between 20 ° C and 180 ° C, for a period of time between 30 minutes and 240 minutes , and preferably between 90 minutes and 120 minutes. The step of the polymerization process may optionally include adding a reactive nonionic monomer to the dispersion, stirring it in a temperature range between 20 ° C and 180 ° C and acidifying the pigment slurry to a pH in the range of 0.5 to 4.0, and preferably between 1.5 and 2.5.
    In one embodiment, the monomer may be selected from one or more of the series of monomers comprising [A] one or more functional polymerizable groups selected from an acrylate group or an unsaturated sulfone group (such as the sodium vinosulfonate or sodium styryl sulfonate), and [B] one or more non-ionic monomers such as, but not limited to, an alcohol monomer, an epoxide monomer, an organosilane monomer, an organo-modified
    BE2017 / 5674 siloxane monomer, a thiol monomer, an amine monomer, an unsaturated carboxylic acid derivative monomer (such as methacrylate, acrylamide, anhydride monomers), a vinyl monomer, a vinylamine monomer, or any combination thereof
    A preferred chelating agent used in Embodiment 2 may be polyvinyl sulfonate.
    After the polymerization has been carried out, the method 200 proceeds to step 208 in which the final processing of the encapsulated pigment is performed, followed by drying in step 210 to obtain a desired encapsulated pigment.
    Final processing is generally dependent on the type of process used for the synthesis of the pigment. For example, in some embodiments, the final processing includes dispersing and grinding the encapsulated pigment. In some other embodiments, the final processing step again comprises separation and purification of the encapsulated pigments. The encapsulated pigment thus obtained with improved resistance to alkaline conditions is dried and packaged in step 210. Embodiment 3:
    In some embodiments, such as
    BE2017 / 5674 illustrated in FIG.
    3, a chelating agent solution is first prepared in step 304. Such a solution generally comprises a chelating agent present in water in a concentration region between 10% and 50% and preferably between 20-25%. Thereafter, a obtained dried bismuth-based pigment is added to the chelating agent-based solution, resulting in an encapsulation of bismuth-based pigments in step 306. Thereafter, final processing of the encapsulated pigment is performed in step 308, followed by drying and packaging in step 310 as disclosed in methods 100 and 200.
    Preferred chelating agents used in embodiment 3 may be polyalkyl glycoside derivatives.
    In all of the above embodiments, the bismuth-based pigment may be one of, but not limited to, a bismuth vanadate pigment, a bismuth oxyhalide pigment, or a combination thereof. The encapsulation process involves the addition of a predetermined amount of chelating agent in the slurry of the bismuth-based pigment. In one embodiment of the present invention, the chelating agent becomes
    BE2017 / 5674 added at a level that varies between 0.1% and%, and more preferably between 10% and 20%
    of the weight from the bismuth-based pigment. In some embodiments can the chelating agent turn into introduced just before
    spray drying of the pigment. Spray drying of the pigment is necessary to achieve homogeneity of the encapsulation to ensure distribution of the chelating agent around the pigment. Optionally, the pigment can be slurried in an aqueous solution of the chelating agent in a concentration range between preferred
    In one example, in order to obtain a 10 nm uniform, homogeneous, closed shell encapsulation, the coating should mean at least% by weight of the chelating agent / encapsulant relative to the pigment. Starting from a spherical model of being.
    a smooth-surface pigment whose radius is 0.25 μm, the radius of the coating would be 0.01 μm, the volume of the pigment would be 0.0654 μm 3 , while the volume of the coating would be 0.0082 μm 3 and the ratio of the coating would be 12% by weight of the pigment
    BE2017 / 5674
    In the method of the above invention, the following products, both alone and in combination, can be used as chelating agents:
    EDTA, their corresponding alkali metal salts and EDTA derivatives
    - HEDTA and their corresponding alkali metal salts
    - NTA and their corresponding alkali metal salts
    - Glycosides and polyglycoside derivatives
    - Sorbitane and its derivatives (Co) polymers of sodium vinyl sulfonate, sodium styryl sulfonate, (meth) acrylic acid and their corresponding alkali metal salts, preferably in combination with non-ionic monomers
    Di- to polycarboxylic acids such as citric acid, sorbic acid, oxalic acid, succinic acid, itaconic acid, succinic acid and their corresponding alkali metal salts
    Trimercaptotriazine and their corresponding alkali metal salts
    In some embodiments of the present invention, the step of encapsulating disclosed in methods 100, 200, and 300 further comprises adding one or more inorganic compounds prior to adding the chelating agent. The inorganic compound may be independently selected from one or more salts, or one or more oxides, heteropolyacids, organic acids, sulfites, sulfides, sulfates, phosphates, pyrophosphates, polyphosphates, hydrates, carbonates, silicates, or a combination thereof, or their combination
    BE2017 / 5674 salts selected from the group consisting of alkali earth metals, metals, non-metals, transition metals or lanthanides, or a combination thereof. The addition
    from inorganic connections creates a thin one low from the inorganic link : round it pigment Which then continues encapsulated through addition from the
    chelating agent.
    Furthermore, in such embodiments, the methods of the present invention may further comprise the addition of a silane of the general formula R-Si (OR ') 3 at a level in the range of 0.5 to 10% by weight of the pigment, R is an alkyl group that is substituted with at least one electron donating group, preferably an alcohol or an amino group, and wherein R 'is an alkyl or an aryl group.
    In still other embodiments of the present invention, the method comprises 100, 200 and
    300 further the addition of a foam-resistant additive
    BE2017 / 5674 and a silica derivative for improving the powder property of the dried pigment that improves the flowability of the powder. In some embodiments, 0 to 5% post-treated fumed silica product of preferably 0.2 to 0.7% by weight relative to the pigment is used. However, in other embodiments, any known silica derivative and / or foam inhibiting addition known in the art can be used.
    In some other embodiments of the present invention, the method may
    0 0 and
    300 further comprises adding one or more organic compounds together with the chelating agents, thereby forming a layer of the organic compound around the encapsulated pigment. The organic compound (s) are generally added together with the chelating agent. In some embodiments, however, the organic compound layer can be added just after the addition of the chelating agent. The layer of organic compound formed around the encapsulated pigment facilitates prevention of the interactions of the bismuth pigment with the alkaline salt.
    BE2017 / 5674
    The added organic compound can be selected from one or more of, but not limited to, organo-modified polysiloxanes, PNVA (poly-Nvinylacetamide) and EO-PO block copolymers.
    EXAMPLE 1:
    Treatment of 6606B (BiVa) with a copolymer of vinyl sodium sulfonate and dipropylene glycol diacrylate as a chelating agent results in improved resistance to alkaline conditions.
    Experiment:
    330 g of a bismuth vanadate pigment obtained by the conventional state of the art is slurry in water with a high speed mixer. 33 parts of vinyl sodium sulfonate monomer are added to the pigment slurry, followed by 11.16 parts of a 10% aqueous solution of ammonium peroxodisulfate in water at 30 ° C. After stirring for 15 minutes at 30 ° C, an additional amount of 5.8 parts of a 10% aqueous solution of ammonium peroxodisulfate was added. The slurry is then heated at 80 ° C and stirred for an additional 2 hours at 80 ° C. 15.35 parts of dipropylene glycol diacrylate are added to the pigment slurry in 30 minutes and the slurry is further heated at 95 ° C. The pH of the slurry is brought to pH = 2.5 with dilute sulfuric acid.
    13, 98 parts of 3 aminopropyltriethoxysilane are added and the slurry becomes one again
    BE2017 / 5674 hours stirred. The pigment is then filtered and washed. 338.8 parts of the treated pigment are thus obtained.
    Resistance to alkaline conditions after treatment of 6606B (BiVa) with a copolymer of vinyl sodium sulfonate and dipropylene glycol diacrylate as a chelating agent:
    steel K2CO3 25% Reference Bivanon-treated pigment 46.6% Treated pigment 64.7%
    EXAMPLE 2:
    Treatment of the commercial pigment Lysopac Orange 6820B with glycoside additive 50% as a chelating agent also results in improved resistance to alkaline conditions.
    An experiment was conducted to improve alkaline stability of Bi-based pigments by alkyl polyglycoside
    as a chelating agentdispersion / grinding process.Experiment: to to test through a Step 1 : Grind paste formulation in front of surface treatment of 6820B
    Mod. 1
    Mod. 2
    BE2017 / 5674
    6820B 70.00 70.00 Disperbyk 190/40% Alkyl polyglycoside 50% 12.60 7.00Gedist. water 17.30 22, 90 Tego Airex 901W 0.10 0.10 Total 100.00 100.00 % Alkyl polyglycoside 6820B 9.00 5.00
    Volume = 1 liter
    In both embodiments, spray drying occurs to convert the dispersions into powder material.
    Step 2: Grinding paste formulation for producing pigment paste
    All powder pigments are redispersed with untreated 6820B as a reference according to the following grind paste formulations:
    6820B
    6820B-Mod.1
    6820B-Mod.2
    60.00
    Disperbyk 190/40%
    15.00
    Reference
    60.00
    15.00
    Mod. 1
    60.00
    15.00
    Mod. 2
    28 BE2017 / 5674 Alkyl polyglycoside 50% ----- ----- ----- Gedist. Water 24, 90 24, 90
    24, 90
    Tego Airex 901W 0, 10 0, 10 0, 10 Total 100.00 100.00
    100.00
    Dispersion is performed with a laboratory shaker for 60 minutes at room temperature.
    Step 3 : Composition of white emulsion paint;
    % TiO 2 content
    Gedist. water 187.50 g Calgon N Neu 0.50 g Pigment distributor A 5.00 g Mergal S97 5.00 g Agitan 218 3.00 g Subtotal 201.00 g
    These components are mixed in a dissolver.
    TiO 2 CL 2310 200.00 g
    Calcilite 1G 75.00 g
    Finn Talk 25.00 g Calcilit 6G 150.00 g Subtotal 651.00 g These components be dispersed with dispermat
    gedurende 10 minutenCA4 for 10 minutes
    BE2017 / 5674
    The following ingredients are added with slow stirring:
    Texanol 14.00 g Rheolate 278 5.00 g Acronal 290D (50%; 330.00 g Total 1000.00 g
    These components are mixed with CA40 dispermat for 10 minutes at 10 m / s
    % TiO 2 20.00%
    PVC (pigment and fillers) 46.32%
    Step 4: Production of 1/9 TiO 2 Reduction (solids ratio) in white latex paint part = colored pigment (Reference, Mod. 1, Mod. 2) part = TiO 2 (white latex paint with 20% TiO 2 charge)
    Gravimetric
    White latex paint (20% TiO 2 content) 96.42 g
    Colored pigment paste of 60% pigment charge 3.58 g (reference, Mod. 1, Mod. 2)
    The white latex paint and colored pigment paste are mixed together according to a.m. Ratio and homogenized with Hausshild as laboratory homogenizer.
    The paint is then applied to aluminum panels and dried at room temperature for 24 hours.
    BE2017 / 5674
    After the drying process, half of the panels are immersed in an alkaline solution for 24 hours.
    After this immersion test, the panels are rinsed and dried and colorimetrically evaluated to see the color stability of the pigments in alkaline agents.
    The types of alkaline agents used as immersion solutions are:
    a) 25 O0 K2CO3 b) 10 O0 NaOH c) 10 O0 KOH Step 5: Test results after immersion test (1/9
    TiO2 white reduction)
    The color difference between submerged and non-submerged
    submerged surface from same panel is going to be colorimetrically evaluated.a) Alkaline stability in 25% K 2 CO 3 after 24 hour immersion time dThe color difference and the Resultsfrom the colorimetric analysis displayed in the table shown in FIG. 4.b) Alkaline stability in 10% NaOH after 24 hour
    immersion time d
    BE2017 / 5674
    The color difference and the Resultsfrom the colorimetric analysis displayed in the table shown in FIG. 5.c) Alkaline stability in 10% KOH after 24 hour immersion time dThe color difference and the Resultsfrom the colorimetric analysis displayed in the table
    shown in FIG. 6.
    Interpretation of the test results:
    The lower the total tin deviation (dE) or the higher the color strength, the better the alkaline stability of the Bi-based pigment. Mod. 1 and Mod. 2 show a significant improvement in the three alkaline environments.
    The table shown in FIG. 7 shows the results of the experiment performed to determine the alkaline-resistance resistance of bismuth-based pigment coated with 15% of an alkyl glycoside derivative in which the colored plates were immersed in aqueous solutions of 25% K 2 CO 3, 10% NaOH, and 10% KOH and the results show the color strength of the submerged portion of the plate as compared to the non-exposed portion of the plate.
    BE2017 / 5674
    INDUSTRIAL APPLICABILITY
    The present disclosure relates to a bismuth-based pigment encapsulated by a chelating agent. These pigments get an improved resistance to alkaline conditions in addition to properties such as high resistance to extreme weather conditions. Furthermore, the pigments offer higher heat resistance, weather resistance, acid resistance and SO2 resistance and are extremely stable under various light conditions.
    Although these pigments are lead-free and chromate-free, they largely meet the requirements for outside performance while being suitable for most industrial applications. Accordingly, these pigments can be advantageously used in various industries such as paint and coating industries, automotive and transportation industries, cosmetic industries, or the like. These pigments are especially recommended for coatings as well as for various plastic applications.
    Furthermore, pigments are ideal for applications such as deck paint in cars (OEM and refinish), high-quality industrial paints, production of colored plastic products. Some bismuth-based pigments such as bismuth oxychloride (BiOCl) may also be used
    BE2017 / 5674 are used in cosmetic products such as pigment in paint for eye shadow, hair spray and nail polish.
    The bismuth-based pigments of the present invention can be used almost anywhere. More specifically in logistics as well as in companies in the chemical, paint, cosmetic, packaging, film, cardboard and automotive industries as well as the aviation industry that require extremely stable pigment with excellent resistance to negative situations.
    The present disclosure further provides a method, generally indicated by the number
    100, for the production of bismuth-based pigment with improved resistance to alkaline conditions. The method is generally a simple, cost-efficient, time-saving method for forming high-quality bismuth pigments.
    权利要求:
    Claims (5)
    [1]
    1, wherein the chelating agent is one from the group consisting of EDTA and their corresponding alkali metal salts, HEDTA and their corresponding alkali metal salts,
    NTA and their corresponding alkali metal salts, glycosides and polyglycoside derivatives, sodium vinyl sulfonate, (meth) acrylic acid and sorbitan derivatives, sodium styryl sulfonate, are corresponding alkali metal salts, di-to-polycarboxylic acids and their corresponding alkali metal salts, trimercaptotriazine and their corresponding alkali metal salts, or their corresponding alkali metal salts.
    The method of claim 1, wherein the method further comprises adding an organic compound together with chelating agents to prevent interactions of the bismuth pigment with the alkaline salt.
    The method of claims 2 and 4, wherein the method further comprises in-situ polymerization of the chelating agent.
    BE2017 / 5674
    The method of claim 10, wherein the polymerization comprises adding an amount of a reactive ion-active monomer followed by a polymerization initiator to the pigment slurry and stirring said dispersion in a temperature range between 20 ° C and 180 ° C, for a time period between 30 minutes and 240 minutes, preferably between 90 minutes and 120 minutes.
    A method according to any of claims 10 or 11, wherein the polymerization comprises adding a reactive non-ionic monomer to the dispersion and stirring said dispersion in a temperature range between 20 ° C and 180 ° C.
    The method of claim 10, wherein the polymerization further comprises acidifying the pigment slurry to a pH between 0.5 and 4, preferably between 1.5 and 2.5.
    A method according to any of claims 11 or 12, wherein the monomer [A] comprises one or more functional polymerizable groups selected from an acrylate group or an unsaturated sulfone group, and [B] comprises one or more non-ionic monomers.
    15. - Bismuth-based pigment encapsulated by a low chelating agent.
    16. Bismuth-based pigment according to
    BE2017 / 5674 claim 15, wherein the chelating agent is one from the group consisting of EDTA and their corresponding alkali metal salts,
    HEDTA and their corresponding alkali metal salts,
    NTA and their corresponding alkali metal salts, glycosides and polyglycoside derivatives, sorbitan derivatives, sodium vinyl sulfonate, sodium styryl sulfonate, (meth) acrylic acid and its corresponding alkali metal salts, ditot polycarboxylic acids and their corresponding alkali metal salts, trimercaptotriazine and their corresponding alkali metal salts of the above-mentioned alkali metal combination salts.
    The bismuth-based pigment according to claim 15, wherein the weight of the chelating agent
    Is 0.1 to 3% by weight and preferably between 10 and 20% by weight of the pigment.
    A bismuth based pigment according to claim 15, further comprising a layer of one or more inorganic compound (s) based on one or more salts, or one or more oxides, heteropolyacids, organic acids, sulfites, sulfides, sulfates, phosphates , pyrophosphates, polyphosphates, hydrates, carbonates, silicates, or their salts selected from the
    BE2017 / 5674 group consisting of alkaline earth metals, metals, non-metals, transition metals or lanthanides, or a combination thereof.
    19. Bismuth-based pigment according to
    1.- Method for producing an op
    BE2017 / 5674
    CONCLUSIONS bismuth based pigment with improved resistance to alkaline conditions, the method comprising:
    i) obtaining a dried bismuth-based pigment;
    ii) encapsulation of the bismuth-based pigment by a chelating agent;
    iii) final processing of the encapsulated pigment; and iv) drying the pigment.
    [2]
    A method according to claim 1, wherein the method comprises the step of re-slurrying the pigment by adding an amount of water, preferably reverse osmosis water;
    rotating said dispersion in a temperature range between
    10 ° C and
    100 ° C, preferably between 35 ° C and ° C for a period of time in the range of minutes to
    120 minutes, preferably between minutes and 70 minutes.
    [3]
    The method of claim 2, wherein the step of re-slurrying is performed before the encapsulation step.
    BE2017 / 5674
    [4]
    The method of claim 1, wherein the encapsulation comprises adding the chelating agent in a range between 0.1 and 30% by weight, and preferably between 10 and 20% by weight relative to the pigment.
    The method of claim 4, wherein the encapsulation comprises slurrying the pigment in an aqueous solution of chelating agent in a concentration range between 0.1% and 50%, and preferably between 20-25%.
    The method of claim 1, wherein the encapsulation further comprises adding one or more inorganic compounds prior to adding the chelating agent, said inorganic compounds being selected from one or more salts, or one or more oxides, heteropolyacids, organic acids , sulfites, sulfides, sulfates, phosphates, pyrophosphates, polyphosphates, hydrates, carbonates, silicates, or a combination thereof, or their salts selected from the group consisting of alkali metals, metals, non-metals, transition metals or lanthanides, or a combination thereof.
    The method of claim 6, wherein the method further comprises adding a silane of the general formula R-Si (OR ') 3, wherein R is an alkyl group
    BE2017 / 5674, which is substituted with at least one electron donating group, preferably an alcohol or an amino group, and wherein
    R 'is an alkyl or an aryl group according to claim
    [5]
    Claim 18, further comprising 0.5 to 10% by weight with respect to the pigment of a silane of the general formula R-Si (OR ') 3, wherein R is an alkyl group substituted with at least one electron donating group, preferably an alcohol or an amino group, and wherein R 'is an alkyl or an aryl group.
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    同族专利:
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3946134A|1973-07-23|1976-03-23|The Harshaw Chemical Company|Method of encapsulating particles and the resultant product|
    US4115141A|1976-06-22|1978-09-19|E. I. Du Pont De Nemours And Company|Process for the preparation of pigmentary bright primrose yellow bismuth vanadate|
    US4063956A|1976-09-16|1977-12-20|E. I. Du Pont De Nemours And Company|Heat stable monoclinic bismuth vanadate pigment|
    DE3135281A1|1981-09-05|1983-03-24|Basf Ag, 6700 Ludwigshafen|BISMUT VANADATE CONTAINING YELLOW PIGMENT OF COMPOSITION BIV0 4 . XBI 2 MO0 6 . YBI 2 WHERE 6 AND METHOD FOR THE PRODUCTION THEREOF|
    DE3643247A1|1986-12-18|1988-06-30|Basf Ag|TEMPERATURE-STABLE BISMUT VANADAT / MOLYBDAT PIGMENTS|
    US5123965A|1989-11-30|1992-06-23|Ciba-Geigy Corporation|Process for stabilizing bismuth vanadate pigments against attack by hydrochloric acid|
    EP0810268B1|1996-05-31|2004-06-30|Ciba SC Holding AG|Bismuth vanadate pigments|
    DE19840156A1|1998-09-03|2000-03-09|Basf Ag|Bismuth vanadate pigments with at least one coating containing metal fluoride|
    US6833026B2|2002-05-10|2004-12-21|Cabot Corporation|Modified pigments and process for preparing modified pigments|
    DE102004023075A1|2004-05-11|2005-12-08|Merck Patent Gmbh|Stabilized BiOCl pigments|
    JP4942294B2|2004-12-16|2012-05-30|東洋アルミニウム株式会社|Metallic pigment and paint containing the same|
    KR101211767B1|2009-06-30|2012-12-12|한국과학기술원|Mutants of PHA Synthases and Method for Preparing PLA and PLA Copolymer Using the Same|
    GB0916171D0|2009-09-15|2009-10-28|Akzo Nobel Coatings Int Bv|Encapsulation of pigments with polymer latex prepared by mini-emulsion polymerization|
    JP5813964B2|2011-02-28|2015-11-17|石原産業株式会社|Bright pigment and method for producing the same|
    DE102011015338A1|2011-03-28|2012-10-04|Eckart Gmbh|Weather-stable pearlescent pigments, process for their preparation and use|
    EP2714817A4|2011-05-31|2015-04-08|Univ Sydney|Polymer particles|
    EP2584009A1|2011-10-17|2013-04-24|Cappelle Pigments N.V.|Bismuth-based pigment and method for its manufacture|
    CN103525128B|2012-07-03|2015-11-25|广东先导稀材股份有限公司|The preparation method of cladded type bismuth vanadium pigments|
    CN104684979B|2012-10-01|2018-03-20|Viavi 科技有限公司|A kind of colouring agent for including pigment composition|EP3546531A1|2018-03-27|2019-10-02|Ferro Performance Pigments Belgium|Method for manufacturing bismuth vanadate pigment having an improved alkaline resistance|
    法律状态:
    2019-02-04| FG| Patent granted|Effective date: 20190117 |
    优先权:
    申请号 | 申请日 | 专利标题
    EP16190051.9A|EP3299424A1|2016-09-22|2016-09-22|Method for manufacturing bismuth based pigment having an improved alkaline resistance by encapsulating said pigment with a chelating agent|
    EP16190051.9|2016-09-22|
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