CN1195005A - Pearl pigment having high iridescent-color effect, process for manufacturing same, and uses thereof - Google Patents
Pearl pigment having high iridescent-color effect, process for manufacturing same, and uses thereof Download PDFInfo
- Publication number
- CN1195005A CN1195005A CN98105926A CN98105926A CN1195005A CN 1195005 A CN1195005 A CN 1195005A CN 98105926 A CN98105926 A CN 98105926A CN 98105926 A CN98105926 A CN 98105926A CN 1195005 A CN1195005 A CN 1195005A
- Authority
- CN
- China
- Prior art keywords
- suspension
- pearl pigment
- coating
- calcium
- magnesium
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
- C09C1/0021—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a core coated with only one layer having a high or low refractive index
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/36—Pearl essence, e.g. coatings containing platelet-like pigments for pearl lustre
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
- C01P2006/64—Optical properties, e.g. expressed in CIELAB-values b* (yellow-blue axis)
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
- C09C2200/10—Interference pigments characterized by the core material
- C09C2200/1004—Interference pigments characterized by the core material the core comprising at least one inorganic oxide, e.g. Al2O3, TiO2 or SiO2
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
- C09C2200/10—Interference pigments characterized by the core material
- C09C2200/102—Interference pigments characterized by the core material the core consisting of glass or silicate material like mica or clays, e.g. kaolin
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
- C09C2200/30—Interference pigments characterised by the thickness of the core or layers thereon or by the total thickness of the final pigment particle
- C09C2200/301—Thickness of the core
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Paints Or Removers (AREA)
- Cosmetics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention develops pearl dye, which enables the pearl dye to be provided with high brightness and high iridescence effects which are produced on the basis of interference colors. Calcium and magnesium are added into a metal oxide coating which is formed on the surface of a sheet-like basal body, the oxide coating is mainly composed of rutile or titanium doffing ore shaped titanium oxide, which can lower the degree of porosity of the coating surface (or improve the smoothness), thereby the pearly luster of the pearl dye and the high iridescence effects (or the chrominance) which are produced on the basis of the interference colors are improved.
Description
The present invention relates to a kind of pearl pigment, it has the brightness and the colourity of excellent interference color, the present invention is specifically related to a kind of like this pearl pigment, in the coating of metal oxides of its covering stratiform matrix, contain calcium and magnesium, and coating mainly is made of titanium oxide, thereby have the surface flatness of high refractive index, height and the height iris effect that interference light produces, also relate to Preparation Method And The Use.
Pearl pigment can buy, and is used in the various pigment field that has the transparent of high refractive index or semi-transparent metals oxide compound such as titanium oxide or iron oxide-coated formation such as using on the micaceous flaky matrix.Should understand, metal oxide with high refractive index is as coating material, (see Nakahara: " Science of Colors " because produce the high surface reflection of incident light according to following equation (1) high refractive index, Baifukan), perhaps high gloss, and can make and adopt little thickness to obtain interference color (iris) to become possibility, thereby prevent any scattering of light and obtained having the pigment of high chroma.Equation (1): R=(n-1)
2(n+1)
2[wherein R means reflectivity, and n means specific refractory power].
Can think that iris is to be interfered mutually and produced by the incident beam of coating of metal oxides surface reflection and the incident beam that reflects on interface between stratiform matrix and the coating of metal oxides surface.Therefore, if being used for the material of coating has high refractive index, be hyaline smooth and have uniform optical property, just can obtain a kind of have height nacreous lustre (brightness) and highly irised pigment by interference.
As everyone knows, the porosity of coating of metal oxides also has very big relation with its specific refractory power on the stratiform matrix surface.Equation (2) below Dr.Yoldas has announced, the relation between its expression specific refractory power and the porosity.
Equation (2): np
2=(n
2-1) (1-p/100)+1[wherein np represent apparent relative refractive index, p represents porosity (%), n represents specific refractory power].
According to above-mentioned equation (2), if for example n is that the rutile titanium dioxide of 2.9 values has 30% porosity p, its np is 2.49, and when porosity was 0%, its reflectivity was 24%, and then when porosity was 30%, its reflectivity was reduced to 18%.If even the material of employing high refractive index is as coating material, then on coating, exist space (highly porous in other words) to reduce its reflectivity, therefore be difficult to the gloss that provides high, and also reduced its slickness, the result is difficult to produce the pigment that obtains good iris effect (perhaps colourity) by interference.
These phenomenons must cause adopting the pearl pigment of conventional commercially available titanium oxide coated mica can not be satisfactory aspect nacreous lustre (brightness), and by interfering the irised effect low (or their low colourity) that produces.
On the other hand, recommended a kind of painted lamellar pigment, it has a metallic compound coating that contains just like calcium or magnesium on flaky matrix, the metallic compound that for example contains calcium or magnesium is (as oxyhydroxide, perhaps insoluble carbonate or oxalate) make pigment dyestuff adhere to the pigment dyestuff (referring to Japanese Patent Application Publication 58-21455) of flaky matrix as inorganic adhesive, perhaps handle (referring to Japanese Patent Application Publication 59-170151), but they do not realize that all this invention expection improves the effect of coking property (reduction porosity) by adding calcium or magnesium by the titanium oxide layer of formation Detitanium-ore-type on flaky mica particle and with the metal halide (thinking improving agent) of any element of cycle Table II family (comprising calcium and magnesium) as rutile.
Therefore, conventional commercially available pearl pigment can not be satisfactory, because their coating of metal oxides has the porosity of height, and is difficult to the gloss that provides satisfied, perhaps iris.
According to the recent research result of the conventional pearl pigment character of our raising, we, the present inventor finds, adds the slickness that a kind of specific metal can produce a kind of sintering effect (reduction porosity) and improve coatingsurface in coating of metal oxides.The present invention is found to be the basis with we these, relates to a kind of pearl pigment of improvement, and this pigment obtains high nacreous lustre and high iris effect by interfering (colourity) there to be best iris.
Therefore, the invention provides a kind of pearl pigment that has as the height iris effect of following (1)～(4) expression, a kind of shown in (5) and (6) the method for preparing pearl pigment and the coating that contains this pearl pigment, plastics, printing ink or the makeup shown in (7).
(1) a kind of pearl pigment has the lip-deep and coating of metal oxides that mainly be made of titanium oxide at flaky matrix, it is characterized in that wherein coating of metal oxides contains calcium and magnesium.
(2) a kind of as (1) said pearl pigment, the amount of titanium oxide in this coating of metal oxides wherein, based on described pearl pigment total amount and in titanium dioxide, be 20～70 weight %, described calcium and magnesium exist with its titanate form respectively, and the total amount of described calcium and magnesium is 0.2～10 weight % in its oxide compound.
(3) a kind of as (1) or (2) said pearl pigment, wherein the atomic ratio of calcium and magnesium (Ca/Mg) is 0.5-5.0 in this coating of metal oxides.
(4) pearl pigment as described in a kind of as (1)-(3) each, wherein titanium oxide is the titanium dioxide of rutile-type in this coating of metal oxides.
(5) a kind of preparation method of pearl pigment, comprise that the mixed aqueous solution that will contain calcium and magnesium ion joins in the suspension of flaky matrix in water, stirring and keeping suspension is under the tart condition, (a) by being joined, calcium and magnesium salts contained the mixing solutions that the titanium ion aqueous solution obtains, splash into this suspension with the alkaline aqueous solution (b) of other preparation, continuation adds this alkaline aqueous solution (b) to suspension and becomes alkalescence and its pH more than or equal to 8 until it, separate solid product from suspension is with its washing, dry and at roasting temperature more than or equal to 700 ℃.
(6) a kind of preparation method of pearl pigment, comprise and to contain Sn, the alkaline aqueous solution (b) of Ca and Mg ionic mixing solutions (a) and preparation is in addition stirring, keeping suspension is to splash under the acid situation in the suspension of flaky matrix in water, to keep suspension simultaneously in stirring be to splash into this suspension under the acid situation with contain the titanium ion aqueous solution (c) and the above-mentioned alkaline aqueous solution (b) of preparation respectively, continuation adds above-mentioned alkaline aqueous solution (b) to suspension becomes alkalescence until it, and its PH is more than or equal to 8, separate solid from this suspension is with its washing, drying is also carried out roasting under more than or equal to 700 ℃ temperature.
(7) a kind of each coating, plastics, printing ink or makeup of pearl pigment of above-mentioned (1)～(4) that contain.
Describe the present invention below in detail.
The said pearl pigment of the present invention be a kind of flash of light and have very strong by interfering the irised pearl pigment that produces, and this pigment has on the surface of flaky matrix the coating of metal oxides of formation and coating mainly is made of titanium oxide, wherein coating of metal oxides contains calcium and magnesium, preferably to small part be its titanate form, and, also has high specific refractory power (mainly referring to " pearl pigment " in this article) owing to calcium and magnesium compound make porosity low as sintering aid.
Flaky matrix as pearl pigment use of the present invention, that can mention is not only natural flaky matrix, as white mica and silk Muscovitum, can also be sintetics, as sheet synthetic mica, lamellar titanium oxide, foliated glass, sheet barium sulfate, sheet silicon oxide, flake ferric oxide and tabular alumina.The size of flaky matrix is equal to or less than under 1 micron situation at mean thickness and recommends to be equal to or less than 200 microns, preferably is equal to or less than 100 microns.
With regard to the method for preparing pearl pigment of the present invention, at first above-mentioned flaky matrix is suspended in the water, this suspension is heated to about 60 ℃ or higher temperature under stirring state, usually near 70～80 ℃.Then,
1) result will prepare the situation of anatase-type titanium oxide,
Calcium and magnesium salts are joined in this suspension, and calcium and magnesium salts are joined mixed aqueous solution (a) and the alkaline aqueous solution (b) that contains the titanium ion aqueous solution and obtain, as sodium hydroxide, potassium hydroxide or ammoniacal liquor, be added drop-wise in this suspension, keep suspension at acid state simultaneously, PH is 1.5～2.5, to form a kind of suspension, the hydrous titanium oxide subparticle that contains some calcium and magnesium ion in this suspension sticks on the flaky matrix surface, keeps most of calcium and magnesium ion to be in dissolved state simultaneously; Perhaps
2) result will prepare the situation of Titanium Dioxide (Rutile) Top grade,
Mixing solutions (a) and alkaline aqueous solution (b) with tin, calcium and magnesium salts, as sodium hydroxide, potassium hydroxide or ammoniacal liquor, be added drop-wise in this suspension, keep PH to be in 1.5～2.5 acidity simultaneously, to form a kind of suspension, flaky matrix has the aqua oxidation tin ultra-fine grain of formation in its surface in this suspension, and contains calcium and magnesium ion.The calcium and the magnesium ion that are in dissolved state are influential to subsequent step, and described subsequent step is the coated particle that forms finely divided hydrous titanium oxide on the flaky matrix surface.Adopt pink salt to be because it that titanium oxide is transformed into rutile-type is effective, and also can use for example zinc or aluminium salt for identical purpose.
Then, the aqueous solution (c) and the above-mentioned basic solution (b) that will contain titanium ion are added drop-wise in this suspension, keeping PH simultaneously is 1.5～2.5, to make a kind of suspension, the fine hydrous titanium oxide particle adhesion that contains some calcium and magnesium ion in this suspension is on the surface of flaky matrix, and remaining most of calcium and magnesium ion are in the dissolved state simultaneously.
As above-mentioned 1) and 2) in calcium and magnesium salts, can adopt any water-soluble salt of these salt, as muriate, vitriol, Silver Nitrate, acetate or oxalate, more particularly, what can mention is for example calcium chloride, nitrocalcite or calcium acetate, magnesium chloride, magnesium nitrate or magnesium acetate.Calcium and magnesium appropriate vol be based on the gross weight of pearl pigment final product, is 0.2～10 weight % in their oxide compound.If less than 0.2 weight %, can't guarantee the nodulizing (for example reducing the effect of porosity) of any satisfaction, if and greater than 10 weight %, coating of metal oxides presents specific refractory power to be reduced, the degree that reduces is bigger than the improvement that obtains by the specific refractory power that reduces its porosity, can't have satisfied interference effect.And any deviation of above-mentioned scope all can influence the dispersiveness as powder-product unfriendly, and causing need be as the grinding and processing of pigment before using.
The atomic ratio of calcium and magnesium (Ca/Mg) is 0.5～5.0th, and is suitable.This ratio can obtain result preferably so preferably as much as possible near 2.Depart from above-mentioned scope and can cause any reduction that can not realize porosity and the powder that generates low dispersity.
Can think, above-mentioned 1) and 2) the suspension of method preparation in, the subparticle of deposition hydrous titanium oxide is so that coating flaky matrix surface, calcium and magnesium ion are trapped on these particulate interfaces simultaneously.Therefore, the present invention need exist calcium and magnesium ion before forming hydrous titanium oxide, therefore needed to add when adding titanium salt at least calcium and magnesium salts, perhaps added before this, as above-mentioned 1) or 2) method described in.
Cheap material, as titanium tetrachloride and titanyl sulfate can recommend as titanium salt, be used to prepare the aqueous solution that the present invention contains titanium ion, and can use the aqueous solution that its dilution is obtained.
Afterwards, alkaline aqueous solution (b) joined splash in the acidic aqueous solution that contains titanium ion, as above-mentioned 1) or 2) as described in, this suspension has just become alkalescence like this, PH is 7～11, keeps dissolved calcium and magnesium ion to form the lip-deep hydrated metal oxide of subparticle that is deposited on hydrous titanium oxide simultaneously within it.
The present invention further makes and adopts the manufacture method based on " thermal hydrolysis " to become possibility.In this case, if suitable, can be with a kind of an amount of calcium, magnesium and titanium ion of containing, and even the solution of tin ion before heating, join in the suspension of flaky matrix in envrionment temperature, and under agitation be heated near boiling.Then, alkaline aqueous solution is joined in this suspension until becoming alkalescence, and PH 7～11 has the suspension that contains hydration calcium oxide and magnesian hydrous titanium oxide subparticle with formation, and be deposited on the surface of flaky matrix.
By filtering above-mentioned 1) or 2) or " thermal hydrolysis " suspension of obtaining come the separate solid product, it is washed with water and drying, and at the roasting temperature that is equal to or greater than 700 ℃, thereby calcium and magnesium are combined in the metal oxide layer, form the compound of calcium and metatitanic acid and magnesium and metatitanic acid and have titanium oxide in its surface, thereby on flaky matrix, form the coating of low porosity.If in the calcination steps process, adopt reducing atmosphere,, form the lower oxyde or the titanium nitride of titanium, with the pearl pigment that obtains having efficient interference and present the black tone of low-light level as nitrogen, ammonia or hydrogen.The metal oxide layer that obtains has as mentioned above found to contain the titanate of calcium and magnesium.
Term used herein " porosity " is meant in the accumulation pore volume mode of measuring sample measures the value (AUTOSORP-6 of Yuasa Ionics Co.Ltd) that the absorption gas volume obtains with full-automatic device, the value that to accumulate pore volume by the coating rate of titanium dioxide on flaky matrix converts the value [A (vol/wt)] based on titanium dioxide to, with its real density (anatase octahedrite: 3.84g/cm
3Rutile: 4.26g/cm
3) remove the shared volume [B (vol/wt)] of titanium dioxide, and according to equation: A
*100/ (A+B) (vol/vol%) calculates.
Should be sure of, the pigment that the present invention has nacreous lustre has the surface-area littler than commercially available conventional products by adopting the measurement of BET method, the surface flatness of higher degree, lower accumulates the porosity that pore volume draws by it, therefore and in the silver color zone and the nacreous lustre (brightness) (under the low coating ratio situation at titanium oxide) of higher degree, perhaps high colourity and high nacreous lustre (brightness) promptly show iris effect (high brightness and high chroma) high in the chromatic color gamut (under the height coating ratio situation of titanium dioxide) under interfering.
As compare other compounds with magnesium compound with the calcium that adopts in the pearl pigment of the present invention with nodulizing, can recommend silicon compound, as silicon tetrachloride, water glass and tetraethyl orthosilicate, aluminum compound, as aluminum chloride and aluminum nitrate and zn cpds, as zinc chloride and zinc nitrate, find that they are obtaining than effective aspect the low porosity.
Be described in further detail the present invention with embodiment and comparative example below.But, should understand the present invention and be confined to the following examples absolutely not.Embodiment 1
With 160 gram diameters is that the natural mica platy shaped particle of 10～60 μ m is suspended in 2.0 premium on currency, and suspension is heated to about 80 ℃ under stirring.Add 1.0 gram CaCl
22H
2O and 1.0 gram MgCl
26H
2O is dissolved in this suspension.Then, by dissolving 5.5 gram CaCl in the diluting soln (dissolving 166 grams in 1 liter) of 838 milliliters of titanium tetrachlorides
22H
2O and 5.5 gram MgCl
26H
2O prepares mixing solutions, this drips of solution is added to by the aqueous sodium hydroxide solution that adopts 20 weight % PH is maintained at about in 1.9 the suspension.After being added dropwise to complete, adopt aqueous sodium hydroxide solution to make the PH of suspension bring up to about 9 once more.
By filtering from suspension separate solid product, wash with water and drying, at about 800 ℃ roasting temperature, generate the silver color pearl pigment that is applied by anatase titanium dioxide with strong nacreous lustre effect.The amount of the titanium oxide of coating is counted 26.4 weight % with titanium dioxide.Embodiment 2
With 200 gram diameters is that the platy shaped particle of the natural mica of 10～60 μ m is suspended in 2.5 premium on currency, and suspension is heated to about 80 ℃ under stirring.Will be by the 6 gram SnCl of dissolving in 192 ml waters
45H
2O, 5.24 gram CaCl
22H
2O and 5.04 gram MgCl
26H
2The mixing solutions of O preparation is added drop-wise to by adopting 32% aqueous sodium hydroxide solution that PH is remained in 1.5 the suspension.
Then the diluting soln (containing 422 grams in 1 liter) of 420 milliliters of titanium tetrachlorides is added drop-wise to by adopting aqueous sodium hydroxide solution that PH is maintained at about in 1.5 the suspension.
After being added dropwise to complete, adopt aqueous sodium hydroxide solution to make the PH of suspension bring up to about 9 once more.
Isolate solid product by filtering suspension liquid, wash with water and drying,, generate the silver color pearl pigment that contains the strong nacreous lustre effect of having of rutile titanium dioxide at about 800 ℃ roasting temperature.The amount of the titanium oxide of coating is counted 26.5 weight % with titanium dioxide.The comparative example 1
Do not adopt CaCl
22H
2O or MgCl
26H
2O, by change final PH be about 5.0 and the identical condition of other basic and embodiment 1 under obtain having the pearl pigment that the anatase titanium dioxide of low gloss applies.The amount of the titanium oxide of coating is counted 26.8 weight % with titanium dioxide.The comparative example 2
Do not adopt CaCl
22H
2O or MgCl
26H
2O, by change final PH be about 5.0 and the identical condition of other basic and embodiment 2 under obtain having the pearl pigment that the rutile titanium dioxide of low gloss applies.The amount of the titanium oxide of coating is counted 26.6 weight % with titanium dioxide.
The following describes the measuring result that relates to the every kind of pearl pigment character that obtains among the foregoing description and the comparative example.
(a) measure specific surface and accumulation pore volume:
They are (AUTOSORP-6 of Yuasa IonicsCo.Ltd) that measure by the amount that adopts full-automatic device to measure absorption gas.
(b) calculate porosity:
After its coating ratio calculates the amount of coating titanium oxide, calculate porosity based on titanium dioxide by adopting equation (3):
Equation (3): the accumulation pore volume of 100* per unit weight titanium oxide/{ not comprising the accumulation pore volume of volume of ideal+per unit weight titanium oxide of titanium oxide of the per unit weight of matrix }, (%) [wherein volume of ideal was meant by with its desirable real density (anatase octahedrite: 3.84g/cm
3Rutile: 4.26g/cm
3) remove the value that the weight (gram) of titanium oxide obtains]
(c) measure and calculate glossiness:
Adopt the monochromatic lid of the dispersion coating base plate that contains 1 weight part sample in the Nitrocellulose of acryl modification of 60 weight parts to prepare sample by applicator; its L value adopts color difference meters (D-25 of Hunter Labo) to measure at two points that input angle/reflection angle is respectively 22.5 °/22.5 ° and 45 °/0 °, and its gloss value calculates by following equation (4):
Equation (4): gloss value=(L (22.5 °/22.5 °)-L (450/00))/{ 100/L (22.5 °/22.5 °) } (%)
The value of these character is listed in following table 1.
The shape of table 1 silver color pearl pigment
| Sample | Specific surface (m 2/g) | Accumulation pore volume (ml/g) | Porosity (%) | Gloss (%) | Crystal formation |
| Embodiment 1 | ???8.348 | ??0.0279 | ????28.9 | ??53.2 | Anatase octahedrite |
| The comparative example 1 | ??18.935 | ??0.0341 | ????32.8 | ??50.1 | Anatase octahedrite |
| Embodiment 2 | ???5.585 | ??0.0167 | ????21.1 | ??56.2 | Rutile |
| The comparative example 2 | ???8.320 | ??0.0289 | ????31.6 | ??54.2 | Rutile |
| ????#103 | ??11.208 | ??0.0273 | ????29.3 | ??53.6 | Rutile |
In this table, #103 represents IRIODIN 103 (Merck), and it is the silver color pearl pigment that contains 28% titania coating.
Can obviously find out from table 1, can determine that pearl pigment of the present invention has high irised silver color.Embodiment 3
With 100 gram diameters is that the natural mica platy shaped particle of 10～60 μ m is suspended in 2 premium on currency, and this suspension is heated to about 75 ℃ under stirring.Will be by the 9 gram SnCl of dissolving in 86 ml waters
45H
2O, 5.24 gram CaCl
22H
2O and 5.04 gram MgCl
26H
2The mixing solutions of O preparation is added drop-wise to by adopting 32% aqueous sodium hydroxide solution that PH is remained in 1.5 the suspension.
Then the diluting soln (containing 418 grams in 1 liter) of 430 milliliters of titanium tetrachlorides is added drop-wise to by adopting aqueous sodium hydroxide solution that PH is maintained at about in 1.5 the suspension.
After being added dropwise to complete, adopt aqueous sodium hydroxide solution to make the PH of suspension bring up to 9.0 once more.
Filtering suspension liquid is isolated solid product, washes with water and drying, at about 850 ℃ roasting temperature, generates the silver color pearl pigment that contains the strong nacreous lustre effect of having of rutile titanium dioxide.The amount of the titanium oxide of coating is counted 41.3 weight % with titanium dioxide.Embodiment 4
With 100 gram diameters is that the natural mica platy shaped particle of 10～60 μ m is suspended in 2 premium on currency, and suspension is heated to about 75 ℃ under stirring.Will be by the 9 gram SnCl of dissolving in 86 ml waters
45H
2O, 5.24 gram CaCl
22H
2O and 5.04 gram MgCl
26H
2The mixing solutions of O preparation is added drop-wise to by adopting 32% aqueous sodium hydroxide solution that PH is remained in 1.5 the suspension.
Then the diluting soln (containing 418 grams in 1 liter) of 570 milliliters of titanium tetrachlorides is added drop-wise to by adopting aqueous sodium hydroxide solution that PH is maintained at about in 1.5 the suspension.
After being added dropwise to complete, adopt aqueous sodium hydroxide solution to make the PH of suspension bring up to about 9.0 once more.
By filtering suspension liquid separate solid product, wash with water and drying, at about 850 ℃ roasting temperature, generate the silver color pearl pigment that contains the strong nacreous lustre effect of having of rutile titanium dioxide.The amount of the titanium oxide of coating is counted 48.2 weight % with titanium dioxide.
Pearl pigment that obtains in embodiment 3 and 4 and commercially available pearl pigment carry out service check, the results are shown in top table 1, and value and look angle ∠ H ° value by calculating tone (value of a and b) and chrominance C.
With regard to the tone that relates to is measured, be evenly dispersed in by every kind of pigment in the ink medium of 9 weight parts and prepare sample 1 weight part, be coated with device with the No.20 rod and its dispersion is applied the monochromatic base plate that covers prepare sample, with monochromator (D-25 type, Hunter Labo) measures its L, a, the value of b.Calculate the chrominance C and the look angle ∠ H ° value of each sample with data that measure and equation:
Gloss: adopt the value shown in equation (4) reckoner 1;
Colourity: C={a
2+ b
2}
1/2
Look angle: ∠ H °=tan
-1(b/a).The results are shown in table 2.
The performance of the pearl pigment of table 2 performance interference color
| Sample | Specific surface (m2/g) | Accumulation pore volume (ml/g) | Porosity (%) | Gloss (%) | ????a | ????b | ????c | ????H | Crystalline state |
| Embodiment 3 | ??3.936 | ??0.0149 | ??13.3 | ??43.6 | ??-2.2 | ???28.2 | ??28.3 | ??94.5 | Rutile |
| ??#205 | ??8.504 | ??0.0323 | ??25.1 | ??39.5 | ??-1.4 | ???24.4 | ??24.4 | ??93.1 | Rutile |
| Embodiment 4 | ??4.451 | ??0.0140 | ??11.0 | ??43.0 | ??29.4 | ??-30.7 | ??42.5 | ??313.7 | Rutile |
| ??#219 | ??9.873 | ??0.0426 | ??28.9 | ??41.4 | ??24.5 | ??-26.3 | ??36.0 | ??312.9 | Rutile |
#205 and #219 mean " Iriodin 205 " and " Iriodin 219 " (both are the Merck product all) in the table 2, be respectively on the mica matrix, to form to have the pearl pigment of 41 weight % and 45 weight % rutile titanium dioxides, and present golden and purplish red interference color respectively.
Table 2 obviously finds out, finds that product of the present invention (embodiment 3 and 4) compares with the #219 product with commercially available #205, and (embodiment 3 and #205, or embodiment 4 compares with #219) porosity is low at the look angle when identical, the chrominance C height.
The above is obviously learnt, pearl pigment of the present invention surpasses the commercially available prod aspect the colourity of pearliness and interference color, and the bright-coloured silver color pearl mediation lightness of colour of performance when being used for automobile and general industry with lacquer, it is like this equally when not only just laser labelling or other are decorated but also also can be used, and be used for to color such as printing ink and cosmetic field when easily incrustation taking place to be used for plastics.
Purposes embodiment
Describing in detail as above below, embodiment obtains the purposes embodiment that pearl pigment is used for coating, plastics, printing ink and makeup:
(1) is used for the embodiment (finishing paint of automobile) of coating
{ primary coat coating compositions }
＜vinylformic acid-melmac 〉
ACRYDIC 47-712 (Dainippon Ink Co., Ltd. product): 70 weight parts
SUPERBECCAMINE G812-60 (the same company product): 30 weight parts
Toluene: 30 weight parts
Ethyl acetate: 50 weight parts
Propyl carbinol: 10 weight parts
SOLVESSO#150 (Tonen Chemical Co., Ltd. product): 40 weight parts
The arbitrary pearl pigment that the foregoing description 1-4 of 100 weight part aforesaid propylene acid-melmac compositions and 20 weight parts is obtained having high rainbow effect mixes preparation primary coat lacquer, add vinylformic acid-melmac to this mixture and regulate its viscosity to the degree (#4 Ford viscosity cup 12-15 second) that is fit to spraying, spray coating forms undercoat.
On undercoat, form colourless finishing paint coating then with following composition:
The ACRYDIC44-179:14 weight part
SUPERBECCAMINE L117-60:30 weight part
Toluene: 4 weight parts
Ethylene glycol butyl ether: 3 weight parts
This finishing paint coating was revealed naked 30 minutes in air in 40 ℃, solidified in 30 minutes 135 ℃ of heating then.
(2) be used for the embodiment of plastics
Polyvinyl resin (spherolite): 100 weight parts
Embodiment 1-4 obtains arbitrary pearl pigment of high rainbow effect: 1 weight part
Zinic stearas: 0.2 weight part
Whiteruss: 0.1 weight part
The dry kneaded material that will contain these material spherolites with injection moulding machine forms desired shape.
(3) be used for the embodiment (gravure ink) of printing ink
CCST medium (Toyo Ink Co., the Nitro cellulose resin of Ltd.): 10 weight parts
Embodiment 1-4 obtains arbitrary pearl pigment of high rainbow effect: 8 weight parts
(Toyo Ink Co. Ltd.) joins in the former printing ink solution of above-mentioned composition so that preparation is fit to the solution of printshop with viscosity with the NC102 solvent of appropriate amount.
(4) be used for the embodiment (lipstick) of makeup:
Ceresine: 5 weight parts
Ceresin (crystallite): 5 weight parts
Paraffin: 10 weight parts
Caprylin: 20 weight part toxilic acid stearyl: 42 weight part tetradecanoic acid stearyl: 10 weight part embodiment 1-4 obtain arbitrary pearl pigment of high rainbow effect, and coloring material: an amount of antioxidant, sanitas and spices: the mixture of the thorough kneading of a small amount of above-mentioned composition is made the lipstick shape.
Claims (7)
1. a pearl pigment has the lip-deep and coating of metal oxides that mainly be made of titanium oxide at flaky matrix, it is characterized in that wherein coating of metal oxides contains calcium and magnesium.
2. according to the pearl pigment of claim 1, the amount of titanium oxide in described coating of metal oxides wherein, based on described pearl pigment total amount in titanium dioxide, be 20～70 weight %, described calcium and magnesium exist with its titanate form respectively, and the total amount of described calcium and magnesium is 0.2～10 weight % in its oxide compound.
3. according to the pearl pigment of claim 1 or 2, wherein the atomic ratio (Ca/Mg) at calcium described in the described coating of metal oxides and magnesium is 0.5-5.0.
4. according to each the pearl pigment of claim 1-3, be the titanium dioxide of rutile-type wherein at titanium oxide described in the described coating of metal oxides.
5. the preparation method of a pearl pigment, comprise that the mixed aqueous solution that will contain calcium and magnesium ion joins in the suspension of flaky matrix in water, stirring and keeping suspension is under the tart condition, (a) calcium and magnesium salts joined contain the mixing solutions that the titanium ion aqueous solution obtains, (b) alkaline aqueous solution of preparation splashes into this suspension in addition, continuation adds this alkaline aqueous solution (b) to suspension and becomes alkalescence and its pH more than or equal to 8 until it, separate solid product from suspension is with its washing, dry and at roasting temperature more than or equal to 700 ℃.
6. the preparation method of a pearl pigment, comprise and to contain Sn, the alkaline aqueous solution (b) of Ca and Mg ionic mixing solutions (a) and preparation is in addition stirring, keeping suspension is to splash under the acid situation in the suspension of flaky matrix in water, to keep suspension simultaneously in stirring be to splash into this suspension under the acid situation with contain the titanium ion aqueous solution (c) and the above-mentioned alkaline aqueous solution (b) of preparation respectively, continuation adds above-mentioned alkaline aqueous solution (b) to suspension becomes alkalescence until it, and its PH is more than or equal to 8, separate solid from this suspension is with its washing, drying is also carried out roasting under more than or equal to 700 ℃ temperature.
7. one kind contains each coating, plastics, printing ink or the makeup of pearl pigment of above-mentioned (1)～(4).
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP094342/1997 | 1997-03-31 | ||
| JP9434297A JPH10279828A (en) | 1997-03-31 | 1997-03-31 | Pearl pigment with high interference color effect and its production and use |
| JP094342/97 | 1997-03-31 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1195005A true CN1195005A (en) | 1998-10-07 |
| CN1112414C CN1112414C (en) | 2003-06-25 |
Family
ID=14107623
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98105926A Expired - Fee Related CN1112414C (en) | 1997-03-31 | 1998-03-30 | Pearl pigment having high iridescent-color effect, process for manufacturing same, and uses thereof |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPH10279828A (en) |
| KR (1) | KR100523226B1 (en) |
| CN (1) | CN1112414C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109085730A (en) * | 2018-08-18 | 2018-12-25 | 南阳理工学院 | A kind of eye-witness report reflector |
| CN111908502A (en) * | 2020-06-25 | 2020-11-10 | 江阴市友佳珠光云母有限公司 | Production process of colorful ultrathin synthetic mica sheet |
| CN114426780A (en) * | 2021-12-29 | 2022-05-03 | 浙江凯色丽科技发展有限公司 | Preparation method of barium sulfate-based conductive composite pearlescent pigment |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW460548B (en) * | 1998-12-23 | 2001-10-21 | Merck Patent Gmbh | Pigment mixture |
| MXPA02010348A (en) | 2000-04-20 | 2003-06-06 | Berol Corp | Shear-thinning writing compositions, writing instruments, and methods. |
| DE60105812T2 (en) | 2000-07-03 | 2005-02-03 | Berol Corp., Freeport | PEARL INK, WRITING INSTRUMENTS AND METHOD |
| AU2001271756A1 (en) | 2000-07-03 | 2002-01-14 | Berol Corporation | Erasable inks, writing instruments, and methods |
| TWI292773B (en) * | 2001-05-09 | 2008-01-21 | Merck Patent Gmbh | Effect pigments based on coated glass flakes |
| WO2003006558A2 (en) | 2001-07-12 | 2003-01-23 | Merck Patent Gmbh | Multilayer pigments based on glass flakes |
| JP4334204B2 (en) * | 2002-11-21 | 2009-09-30 | メルク株式会社 | High-luminance and high-saturation iris pigment and method for producing the same |
| JP5105731B2 (en) * | 2005-09-16 | 2012-12-26 | 大日精化工業株式会社 | Thermoplastic resin composition for molded articles having flip-flop metallic feeling |
| DE102006014095A1 (en) | 2006-03-24 | 2007-09-27 | Merck Patent Gmbh | Glass slides and their use as a transparent filler |
| DE102006027025A1 (en) * | 2006-06-08 | 2007-12-13 | Merck Patent Gmbh | Silver-white effect pigments |
| JP5535425B2 (en) * | 2006-12-22 | 2014-07-02 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング | Filler, method for producing the same, and cosmetics |
| JP2009280542A (en) * | 2008-05-26 | 2009-12-03 | Shiseido Co Ltd | Composite powder, its manufacturing method and cosmetic comprising the composite powder |
| JP4990303B2 (en) * | 2009-01-27 | 2012-08-01 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング | High-luminance and high-saturation iris pigment and method for producing the same |
| CN103124625B (en) | 2010-09-30 | 2016-07-13 | 旭化成株式会社 | Injection-molded body |
| WO2013085050A1 (en) | 2011-12-09 | 2013-06-13 | 日本板硝子株式会社 | Photoluminescent pigment; cosmetic, paint composition, and resin composition containing same; and photoluminescent pigment production method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5433779A (en) * | 1993-12-06 | 1995-07-18 | The Mearl Corporation | Rutile titanium dioxide coated micaceous pigments formed without tin |
-
1997
- 1997-03-31 JP JP9434297A patent/JPH10279828A/en active Pending
-
1998
- 1998-03-30 CN CN98105926A patent/CN1112414C/en not_active Expired - Fee Related
- 1998-03-31 KR KR10-1998-0011142A patent/KR100523226B1/en not_active IP Right Cessation
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109085730A (en) * | 2018-08-18 | 2018-12-25 | 南阳理工学院 | A kind of eye-witness report reflector |
| CN111908502A (en) * | 2020-06-25 | 2020-11-10 | 江阴市友佳珠光云母有限公司 | Production process of colorful ultrathin synthetic mica sheet |
| CN114426780A (en) * | 2021-12-29 | 2022-05-03 | 浙江凯色丽科技发展有限公司 | Preparation method of barium sulfate-based conductive composite pearlescent pigment |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1112414C (en) | 2003-06-25 |
| JPH10279828A (en) | 1998-10-20 |
| KR19980080907A (en) | 1998-11-25 |
| KR100523226B1 (en) | 2005-12-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1112414C (en) | Pearl pigment having high iridescent-color effect, process for manufacturing same, and uses thereof | |
| RU2311433C2 (en) | Highly anticorrosive metallic pigments | |
| JP5717343B2 (en) | Method for forming platelet pigment coated with (rutile) titanium dioxide | |
| CN1058279C (en) | Electrically conductive pigments | |
| CN101389714B (en) | Titanium dioxide pigment coated with hollow bodies, and production method | |
| CN101517011B (en) | Synthetic mica based pearlescent pigments containing ferrites | |
| CN1673284A (en) | Colored interference pigments having metallic luster, preparing method and use of same | |
| CN1732234A (en) | Improved effect pigment comprising a mixture of at least 2 substrate materials | |
| JP6012626B2 (en) | Glittering pigment, cosmetics containing it, coating composition and resin composition, and method for producing glittering pigment | |
| CN1150165A (en) | Flaky aluminium oxide and pearlescent pigment, and production thereof | |
| JP4916659B2 (en) | Rutile titanium dioxide effect pigment and its production | |
| CN1072696C (en) | Novel macreous pigment and preparing method | |
| CN1738869A (en) | Improved effect pigment including reflected layer | |
| CN1784476A (en) | Interference pigment with a high covering power | |
| CN1290934C (en) | Goniochromatic bright pigments | |
| CN1137220C (en) | Multilayer coated powder | |
| CN104619785B (en) | gold pigment | |
| JP4739008B2 (en) | Method for producing pearl pigment | |
| CN1117125C (en) | high-chroma orange pearl pigment | |
| JP2568480B2 (en) | Coated pigment and method for producing the same | |
| JP4195254B2 (en) | Rutile type titanium dioxide fine particles and method for producing the same | |
| EP0509352B1 (en) | Flaky pigments based on oxidized graphite flaky particles | |
| JP2568481B2 (en) | Coated pigment and method for producing the same | |
| CN1789342A (en) | Pearlescent pigment | |
| JP2971996B2 (en) | Rutile-type titanium dioxide-coated graphite flake pigment and method for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |