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    • 专利摘要:
    The present invention is directed to a coated bismuth oxyhalide based pigment with a coating comprising an antioxidant. Furthermore, the present invention is directed to a composition comprising a paint, a lacquer, an ink, a cosmetic, a resin, a plastisol or a polymer formulation, and such a pigment. In addition, the present invention is directed to a method for producing a coated bismuth oxyhalide based pigment, said method comprising the steps of: - providing a dispersion of a bismuth oxyhalide based pigment, - adding a dispersion of an antioxidant, - mixing and drying.
    公开号:BE1023555B1
    申请号:E2016/0117
    申请日:2016-06-30
    公开日:2017-05-02
    发明作者:Greta Verspaille；Jürgen D'haeveloose；Vincent Devreux；Emmanuelle Clabaux
    申请人:Cappelle Pigments Nv；
    IPC主号:
    专利说明:

    Coated bismuth oxyhalide based pigment
    FIELD OF THE INVENTION
    The present invention relates to a coated bismuth oxyhalide based pigment, to a composition comprising a paint, a lacquer, an ink, a cosmetic, a resin, or a plastic and such a pigment, and to a method of producing a such coated bismuth oxyhalide based pigment.
    BACKGROUND OF THE INVENTION
    Mass coloring of polymer processed at high temperatures, such as technical plastics and in particular polyamide (PA), is usually carried out with so-called solvent dyes, which are soluble in the polyamide mass at high processing temperatures and which, in addition to the required resistance to high heat, also have adequate chemical has stability to, for example, the highly reductive medium of the polyamide melt. However, as stated in US 8 461 229, soluble dyes generally have much poorer lightfastness compared to pigments.
    With regard to organic pigments in the orange spectrum, there is only a limited availability of pigments that meet the requirements for high temperature thermal stability as required on the technical plastics market and more specifically of polyamide or glass fiber reinforced polyamide. Most organic pigments (e.g. P036, P064, P072) do not meet the requirements due to pigment degradation.
    With regard to inorganic pigments in the orange spectrum, a first type thereof is based on cerium sulfide. These are high performing pigments in terms of thermal and chemical stability, light resistance and weather resistance in most thermoplastics, including polyolefins, acrylonitrile butadiene styrene (ABS), polycarbonate (PC) and polymethyl methacrylate (PMMA). Due to the extreme temperature and shear conditions in (fiberglass-reinforced) polyamide technical plastic, the chemical stability of the cerium sulfide pigments can be affected and H2S emissions can be detected. In addition, they are also not recommended for durable polyvinyl chloride (PVC) applications and fluoropolymers because discoloration is observed in the presence of HCl or HF formed at high temperatures. (Berte, J.-N. Cerium Pigments. In High Performance Pigments; Faulkner E.B., Schwartz, R.J., Eds .; Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 2009; pp 27-40).
    A second type of inorganic pigments in the orange spectrum is based on complexes of titanium, tin and zinc oxides with different modifiers or dopants. Despite their high thermal and chemical resistance, these pigments cannot fully meet the coloristic requirements for plastic coloring, especially not with regard to the color value.
    A third type of pigments is described in US 6 458 197 B1 in which a modified B1VO4 based pigment is disclosed which is coated with a plurality of layers of inorganic compounds, the last layer being based on a zinc and boron compound. This pigment has a light yellow to orange color and shows excellent resistance to heat in HDPE, but not in PA. In addition, boric acid is subject to strict rules because this substance is very concerned about reproductive toxicity and is therefore excluded for many applications. A maximum permissible zinc content on pigment is also subject to rules for food contact applications, such as European legislation EU / 10/2011 and the Swiss regulation on materials and articles in contact with food SR 817.023.21. The mentioned European legislation and the Swiss regulation limit the maximum allowable amount of zinc that can migrate from the packaging to the food to 25 mg Zn per kg of food.
    An example of a pigment that attempts to eliminate the above problems is described in EP 2 584 010 B1, wherein a coated bismuth oxy iodine bromide is disclosed comprising a first coating containing silica and one or more functionalized silanes, and a second coating containing one or more functionalized contains silanes. In addition to high alkaline resistance for use in watercolors, this pigment exhibits good coloristic properties and moderate heat stability in polyolefins. However, heat stability with mass coloring of polyamide is still lacking.
    Taking into account the above, it is a first object of the present invention to provide a pigment with not only improved and sufficient heat stability for mass coloring of polyolefins, but in particular also for mass coloring of polyamide.
    The present invention is furthermore also directed to providing improved weathering and chemical stability in polyamide and fluoropolymers.
    Another object of the present invention is to provide a pigment with improved alkaline resistance for use in watercolors.
    Furthermore, a pigment according to the present invention can provide clear shade and color consistency in the orange spectrum.
    In addition, a pigment according to the present invention may be less sensitive to discoloration in PVC.
    Another advantage of a pigment of the present invention can be minimal warpage and improved shrinkage resistance in partially crystalline polymers (e.g., PE, PA) and minimal migration in LDPE and PVC.
    It is clear that the production of such a pigment can result. In general, it is an object of the present invention to provide a pigment that has the required properties to be used in a variety of applications, such as water-based applications and mass coloring. of polyolefins and technical plastics such as, but not limited to, polyamides and PVC. In a significant reduction of general pigment production costs compared to the production of different specific pigment types for different applications.
    Summary of the invention
    The present invention is directed to a coated bismuth oxyhalide based pigment with a coating comprising an antioxidant.
    Furthermore, the present invention is directed to a composition comprising a paint, a varnish, an ink, a cosmetic, a resin, a polymer, a plastisol, and such a pigment.
    In addition, the present invention is directed to a method for producing a coated bismuth oxyhalide-based pigment, said method comprising the steps of: - providing a dispersion of a bismuth oxyhalide-based pigment. - adding an antioxidant dispersion, - Mixing and drying.
    Detailed description of the invention
    In a first embodiment of the present invention, a coated bismuth oxyhalide-based pigment with a coating comprising an antioxidant is provided.
    Coating a pigment based on bismuth oxyhalide with an antioxidant makes the coated pigment compatible for a range of applications. The coated pigment not only provides sufficient heat resistance and color stability with mass coloring of polyolefins, but also with mass coloring of polyamide. Moreover, it is still compatible with water-based applications.
    In addition, a coated pigment according to the present invention can provide improved clear tint and color consistency and can provide added value in terms of color in all applications that depend on the use of inorganic pigments, more specifically for the orange spectrum.
    In an embodiment of the present invention, the antioxidant may be a phenol-based, a phosphite or phosphonite-based, or a thioether-based stabilizer, or a combination thereof.
    The antioxidant may be an organic phosphite or phosphonite stabilizer, such as, for example, triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythrityl triphosphityl triphosphityl triphosphite triphosphite triphosphite tri-phosphite pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bisdodecyloxy-pentaerythritol diphosphite, bis (2,4-di- tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4'- biphenylene diphosphite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-dibenzo [d, f] [1,3,2] dioxaphosphepine, 6-fluoro-2,4,8,10-tetra -tert-butyl-12-methyl-dibenzo [d, g] [1,3,2] dioxaphosphocin, bis (2,4-di-tert-butyl-6-methylphenyl) methyl phosphite, bis (2,4-di- tert-butyl-6-methylphenyl) ethyl phosphite.
    Examples of phenol-based stabilizer that can be used within the meaning of the present invention can be:
    Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert- butyl 4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2, 6-dicyclopentyl-4-methylphenol, 2- (a-methylcyclohexyl) -4,6-dimethylphenol, 2,6- dioctadecyl-4-methylphenol, 2,4, β-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, unbranched or branched nonylphenol, for example 2,6-di-nonyl-4-methylphenol, 2,4- dimethyl-6- (1'-methyl-undec-1'-yl) -phenol, 2,4-dimethyl-6- (1'-methylheptadec-1'-yl) -phenol, 2,4-dimethyl-6- (1 1'-methyltridec-1'-yl) phenol and mixtures thereof.
    Alkylthiomethylphenols, for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol.
    Hydroquinones and alkylated hydroquinones, for example 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butyl hydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4 hydroxypphenyl stearate, bis (3,5-di-tert-butyl-4-hydroxyphenyl) adipate.
    Tocopherols, for example α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof. O-, N- and S-benzyl compounds, for example 3,5,3 ', 5' tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl 4-hydroxy-3,5-dimethylbenzyl mercaptoacetate, trideyl 4-hydroxy -3,5-di-tert-butylbenzyl mercaptoacetate tris (3,5-di-tert-butyl-4-hydroxybenzyl) amine, bis (4-tert-butyl-3-hydroxy-2, β-dimethylbenzyl) dithiotherephthalate, bis ( 3,5-di-tert-butyl-4-hydroxybenzyl sulfide, isooctyl 3,5-di-tert-butyl-4-hydroxybenzyl mercaptoacetate.
    Hydroxybenzyl malonates, for example dioctadecyl 2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, dioctadecyl 2- (3-tert-butyl-4-hydroxy-5-methylbenzyl) malonate, didodecyl mercaptoethyl-2 1,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, di- [4- (1,1,3,3-tetramethylbutyl) phenyl] 2,2-bis (3,5-di -tert-butyl-4-hydroxybenzyl) malonate.
    Aromatic hydroxybenzyl compounds, for example 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3,5-di-tert-butyl) 4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) phenol.
    Triazine compounds, for example 2,4-bisoctylmercapto-6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di -tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,3,5-triazine 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,2,3-triazine, 1,3,5-tris (3,5-di-tert-butyl) 4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris (3,5-di-tert-butyl) 4-hydroxyphenylethyl) -1,3,5-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexahydro-1,3,5-triazine, 1.3, 5 -tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.
    Acylaminophenols, for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate.
    Esters of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol (e.g. octadecyl 3- (3 (5-di-tert-butyl-4-hydroxyphenyl) propionate (= Irganox R 1076)), 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol (e.g. pentaerythritol tetrakis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate) (= IrganoxR1010)), tris (hydroxyethyl) isocyanurate, N, N '- bis (hydroxyethyl) oxalamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-fofha-2,6,7-trioxabicyclo [2.2.2] octane.
    Esters of β- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxalamide, 3-thiaundecanol, 3-thiapenthexethyl hexanol, , trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.
    Esters of β- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1, 2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) -oxalamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylheolpropane-4-hydroxy, trimethylhexanediol-trimethyl phospha-2,6,7-trioxabicyclo [2.2.2] octane.
    Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1, 2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis- (hydroxyethyl) oxalamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylheolpropane-4-hydroxy, trimethylheol-propanediol, trimethyl phospha-2,6,7-trioxabicyclo [2.2.2] octane.
    Amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid e.g. N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamine, N, N '- bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylenediamine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine.
    Examples of thioether-based stabilizers that can be used within the meaning of the present invention can be hydroxylated thiodiphenyl ethers, e.g., 2,2'-thiobis (6-tert-butyl-4-methylphenol), 2,2'-thiobis (4- octylphenol), 4,4'-thiobis (6-tert-butyl-3-methylphenol), 4,4'-thiobis (6-tert-butyl-2-methylphenol), 4,4'-thiobis (3,6- di-sec-amylphenol), 4,4'-bis (2,6-dimethyl-4-hydroxyphenyl) disulfide, thiobis [2- (1,1-dimethylethyl) -5-methyl-4,1-phenylene] bis [ 3- (dodecylthio) propionate] (AO-26), thiodipropionic acid dilauryl ester (IrganoxR PS800), distearyl thiodipropionate (IrganoxR PS802), 2,2-bis [[3- (dodecylthio) -1-oxopropoxy] methyl] propane-1, 3-diyl bis [3- (dodecylthio) propionate] (AO -412S), ditridecyl 3,3'-thiodipropionate (AO-503)
    In an embodiment of the present invention, a coated bismuth oxyhalide-based pigment may be provided wherein the coating comprises at least two coating layers, one of which and the antioxidant.
    In an embodiment of the present invention, a coated bismuth oxyhalide-based pigment may be provided wherein the coating comprises an inner coating and an outer coating, the outer coating comprising the antioxidant. Without wishing to be bound by theory, an inner coating can contribute to the protection of the polybismuth oxyhalide-based pigment so that the combination of an inner coating and an outer antioxidant coating results in higher heat resistance and color stability. In addition, this combination can result in improved alkaline resistance, QUV resistance (resistance to the impact of sunlight) and resistance to weathering in water-based paints.
    The inner coating can be composed by one or more salts, or one or more oxides, heteropolyacids, organic acids, sulfites, sulfides, sulfates, phosphates, pyrophosphates, polyphosphates, or a combination thereof selected from the group of alkali earth metals, metals , non-metals, transition metals or lanthanides. One or more calcium salts or oxides, or one or more aluminum salts or oxides, or even more preferably a combination thereof, may be chosen. More specifically, aluminum salts or oxides improve QUV resistance, while calcium salts or oxides provide sufficient protection at low material costs.
    In another embodiment of the present invention, the inner coating can be composed of a plurality of layers. It may comprise a first layer comprising one or more salts, or one or more oxides, heteropolyacids, organic acids, sulfites, sulfides, sulfates, phosphates, pyrophosphates, polyphosphates, or a combination thereof selected from the group of alkali earth metals, metals, non-metals, transition metals or lanthanides, preferably one or more calcium salts or oxides, one or more aluminum salts or oxides, or a combination thereof, and a second layer of silica and functionalized or organo-modified silane. In addition, the inner coating may comprise a third layer comprising a functionalized silane or an organo-modified siloxane or a combination thereof. Without wishing to be bound by theory, it is assumed that the multitude of layers in the inner coating and the antioxidant in the outer coating have a synergistic protection effect for heat treatment, protection against weathering and acid rain (containing sulfur dioxide) and protection against chemical substances , more specifically alkaline media. The above-mentioned first layer may preferably be an outer layer of the inner coating and the second and third layer may be the inner layers of the inner coating.
    According to the present invention, the bismuth oxyhalide-based pigment to be coated may be of the general formula BiOIaBrbClcFd, where a is a number from 0 to 1, preferably from 0.35 to 0.90, more preferably from 0.50 to 0.70; and wherein b is a number from 0 to 1, preferably from 0.10 to 0.65, more preferably from 0.30 to 0.50, wherein c is a number from 0 to 1, preferably from 0 to 1 0.4 where d is a number from 0 to 1, preferably from 0 to 0.4.
    In addition, the bismuth oxyhalide-based pigment to be coated may be of the general formula BiOnlaBrbClcFd, where a + b + c + d> 0 and n> = a + b + c + d.
    Furthermore, the bismuth oxyhalide-based pigment to be coated can be mixed with bismuth vanadate, and / or of the formula: BiV (ln) XnO (4-3n) with (n> 0 and <or = 1), where X stands for I, Br, Cl, or F or a combination thereof.
    In addition, the bismuth oxyhalide-based pigment to be coated may contain additional coating layers based on one or more salts, oxides, hydrates, (pyro) phosphates, silicates or carbonates from an incomplete list of aluminum, silicon, titanium, calcium, rare earth metals or transition metals, one or more functionalized silanes or a combination thereof. The percentage of additional coating layers can preferably be between 0.1 and 30%. The additional coating on the bismuth oxyhalide-based pigment to be coated may advantageously have a first level of stabilization of the base pigment.
    Another embodiment of the present invention provides a composition comprising a paint, a varnish, an ink, a cosmetic, a resin, a polymer, or a plastisol and a coated bismuth oxyhalide-based pigment as described in the preceding paragraphs. Such a composition can provide an improved clear shade and color consistency and is less susceptible to discoloration in the orange spectrum compared to compositions of the prior art.
    More specifically, such a composition may comprise a polyamide and a coated bismuth oxyhalide based pigment as described in the preceding paragraphs. As already mentioned above, colored, optionally glass fiber reinforced polyamide under heat treatment may exhibit improved color stability by coloring it with a coated bismuth oxyhalide based pigment as described in the preceding paragraphs.
    Another more specific composition may include watercolor and a coated bismuth oxyhalide based pigment as described in the preceding paragraphs. As already mentioned above, watercolor can exhibit improved alkali resistance by coloring it with a coated bismuth oxyhalide based pigment as described in the preceding paragraphs.
    In addition, the present invention provides a method for producing a coated bismuth oxyhalide based pigment as described in the preceding paragraphs, said method comprising the steps of: - providing a dispersion of a bismuth oxyhalide based pigment, adding a dispersion of an antioxidant, - mixing and drying.
    By adding antioxidant in the pigment production phase, the coated bismuth oxyhalide-based pigment obtains suitable properties for use in a variety of applications as described above, so that different base mixtures for different types of applications can be produced without adding similar or equivalent additives to the production phase of the basic mixture.
    In addition, against all odds, it was surprisingly found that the efficiency of the antioxidant (e.g., the color stability under heat treatment) in the end product has at least a comparable level for the consumer by adding it in the pigment production phase as compared to adding it in the base mixture .
    The antioxidant dispersion may be a dispersion of a phenol-based, phosphite or phosphonate-based, or a thioether-based stabilizer, or a combination thereof. It may be, preferably, a dispersion of an organic phosphite or phosphonite stabilizer prepared in the presence of one or more non-ionic, cationic or anionic dispersants, or a combination thereof.
    In one embodiment of a method according to the present invention, before adding the dispersion of antioxidant, a mixture of one or more dissolved salts, or one or more oxides, heteropolyacids, organic acids, sulfites, sulfides, sulfates, phosphates, pyrophosphates or a combination thereof selected from the group of alkaline earth metals, metals, non-metals, transition metals or lanthanides are added. By adding this mixture before adding the dispersion of antioxidant, an inner coating is formed before coating with antioxidant.
    The mixture is preferably an aqueous mixture of calcium salts or oxides, and / or aluminum salts or oxides, and even more preferably a mixture of CaCl 2 .2H 2 O and Al 2 (SO 4) 3 xH 2 O.
    The dispersion of a bismuth oxyhalide based pigment can be heated to a temperature in a range between 40 ° C and boiling temperature, preferably between 70 ° and 99 ° C.
    In an embodiment of a method according to the present invention, before adding the mixture of salts, or oxides or acids, etc., an amount of silicate solution and a first amount of functionalized silane can be added and the dispersion can then be stirred while an amount of acid is added until a predetermined pH value between 1 and 5, preferably pH 2.5, is reached. The added silane is preferably of the general formula R-Si (OR ') 3, wherein R is an alkyl group, preferably an alkyl group with from 1 to 22 carbon atoms, an aryl group, or a combination thereof (which is then said alkyl group substituted with at least one aryl group); or R is an alkyl group, preferably an alkyl group having from 1 to 16 carbon atoms, wherein this alkyl group is substituted with at least one electron donating group, preferably an alcohol group or an amino group; and R 'is an alkyl group, preferably an alkyl group with from 1 to 3 carbon atoms, or an aryl group. An example thereof is amino-3-propyltriethoxysilane (or 3-aminopropyltriethoxysilane).
    In addition, a second amount of functionalized silane or an amount of organo-modified siloxane or a combination thereof can be added, preferably after the predetermined pH level after the first amount of functionalized silane is added.
    By adding the silicate solution and the functionalized silane, and optionally the second amount of functionalized silane in successive steps, an inner coating is formed, composed of a number of different coating layers. As mentioned above, it is believed that the multitude of layers in the inner coating and the antioxidant in the outer coating improve protection for heat treatment (mainly for polyamide), protection against weathering and protection against chemical substances, more specifically alkaline media.
    In one embodiment of the present invention, before the step of filtering, washing and drying the coated pigment, the pH can be adjusted between 5 and 9.
    The oxyhalide-based pigment to be coated in a method according to the present invention can be of the general formula BiOIaBrbClcFd, where a is a number from 0 to 1, preferably from 0.35 to 0.90, more preferably from 0.50 to 0.70; and b is a number from 0 to 1, preferably from 0.10 to 0.65, more preferably from 0.30 to 0.50, wherein c is a number from 0 to 1, preferably from 0 to 0 , 4 and wherein d is a number from 0 to 1, preferably from 0 to 0.4.
    Furthermore, the bismuth oxyhalide-based pigment to be coated in a method according to the present invention may be of the general formula BiOnlaBrbClcFd, where a + b + c + d> 0 and n> = a + b + c + d.
    In addition, the bismuth oxyhalide-based pigment to be coated can be mixed with bismuth vanadate, and / or of the formula: BiV (ln) XnO (4-3n) with (n> 0 and <or = 1) where X stands for I , Br, Cl, or F or a combination thereof. EXAMPLE:
    Preparation of a coated oxyhalide based pigment according to the present invention: The commercially available bismuth oxyhalide based pigment Lysopac Orange 6821B from Cappelle Pigments is chosen as the starting material.
    The percentages or moles listed below are calculated based on the pigment to be coated (i.e., the pigment as introduced as starting material). • A dispersion is made of the bismuth-based pigment in the presence of a silicate solution. The dispersion is heated to a temperature in a range between 40 ° C and boiling temperature, preferably 90 ° in about 1 hour. • An amount of sodium silicate solution is added: 0.001 to 2.5 moles (expressed as silicon) per mole of pigment to be coated, preferably 1.5 moles, in 5 'to 60', preferably 30 ', at a temperature still always between 40 ° C and boiling temperature • An amount of functionalized silane is added: 0.001 to 0.25 mole per mole of pigment to be coated, preferably 0.06 mole, in 1 'to 30', preferably 15 ', at a temperature still between 40 ° C and boiling temperature • Sulfuric acid is added until a certain pH level is reached between pH 1 and 5, preferably pH 2.5, in 30 'to 4 hours, preferably 2 hours, at a temperature still between 40 ° C and boiling temperature • A second amount of functionalized silane is added: 0.001 to 0.25 mole per mole of pigment, preferably 0.03 mole, in 1 'to 30', preferably 15 ', at a temperature still between 40 ° C and boiling temperature • An amount of organo-modification is made Add siloxane (e.g., but not limited to, Tegopren 6875-45 or Tegopren 6877-45): between 0 and 15% by weight compared to the bismuth-based pigment to be coated, preferably 4%, at a temperature still between 40 ° C and boiling temperature • A (combination of) aqueous mixture (s) of salts, oxides, acids, heteropolyacids, sulfites, sulfides, sulfates, phosphates, pyrophosphates, polyphosphates is selected from a non-exhaustive list of elements from the group of alkali earth metals (e.g. Ca, Mg, Sr), metals (e.g. Al, Sn), non-metals (e.g. P), transition metals (e.g. Zn, W, Zr, Y, Ti, Nb, Mo, Mn, Fe) and / or Lanthanide (e.g. Ce), preferably an aqueous mixture of CaCl 2 .2H 2 O and Al 2 (SO 4) 3 xH 2 O added: Each element in an amount of 0 to 1 mole per mole of pigment to be coated, preferably 0 to 0, 25 moles per mole of pigment to be coated. • A dispersion of an organic phosphite stabilizer is prepared in the presence of a (combination of) non-ionic, cationic or anionic dispersant (s) and then added. The amount of organic phosphite stabilizer is 0.1 to 20% by weight relative to the pigment to be coated, preferably 8% by weight. The dispersant is present in an amount of 0.01 to 10% by weight compared to the organic phosphite stabilizer. At this stage in the process, the pH is brought in a range between 6.5 and 7.5 with a solution of 20% by weight of sodium carbonate (Na 2 CO 3), sodium hydroxide (NaOH), or potassium hydroxide (KOH), preferably sodium carbonate. • The pigment slurry is filtered, washed, oven dried at 90 ° C and ground. Control method of coated bismuth oxyhalide pigment in polyamide: • Production of a base blend: The coated bismuth oxyhalide pigment is premixed with a modified poly (ethylene / acrylic acid) copolymer (specifically Aclyn 295A, Honeywell) at 60% pigment charge for 5 '. The premix was fed to the hopper of a co-rotating twin screw extruder (ZK25 Collin) at a temperature of 120 ° C at 100 rpm. Finally, the pelletized base mixture is dried in an oven at 50 ° C for 2 hours. • Dilution of the basic mixture with polyamide-6: the above-mentioned basic mixture is mixed with polyamide (Akulon K222D, DSM) to a pigment concentration of 0.5% by weight. The mixture is poured into the hopper and extruded by means of a single screw extruder (Collin Teach-Line E20T) at temperature zones 235 ° C-2350C-2350C-225 ° C, followed by granulation. The final granulated plastic compound at 0.5% pigment charge is dried in an oven at 75 ° for at least 16 hours. • Evaluation of coloristic properties and heat resistance: 20 plates are produced by injection molding of the above-mentioned plastic compound in a matrix (thickness 2 mm) on a BOY 22S Dipronic at 240 ° C for 30 (") seconds, the end plate of which was used as a reference to measure the coloristic values The temperature is increased in steps of 10 ° C with a residence time of 5 minutes CIELa * b * coloristic values are measured against the reference of 30 seconds 240 ° C to evaluate the heat resistance.
    权利要求:
    Claims (16)
    [1]
    CONCLUSIONS
    1. - Coated bismuth oxyhalide based pigment with a coating comprising an antioxidant.
    [2]
    Coated bismuth oxyhalide-based pigment according to claim 1, wherein the antioxidant is a phenol-based, phosphite or phosphonate-based, or a thioether-based stabilizer.
    [3]
    Coated bismuth oxyhalide based pigment according to claim 1 or 2, wherein the coating comprises an inner coating and an outer coating, wherein the outer coating comprises the antioxidant, and wherein the inner coating comprises a layer with one or more salts, or a or more oxides, heteropolyacids, organic acids, sulfites, sulfides, sulfates, phosphates, pyrophosphates, polyphosphates, hydrates, carbonates, or a combination thereof selected from the group of alkali metals, metals, non-metals, transition metals or lanthanides.
    [4]
    Coated bismuth oxyhalide-based pigment according to claim 3, wherein the inner coating comprises a second layer with silica and functionalized or organo-modified silane, and / or a third layer with a functionalized silane or an organo-modified siloxane or a combination thereof .
    [5]
    Coated bismuth oxyhalide based pigment according to any of the preceding claims, wherein the bismuth oxyhalide based pigment to be coated is of the general formula BiOIaBrbClcFd, where a, b, c, d are numbers from O to 1 and where a + b + c + d> 0.
    [6]
    Coated bismuth oxyhalide based pigment according to any of claims 1 to 4, wherein the bismuth oxyhalide based pigment to be coated is of the general formula BiOnlaBrbClcFd, where a + b + c + d> 0 and n> = a + b + c + d.
    [7]
    A coated bismuth oxyhalide based pigment according to any one of claims 1 to 4, wherein the bismuth oxyhalide based pigment to be coated is mixed with bismuth vanadate, and / or of the formula: BiV (1-n) XnO (4 -3n) with (n> 0 and <or = 1), wherein X is I, Br, Cl, or F or a combination thereof.
    [8]
    A coated bismuth oxyhalide based pigment according to any one of the preceding claims, wherein the bismuth oxyhalide pigment to be coated contains additional coating layers based on one or more salts, or one or more oxides, or one or more heteropolyacids, organic acids, or one or more sulfites, sulfides, sulfates, phosphates, pyrophosphates, polyphosphates, hydrates, carbonates, or a combination thereof selected from the group of alkaline earth metals, metals, non-metals, transition metals or lanthanides, one or more functionalized or organo-modified silane, organo-modified siloxane, or a combination thereof.
    [9]
    A composition comprising a paint, lacquer, ink, cosmetic, resin, plastisol or polymer formulation, or a pigment paste concentration and a coated bismuth oxyhalide-based pigment according to any of claims 1 to and with 8.
    [10]
    A composition comprising polyamide and a coated bismuth oxyhalide based pigment according to any one of claims 1 to 8.
    [11]
    A composition comprising water-based paint and a pigment according to any one of claims 1 to 8.
    [12]
    A method for producing a coated bismuth oxyhalide based pigment according to claims 1 to 8, said method comprising the steps of: - providing a dispersion of a bismuth oxyhalide based pigment, - adding a dispersion of a antioxidant, - mix and dry.
    [13]
    A method for producing a coated bismuth oxyhalide-based pigment according to claim 12, wherein the antioxidant is a phenol-based, a phosphite or phosphonate-based, or a thioether-based stabilizer.
    [14]
    A method for producing a coated bismuth oxyhalide based pigment according to any of claims 12 or 13, comprising the step of adding a mixture of one or more salts, or one or more oxides, heteropolyacids, organic acids, sulfites , sulfides, sulfates, phosphates, pyrophosphates, polyphosphates, or a combination thereof selected from the group of alkaline earth metals, metals, non-metals, transition metals or lanthanides, preferably before adding the antioxidant dispersion.
    [15]
    Method for producing a coated bismuth oxyhalide based pigment according to claim 14, further comprising the steps of adding, before adding the mixture, an amount of silicate solution and a first amount of functionalized silane and stirring the dispersion under addition of an amount of acid until a predetermined pH level is reached.
    [16]
    A method for producing a coated bismuth oxyhalide-based pigment according to claim 15, further comprising the steps of adding, prior to adding the mixture, a second amount of functionalized silane or an amount of organo-modified siloxane or a combination thereof.
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    公开号 | 公开日
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    JP6694066B2|2020-05-13|
    ES2891315T3|2022-01-27|
    JP2018538414A|2018-12-27|
    US20180362771A1|2018-12-20|
    US11168217B2|2021-11-09|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    EP15199898.6|2015-12-14|
    EP15199898.6A|EP3181643A1|2015-12-14|2015-12-14|A coated bismuth oxy halide-based pigment|
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