WO2013111771A1 - 酸化鉄被覆層状ケイ酸塩顔料 - Google Patents
酸化鉄被覆層状ケイ酸塩顔料 Download PDFInfo
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- WO2013111771A1 WO2013111771A1 PCT/JP2013/051279 JP2013051279W WO2013111771A1 WO 2013111771 A1 WO2013111771 A1 WO 2013111771A1 JP 2013051279 W JP2013051279 W JP 2013051279W WO 2013111771 A1 WO2013111771 A1 WO 2013111771A1
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/0241—Containing particulates characterized by their shape and/or structure
- A61K8/0254—Platelets; Flakes
- A61K8/0258—Layered structure
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/25—Silicon; Compounds thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
- A61Q1/04—Preparations containing skin colorants, e.g. pigments for lips
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- A—HUMAN NECESSITIES
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- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
- A61Q1/08—Preparations containing skin colorants, e.g. pigments for cheeks, e.g. rouge
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
- A61Q1/10—Preparations containing skin colorants, e.g. pigments for eyes, e.g. eyeliner, mascara
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q3/00—Manicure or pedicure preparations
- A61Q3/02—Nail coatings
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- 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
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/20—Chemical, physico-chemical or functional or structural properties of the composition as a whole
- A61K2800/26—Optical properties
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/42—Colour properties
- A61K2800/43—Pigments; Dyes
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/60—Particulates further characterized by their structure or composition
- A61K2800/61—Surface treated
- A61K2800/62—Coated
- A61K2800/621—Coated by inorganic compounds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/60—Particulates further characterized by their structure or composition
- A61K2800/65—Characterized by the composition of the particulate/core
- A61K2800/651—The particulate/core comprising inorganic material
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- C01—INORGANIC CHEMISTRY
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- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
- C01P2006/63—Optical properties, e.g. expressed in CIELAB-values a* (red-green axis)
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- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
- C01P2006/64—Optical properties, e.g. expressed in CIELAB-values b* (yellow-blue axis)
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- 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
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- 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
- C09C2200/306—Thickness of an absorbing layer
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- C09C2220/00—Methods of preparing the interference pigments
- C09C2220/10—Wet methods, e.g. co-precipitation
Definitions
- the present invention relates to an iron oxide-coated layered silicate pigment, and in particular to improvement in colorability and gloss.
- Patent Document 1 is an iron-containing pigment based on mica flakes, and uses black iron oxide (Fe 3 O 4 ) as the iron oxide coated on the surface, on muscovite particles and TiO 2 or A low-gloss black iron oxide-coated black scale pigment in which Fe 3 O 4 is precipitated on muscovite particles coated with ZrO 2 is described.
- Patent Document 2 discloses that a small-sized substrate such as mica is covered with a smooth iron (III) oxide layer in which very fine crystals are uniformly and densely packed, and this is reduced to a reducing atmosphere at 100 ° C. or higher. It is described that a pearlescent pigment having an interference color with Fe 3 O 4 as a coating layer can be obtained by subjecting it to a layer containing iron (II) oxide by exposure to water.
- Patent Document 3 describes a black bright pigment in which a flaky glass substrate surface is coated with Fe 3 O 4 and / or a low-order titanium oxide thin film having a thickness of 10 nm to 1 ⁇ m. Due to its high smoothness, it is possible to obtain a pigment with excellent luster by using this as a base material, and when the thickness of the coating layer exceeds 300 nm, the interference color becomes weak and black color development becomes strong, thereby concealing. It is described that the rate is also increased.
- the present invention has been made in view of the background art described above, and an object of the present invention is to provide an iron oxide-coated layered silicate pigment that does not have an interference color, exhibits an original color of iron oxide more strongly, and is excellent in gloss. It is to provide.
- iron oxide-coated layered silicate pigment iron oxide is non-selectively coated on the entire surface and edges of the plate-like particles as a substrate, and the iron oxide is uniformly or scattered on the plate-like particles. It was a thing. As a result of intensive studies by the present inventors, iron oxide-coated layered silicate in which iron oxide is preferentially and selectively coated at the end portion rather than the surface portion of the lamellar silicate plate-like particle A pigment was obtained. And this pigment discovered that it was excellent in the intensity
- the iron oxide-coated layered silicate pigment according to the present invention is an iron oxide-coated layered silicate pigment comprising plate-like particles of layered silicate as a substrate and iron oxide covering the plate-like particles.
- the iron oxide-coated layered silicate pigment is characterized in that the iron oxide does not cover the surface portion of the plate-like particle, or is unevenly distributed at the end portion rather than the surface portion of the plate-like particle. It is.
- the end iron oxide thickness which is the thickness of the iron oxide coating layer in the direction parallel to the surface of the substrate plate-like particle, is in the direction parallel to the thickness of the substrate plate-like particle.
- an iron oxide-coated layered silicate pigment characterized by being larger than the surface iron oxide thickness which is the thickness of the iron oxide coating layer.
- the present invention also provides an iron oxide-coated layered silicate pigment characterized in that the edge iron oxide thickness is 1.5 times or more of the surface iron oxide thickness in the pigment.
- the present invention also provides an iron oxide-coated layered silicate pigment characterized in that, in any of the pigments described above, the entire end of the substrate plate-like particle is coated with iron oxide.
- the present invention also provides an iron oxide-coated layered silicate pigment characterized in that the surface portion of the substrate plate-like particle is not coated with iron oxide in any of the pigments described above.
- the present invention also provides an iron oxide-coated layered silicate pigment characterized in that, in any of the pigments described above, a part of the surface portion of the substrate plate-like particle is coated with iron oxide.
- the present invention also provides an iron oxide-coated layered silicate pigment characterized in that, in any of the pigments described above, the entire surface of the substrate plate-like particle is coated with iron oxide.
- the present invention also provides an iron oxide-coated layered silicate pigment characterized in that, in any of the pigments described above, the layered silicate is a mica group layered silicate.
- the present invention also provides an iron oxide-coated layered silicate pigment characterized in that in the pigment, the layered silicate is synthetic mica.
- the present invention is characterized in that the iron oxide is at least one selected from black iron oxide (Fe 3 O 4 ) and red iron oxide (Fe 2 O 3 ).
- An iron oxide coated layered silicate pigment is provided.
- the present invention also provides an iron oxide-coated layered silicate pigment characterized in that, in any of the pigments described above, the iron oxide is black iron oxide (Fe 3 O 4 ).
- the present invention is iron oxide by oxidizing the pigment according to the any one is a black iron oxide (Fe 3 O 4), at least part of red iron oxide (Fe black iron oxide (Fe 3 O 4)
- An iron oxide-coated layered silicate pigment characterized by being converted to 2 O 3 ) is provided.
- the present invention also provides an iron oxide-coated layered silicate pigment characterized by having no interference color in any of the pigments described above.
- the present invention also provides a cosmetic comprising the iron oxide-coated layered silicate pigment as described above.
- the surface part of the layered silicate plate-like particle is not coated with iron oxide, or iron oxide is unevenly distributed at the end part of the surface part of the plate-like particle. Therefore, it strongly colors the original color of iron oxide and has excellent gloss.
- the iron oxide-coated layered silicate pigment of the present invention comprises layered silicate plate-like particles as a substrate, and the plate-like particles are coated with iron oxide. These surface portions are not covered, or are unevenly distributed at the end portions rather than the surface portions of the plate-like particles.
- the iron oxide does not cover the surface portion of the plate-like particle or is unevenly distributed at the end portion rather than the surface portion of the plate-like particle” as shown in FIG.
- the thickness x of the iron oxide coating layer at the end of the plate-like particle in the direction X parallel to the surface of the plate-like particle is the thickness of the substrate plate-like particle. It means that it is larger than the thickness y of the iron oxide coating layer in the plate-like particle surface portion in the direction Y parallel to (in the present invention, this is referred to as “surface iron oxide thickness”, y may be zero).
- the end iron oxide thickness can be 1.5 times or more the surface iron oxide thickness. In conventional iron oxide-coated layered silicate pigments, the end iron oxide thickness is approximately equal to or less than the face iron oxide thickness.
- x and y can be measured with an electron microscope.
- the entire edge of the substrate plate-like particle is coated with iron oxide.
- the thickness of the end iron oxide is preferably at least equal to or greater than the thickness of the substrate plate-like particles.
- the surface iron oxide thickness is smaller than the end iron oxide thickness.
- a part or the whole of the layered silicate may be exposed without being partly or entirely covered with iron oxide. In this case, the gloss inherent in the layered silicate plate-like particles is sufficiently exhibited.
- the entire surface of the substrate plate-like particles may be coated with iron oxide, and the layered silicate of the substrate may not be exposed.
- the surface iron oxide thickness is reduced to such an extent that no interference color is generated.
- it is preferably 60 nm or less.
- the iron oxide coating layer in the surface portion has as uniform a thickness as possible and has few irregularities on the surface. Thereby, the original color of iron oxide is strongly exhibited and the gloss is also excellent.
- layered silicate plate-like particles used as the substrate in the present invention known particles can be used, but usually a layered silicate that is non-swellable with respect to water is used.
- a layered silicate that is non-swellable with respect to water is used.
- Preferable examples include mica group silicates such as muscovite and synthetic mica. Synthetic mica is particularly preferred because it has few impurities and is excellent in surface smoothness.
- Potassium phlogopite [KMg 3 (AlSi 3 O 10 ) F 2 ] Potassium tetrasilicon mica [KMg 2 1/2 (Si 4 O 10 ) F 2 ], Potassium teniolite [KMg 2 Li (Si 4 O 10 ) F 2 ], K 2/3 Mg 2 1/3 Li 2/3 (Si 4 O 10 ) F 2 Etc.
- any one obtained by any method such as a melting method, a hydrothermal method, or a solid-solid reaction method can be used.
- synthetic mica powder of good quality crystals is mixed with a certain proportion of compounds containing potassium, sodium, magnesium, aluminum, silicon, fluorine, etc., melted, crystallized, cooled, and then mechanically crushed. It is obtained by carrying out heat treatment, washing with water and drying.
- a general method for producing a synthetic mica powder is that a layered crystal of several mm to several cm obtained by a melt synthesis method is roughly pulverized with a dry pulverizer such as a jaw crusher or a hammer crusher, and further pulverized with a fine pulverizer.
- a dry pulverizer such as a jaw crusher or a hammer crusher
- a fine pulverizer for example, in the case of synthetic fluorine phlogopite (potassium phlogopite), after silicic anhydride, magnesium oxide, aluminum oxide and potassium silicofluoride are weighed and mixed so as to have the above composition, they are melted at 1,400 to 1,500 ° C. Synthetic fluorine phlogopite is obtained by cooling to room temperature. The obtained synthetic fluorophlogopite ore is pulverized and classified if necessary to obtain a synthetic mica powder.
- the particle size of the synthetic mica powder used in the present invention is not particularly limited and can be appropriately selected. Generally, those having an average particle size of 5 to 50 ⁇ m and an aspect ratio of 2 to 300 are preferably used. Further, the layered silicate is used as the substrate particles, it is preferable to use those not covered by another coating material such as TiO 2.
- the iron oxide may be at least one selected from black iron oxide (Fe 3 O 4 ) and red iron oxide (Fe 2 O 3 ).
- Black iron oxide is particularly suitable because it can effectively absorb scattered light at the edge of the substrate plate-like particle. Also, since black iron oxide can be converted to red iron oxide by oxidation, a dark brown to red-brown iron oxide-coated layered silicate pigment is obtained by heat treating the black iron oxide-coated layered silicate pigment in the atmosphere. be able to.
- (A) A method of depositing black iron oxide (Fe 3 O 4 ) by gradually adding an aqueous solution containing Fe 2+ and an aqueous solution of an oxidizing agent simultaneously with stirring into a slurry of substrate plate-like particles.
- the pH of the slurry being added is kept constant between 8-9.
- an acid or an alkali is added as necessary.
- the aqueous solution containing Fe 2+ is about 3.0 ⁇ 10 ⁇ 3 g / min or more in terms of Fe 3 O 4 per 1 m 2 of the surface area of the layered silicate plate-like particles serving as the substrate, Since it is easy to precipitate, it is desirable to drop slowly as much as possible at an addition rate below this.
- the temperature of the slurry is kept constant between 70 to 80 ° C.
- an inert gas such as nitrogen gas or argon gas while bubbling.
- stirring can be continued while maintaining the temperature for about 5 minutes to 2 hours as necessary.
- dehydration, rinsing and drying at 100 ° C. or less are performed so that the black iron oxide is coated preferentially and selectively on the end portion rather than the surface portion of the substrate plate-like particle and is unevenly distributed.
- Acid salt pigments can be obtained.
- the drying is preferably performed under an inert gas such as nitrogen gas or argon gas.
- the slurry of the substrate plate-like particles can be obtained by mixing and stirring the substrate plate-like particles with water.
- the substrate plate-like particle concentration in the slurry is not particularly limited, but is usually 1 to 20% by mass, preferably 5 to 15% by mass.
- the aqueous solution containing Fe 2+ can be prepared by dissolving Fe 2+ salts such as ferrous sulfate (FeSO 4 ), ferrous chloride (FeCl 2 ), and ferrous phosphate in water.
- Fe 2+ salt is unstable in water, and iron (III) hydroxide hydroxide precipitates over time, so acid such as sulfuric acid, hydrochloric acid, nitric acid is added to make the pH of Fe 2+ aqueous solution strongly acidic. It is preferable to stabilize the Fe 2+ salt.
- the amount of Fe 2+ may be set according to the target coating amount, but it is preferable to use an amount that can cover at least the entire edge of the substrate plate-like particle. Usually, Fe 2+ is 20% by mass or more, preferably 30% by mass or more (both are internally divided) in terms of Fe 3 O 4 with respect to the substrate plate-like particles.
- the aqueous oxidizing agent solution can be prepared by dissolving an oxidizing agent such as potassium nitrate (KNO 3 ) in water.
- the oxidizing agent is preferably 0.3 to 1.0 times (molar ratio) with respect to Fe 2+ .
- black iron oxide is preferentially and selectively deposited on the edge of the substrate plate-like particle to form a thick coating layer, and black iron oxide is deposited at all or almost on the surface of the substrate plate-like particle.
- An uncoated black iron oxide coated layered silicate pigment can be obtained.
- the edge portion is preferentially After selectively coating with black iron oxide, non-preferential / non-selective coating of black iron oxide on the surface and edges, or non-priority on the surface and edges of the substrate plate-like particles in advance.
- black iron oxide is coated non-selectively and then black iron oxide is preferentially and selectively coated on the end portion as described above.
- a conventionally known black iron oxide coating method can be used.
- the method of depositing the iron oxide (Fe 3 O 4) include, but are not limited thereto.
- the pH of the slurry during addition is kept constant between 8 and 10.
- an acid or an alkali is added as necessary.
- the temperature of the slurry is kept constant between 70 to 80 ° C.
- an inert gas such as nitrogen gas or argon gas while bubbling.
- the addition time is usually about 5 minutes to 1 hour.
- stirring can be continued while maintaining the temperature for about 5 minutes to 2 hours as necessary.
- the drying is preferably performed under an inert gas such as nitrogen gas.
- a slurry of substrate plate-like particles can be obtained in the same manner as described above. Further, an iron oxide-coated layered silicate pigment in which black iron oxide is preferentially and selectively coated on the end portion as a substrate plate-like particle can also be used.
- An aqueous solution containing Fe 2+ can be obtained in the same manner as described above.
- An aqueous solution containing Fe 3+ can be prepared by dissolving an Fe 3+ salt such as ferric sulfate (Fe 2 (SO 4 ) 3 ) or ferric chloride (FeCl 3 ) in water.
- an acid such as sulfuric acid is preferably added to the Fe 2+ aqueous solution and / or Fe 3+ aqueous solution to make it acidic.
- the amounts of Fe 2+ and Fe 3+ may be set according to the target coating amount, but it is preferable to use an amount that covers the entire surface portion.
- the total amount of Fe 2+ and Fe 3+ is 1 to 15% by mass (internal percentage) in terms of Fe 3 O 4 with respect to the substrate plate-like particles.
- the ratio of Fe 2+ to Fe 3+ is preferably 0.5: 1 to 1: 1 (molar ratio).
- the Fe 2+ solution and Fe 3+ aqueous solution without separately, may be an aqueous solution containing Fe 2+ and Fe 3+.
- a dark brown to red-brown iron oxide coated layered silicate is obtained.
- It can be a pigment.
- the oxidation method a known method can be adopted. For example, a heat treatment method at 500 to 800 ° C. in an oxidizing atmosphere such as air is simple.
- the iron oxide-coated layered silicate pigment of the present invention can be used in applications where conventional iron oxide-coated layered silicate pigments have been used.
- it can be blended in cosmetics, paints, inks, resins and the like.
- the pigment of the present invention is blended in a known cosmetic base material, it is possible to prepare a colored cosmetic material that has both unprecedented gloss and the original color strength of iron oxide.
- the cosmetic is not particularly limited.
- makeup cosmetics such as eye shadow, eyeliner, eyebrow, lipstick, lip gloss, lip gloss, mascara and nail enamel
- hair cosmetics such as hair dyes and hair colors. Is mentioned.
- the blending amount of the iron oxide-coated layered silicate pigment of the present invention is not particularly limited, and is appropriately determined according to the type and dosage form of the cosmetic, the target degree of coloring, and the like.
- the iron oxide-coated layered silicate pigment of the present invention is usually 0.05% by mass or more in the cosmetic, but it is 0.5% by mass or more, and further 1.0% by mass or more is added.
- the effect of the coating layered silicate pigment is more remarkably exhibited.
- the upper limit of the blending amount is also not particularly limited and is appropriately determined and can be 100% by mass in the cosmetic. However, from the viewpoint of blending or formulation of other cosmetic ingredients, it is usually 90% by mass or less, Typically, it is 60 mass% or less.
- an aqueous solution containing Fe 2+ was prepared so as to be about 50% (internal percentage) with respect to mica in terms of Fe 3 O 4 .
- 180.0 g of ferrous sulfate (FeSO 4 ⁇ 7H 2 O), 6.5 g of sulfuric acid (H 2 SO 4 ), and 400 g of pure water are mixed in a beaker to prepare an Fe 2+ aqueous solution. did.
- this iron oxide-coated layered silicate pigment was coated with Fe 3 O 4 on the entire edge of the substrate plate-like particles, but the surface portion of the substrate plate-like particles was extremely small.
- the layered silicate was exposed in almost all of the surface portions only by the presence of Fe 3 O 4 .
- the iron oxide-coated layered silicate pigment of Production Example 1 contained 49.8% by mass of Fe 3 O 4 .
- Face and edge coating While stirring, nitrogen gas is bubbled into the slurry of (1), the Fe 2 + ⁇ Fe 3+ mixed aqueous solution of (2) is dropped at 1.57 g / min, and at the same time, the pH of the slurry is maintained at 8.0. An aqueous NaOH solution was also added dropwise. The dropping time was about 1 hour. The temperature was kept at 80 ° C. After completion of the dropping, stirring was continued at 80 ° C. for 10 minutes, and the Fe compound was uniformly deposited on the entire surface and end portions of the mica plate-like particles.
- an aqueous solution containing Fe 2+ was prepared so as to be about 50% (internal percentage) with respect to mica in terms of Fe 3 O 4 .
- 180.0 g of ferrous sulfate (FeSO 4 ⁇ 7H 2 O), 6.5 g of sulfuric acid (H 2 SO 4 ), and 400 g of pure water are mixed in a beaker to prepare an Fe 2+ aqueous solution. did.
- oxidizing agent aqueous solution In another beaker, 44.5 g of potassium nitrate (KNO 3 ) as an oxidizing agent and 300 g of pure water were taken and mixed to prepare an aqueous oxidizing agent solution.
- KNO 3 potassium nitrate
- the entire surface and end portions of the substrate plate-like particles are coated with Fe 3 O 4 , and the end portion iron oxide thickness is determined by the surface portion. It was larger (about twice) than the iron oxide thickness. Further, as a result of powder X-ray measurement and iron content analysis by ICP, the iron oxide-coated layered silicate pigment of Production Example 2 contained 52% by mass of Fe 3 O 4 .
- Fe 3 O 4 as in Comparative Example 1. Evenly coated.
- ⁇ Glossy> Apply paper double-sided tape (Nystack (R) , manufactured by Nichiban Co., Ltd.) to white cardboard, peel off the peeled paper, and then sprinkle the powder of the test sample until it becomes uniform in one direction with a brush. The powder was deposited on a paper double-sided tape, and finally, the excess powder was removed to prepare a test piece. Using a multi-angle spectrocolorimeter (MA-68II, manufactured by X-rite), light is incident on the test piece at 45 °, and the 45 ° specular reflection is perpendicular to the test piece by 15 °. The reflected L value (luminance: L15 value) was measured. Higher L15 value means higher luminance and stronger gloss.
- gloss evaluation was performed on the above test piece by visual observation. Specifically, the panel of 10 people was given a score for the impression of gloss visually by the criteria shown in Table 1 below, and the gloss was evaluated according to the criteria of Table 2 below from the average score of 10 people.
- the commercially available iron oxide-coated layered silicate pigment of Comparative Example 1 has a black-blue color in which the entire surface and ends of the mica plate-like particles are almost uniformly coated with an Fe 3 O 4 layer of about 100 nm. It is a luster pigment and has excellent luster, but has a blue interference color and is inferior to black.
- the synthetic mica powder coated with Fe 3 O 4 of Comparative Example 3 is almost uniform with a Fe 3 O 4 layer having a surface portion and an entire end portion of mica plate-like particles of about 95 nm as shown in FIG. It is a coated black-red glossy pigment that is excellent in gloss but has a red interference color and is inferior to black.
- the commercially available iron oxide-coated layered silicate pigment of Comparative Example 2 has a surface portion and end portions of mica plate-like particles that are uniformly coated with TiO 2. This is a black pigment in which 3 O 4 particles are non-selectively scattered, which is sufficient in blackness but inferior in gloss.
- the synthetic mica powder coated with Fe 3 O 4 and TiO 2 of Comparative Example 4 also has a surface portion of synthetic mica plate-like particles whose surfaces and edges are uniformly coated with TiO 2 as shown in FIG. This is a black pigment in which Fe 3 O 4 particles of about 100 to 300 nm are non-selectively scattered at the end, and although it is sufficient in blackness, it is inferior in gloss.
- the iron oxide-coated layered silicate pigments of Production Examples 1 and 2 had no interference color and were excellent in black and gloss. The reason is not clear, but one reason is as follows.
- the plate-like particles have high parallel orientation, and as shown in FIG. 8, the incident light on the plate-like particle surface portion regularly regularly reflects in a certain direction, which contributes to the gloss. However, at the edge of the plate-like particle, scattered light is generated due to irregular reflection of light, and this scattered light becomes a factor of reducing gloss.
- the ends of the mica plate-like particles are coated with a thick iron oxide layer.
- the reason why the gloss of the production example 2 is higher than that of the production example 1 is that the ends of the mica plate-like particles are covered with a thick iron oxide layer, and the entire plate-like particle surface portion is an interference color. Since it is coated with a uniform iron oxide layer that does not generate luminescence (about 60 nm or less), light in the surface portion that was transmitted in Production Example 1 is generated at the interface between mica and Fe 3 O 4 in the surface portion. This is considered to be due to the regular reflected light that is converted into gloss.
- the iron oxide-coated layered silicate pigment of the present invention is an iron oxide-coated layered silicate pigment in which the iron oxide layer is unevenly distributed thicker at the end portion than the plate-like particle surface portion, and is excellent in gloss, The original color of iron oxide is exhibited.
- Conventional iron oxide-coated layered silicate pigments are those in which the entire surface and edges of the substrate plate-like particles are almost uniformly coated with the iron oxide layer, or the entire surface and edges of the plate-like particles are not covered. Iron oxide particles are selectively scattered (partially coated), and no iron oxide-coated layered silicate pigment as in the present invention has been reported so far.
- blended the iron oxide coating layered silicate pigment of this invention is shown, it is not limited to these.
- a compounding quantity is the mass%. All of these cosmetics containing the iron oxide-coated layered silicate pigment obtained in Production Example 1 or Production Example 2 were excellent in black color development and gloss. When any of the pigments of Comparative Examples 1 to 4 was used in place of the iron oxide-coated layered silicate pigment, the black color or gloss was inferior to the cosmetic of the present invention.
- Part A All components of Part A were uniformly mixed with a mixer.
- Parts A was kneaded with a roller mill and homogenized, and then part B was added and uniformly dispersed with a disper. Thereafter, the part C was put in and dispersed uniformly with a disper again, and then filled in a predetermined container to obtain a nail color.
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Abstract
Description
例えば、特許文献1では、雲母燐片を基礎とする鉄含有顔料であって、表面に被覆した酸化鉄として黒酸化鉄(Fe3O4)を用いており、白雲母粒子上およびTiO2やZrO2で被覆された白雲母粒子上にFe3O4を沈殿させた光沢の低い黒酸化鉄被覆黒色鱗片顔料が記載されている。
本発明者らが鋭意検討を行なった結果、層状ケイ酸塩の板状粒子の面部よりも端部に酸化鉄が優先的・選択的に被覆されて偏在している酸化鉄被覆層状ケイ酸塩顔料を得た。そして、この顔料は、従来の酸化鉄被覆層状ケイ酸塩顔料に比べて酸化鉄本来の色の強さ及び光沢において優れることを見出し、本発明を完成するに至った。
また、本発明は、前記顔料において、端部酸化鉄厚さが面部酸化鉄厚さの1.5倍以上であることを特徴とする酸化鉄被覆層状ケイ酸塩顔料を提供する。
また、本発明は、前記何れかに記載の顔料において、基板板状粒子の面部が酸化鉄で被覆されていないことを特徴とする酸化鉄被覆層状ケイ酸塩顔料を提供する。
また、本発明は、前記何れかに記載の顔料において、基板板状粒子の面部の一部が酸化鉄で被覆されていることを特徴とする酸化鉄被覆層状ケイ酸塩顔料を提供する。
また、本発明は、前記何れかに記載の顔料において、基板板状粒子の面部全体が酸化鉄で被覆されていることを特徴とする酸化鉄被覆層状ケイ酸塩顔料を提供する。
また、本発明は、前記顔料において、層状ケイ酸塩が合成マイカであることを特徴とする酸化鉄被覆層状ケイ酸塩顔料を提供する。
また、本発明は、前記何れかに記載の顔料において、酸化鉄が黒酸化鉄(Fe3O4)及び赤酸化鉄(Fe2O3)から選ばれる少なくとも1種であることを特徴とする酸化鉄被覆層状ケイ酸塩顔料を提供する。
また、本発明は、前記何れかに記載の顔料において、酸化鉄が黒酸化鉄(Fe3O4)であることを特徴とする酸化鉄被覆層状ケイ酸塩顔料を提供する。
また、本発明は、前記何れかに記載の顔料において、干渉色を持たないことを特徴とする酸化鉄被覆層状ケイ酸塩顔料を提供する。
また、本発明は、前記何れかに記載の酸化鉄被覆層状ケイ酸塩顔料を含有することを特徴とする化粧料を提供する。
基板板状粒子の面部においては、その一部あるいは全体が酸化鉄で被覆されずに、層状ケイ酸塩の一部又は全部が露出していてもよい。この場合には、層状ケイ酸塩板状粒子が本来有する光沢が十分発揮される。
好適な例としては、白雲母や合成マイカなどのマイカ族の層状ケイ酸塩が挙げられるが、不純物が少なく面部の平滑性にも優れていることなどから、合成マイカが特に好ましい。例えば、
カリウム金雲母[KMg3(AlSi3O10)F2]、
カリ四ケイ素雲母[KMg2 1/2(Si4O10)F2]、
カリウムテニオライト[KMg2Li(Si4O10)F2]、
K2/3Mg2 1/3Li2/3(Si4O10)F2
などが挙げられる。
また、基板粒子として用いる層状ケイ酸塩は、TiO2など他の被覆物質により被覆されていないものを用いることが好ましい。
(A)基板板状粒子のスラリー中に、攪拌下、Fe2+を含む水溶液と、酸化剤の水溶液とを同時に徐々に添加して黒酸化鉄(Fe3O4)を沈着させる方法
が挙げられる。
また、スラリーの温度は70~80℃の間で一定に保持することが好適である。また、窒素ガスやアルゴンガスなどの不活性ガスをバブリングしながら添加することが好ましい。添加終了後は、必要に応じて5分~2時間程度、温度を保持したままで攪拌を継続することもできる。
その後、脱水、水洗、100℃以下で乾燥を行なうことにより、黒酸化鉄が基板板状粒子の面部よりも端部に優先的・選択的に被覆されて偏在している黒酸化鉄被覆層状ケイ酸塩顔料を得ることができる。なお、乾燥は窒素ガスやアルゴンガスなどの不活性ガス下で行なうことが好ましい。
Fe2+量は、目的とする被覆量に応じて設定すればよいが、少なくとも基板板状粒子端部全体を被覆できる量を用いることが好適である。通常は、Fe2+を基板板状粒子に対してFe3O4換算で20質量%以上、好ましくは30質量%以上(何れも内割)である。
上記の方法によれば、基板板状粒子の端部に優先的・選択的に黒酸化鉄が沈着して厚い被覆層を形成し、基板板状粒子面部には黒酸化鉄が全くあるいはほとんど沈着せずに被覆されていない黒酸化鉄被覆層状ケイ酸塩顔料を得ることができる。
(B)基板板状粒子のスラリー中に、攪拌下、Fe2+を含む水溶液と、Fe3+を含む水溶液とを同時に添加して、あるいは、Fe2+及びFe3+を含む水溶液を添加して、黒酸化鉄(Fe3O4)を沈着させる方法が挙げられるが、これに限定されない。
その後、脱水、水洗、100℃以下で乾燥を行なうことにより、黒酸化鉄を基板板状粒子の面部及び端部に非優先的・非選択的に均一に被覆することができる。なお、乾燥は窒素ガスなどの不活性ガス下で行なうことが好ましい。
Fe3+を含有する水溶液は、硫酸第二鉄(Fe2(SO4)3)や塩化第二鉄(FeCl3)などのFe3+塩を水に溶解して調製することができる。
Fe2+水溶液及び/又はFe3+水溶液には、上述同様、硫酸などの酸を添加して酸性とすることが好ましい。
Fe2+及びFe3+の量は、目的とする被覆量に応じて設定すればよいが、面部全体が被覆される量を用いるのが好ましい。通常は、Fe2+とFe3+との合計量は基板板状粒子に対してFe3O4換算で1~15質量%(内割)である。
また、黒酸化鉄を沈殿させるためにはFe2+とFe3+との比率を0.5:1~1:1(モル比)とすることが好ましい。
なお、Fe2+水溶液とFe3+水溶液とを別々にせずに、Fe2+及びFe3+を含有する水溶液とすることもできる。
酸化方法としては、公知の方法を採用することができ、例えば大気などの酸化雰囲気中500~800℃で熱処理する方法が簡便である。
<製造例1>
下記の方法で製造を行った。
(1)マイカスラリーの調製:
マイカ粉体(トピー工業(株)製 PDM-20L:合成カリウム金雲母、粒子径約20μm、表面積約2.4m2/g、アスペクト比約70)50gと水450gとを、ビーカー中にて混合・撹拌してスラリーを調製し、80℃に加熱・保持した。
別に、Fe3O4換算でマイカに対し約50%(内割)になるように、Fe2+を含有する水溶液を調製した。具体的には、ビーカーに、硫酸第一鉄(FeSO4・7H2O)180.0g、硫酸(H2SO4)6.5g、及び純水400gをとって混合し、Fe2+水溶液を調製した。
別のビーカーに、酸化剤である硝酸カリウム(KNO3)44.5gと、純水300gとをとって混合し、酸化剤水溶液を調製した。
(1)のスラリーに、攪拌下、窒素ガスをバブリングしながら(2)のFe2+水溶液を1.2g/min、及び(3)の酸化剤水溶液を0.71g/minにて同時に滴下した。このとき、スラリーのpHを8.0に保持するように、NaOH水溶液も同時に滴下した。滴下時間は約8時間であった。温度は80℃に保持した。
滴下終了後、80℃で30分間撹拌を継続し、加熱及び撹拌を停止した。
上記工程後、純水を用いて十分に洗浄した上で、吸引ろ過により脱水した。
得られた含水ケーキを80℃で窒素ガスを流しながら15時間加熱して乾燥を行い、強い黒色で光沢に優れる酸化鉄被覆層状ケイ酸塩顔料の粉体を得た。電子顕微鏡写真を図2に示す。
また、粉末X線測定およびICPによる鉄含有量分析を行なった結果、製造例1の酸化鉄被覆層状ケイ酸塩顔料はFe3O4を49.8質量%含むものであった。
下記の方法で製造を行った。
(1)マイカスラリーの調製:
マイカ粉体(トピー工業(株)製PDM-20L:合成カリウム金雲母、粒子径約20μm、表面積約2.4m2/g、アスペクト比約70)50gと水450gとを、ビーカー中にて混合・撹拌してスラリーを調製し、80℃に加熱・保持した。
別に、Fe3O4換算でマイカに対し約11%(内割)になるように、Fe2+及びFe3+を含有する水溶液を調製した。具体的には、別のビーカーに、硫酸第一鉄(FeSO4・7H2O)7.5g、硫酸第二鉄水溶液(Fe2(SO4)3で41質量%含有)26.3g、硫酸(H2SO4)0.3g、及び水60gをとって混合し、Fe2+・Fe3+混合水溶液を調製した。(なお、Fe2+・Fe3+混合水溶液の代わりに、半量の硫酸及び半量の水に硫酸第一鉄及び硫酸第二鉄をそれぞれ混合してFe2+水溶液とFe3+水溶液とを別々に調製し、両水溶液を次の(3)で同時に滴下してもよい。)
(1)のスラリーに、攪拌下、窒素ガスをバブリングしながら(2)のFe2+・Fe3+混合水溶液を1.57g/minにて滴下し、同時に、スラリーのpHを8.0に保持するようにNaOH水溶液も滴下した。滴下時間は約1時間であった。温度は80℃に保持した。
滴下終了後、80℃で10分間撹拌を継続し、マイカ板状粒子の面部及び端部の全体に均一にFe化合物を沈着させた。
別に、Fe3O4換算でマイカに対し約50%(内割)になるように、Fe2+を含有する水溶液を調製した。具体的には、ビーカーに、硫酸第一鉄(FeSO4・7H2O)180.0g、硫酸(H2SO4)6.5g、及び純水400gをとって混合し、Fe2+水溶液を調製した。
別のビーカーに、酸化剤である硝酸カリウム(KNO3)44.5gと、純水300gとをとって混合し、酸化剤水溶液を調製した。
(3)で得られたスラリーに、窒素ガスをバブリングしながら攪拌下、(4)のFe2+水溶液及び(5)の酸化剤水溶液を製造例1と同様に同時に約8時間にて滴下した。このとき、スラリーのpHを8.0に保持するようにNaOH水溶液も同時に滴下した。温度は80℃に保持した。
滴下終了後、80℃で30分間撹拌を継続し、加熱及び撹拌を停止した。
上記工程後、純水を用いて十分に洗浄した上で、吸引ろ過して脱水した。
得られた含水ケーキを80℃で窒素ガスを流しながら15時間加熱して乾燥を行い、強い黒色で光沢に優れる酸化鉄被覆層状ケイ酸塩顔料の粉体を得た。電子顕微鏡写真を図3に示す。
また、粉末X線測定およびICPによる鉄含有量分析を行なった結果、製造例2の酸化鉄被覆層状ケイ酸塩顔料はFe3O4を52質量%含むものであった。
メルク(株)製Colorona(R) Blackstar Blue(Fe3O4で均一に被覆されたマイカ、構成比率(質量比);Fe3O4:マイカ=58:42、黒青光輝粉体)、粒子径(80%):10.0~60.0μm、D-50:18.0~25.0μm、図4に電子顕微鏡写真を示す。
メルク(株)製Colorona(R) Micablack(Fe3O4及びTiO2で被覆されたマイカ、構成比率(質量比);Fe3O4:TiO2:マイカ=50:7:43、黒色粉体)、粒子径(80%)10.0~60.0μm、D-50:18.0~25.0μm)、図5に電子顕微鏡写真を示す。
製造例1又は2で用いた合成マイカ粉体(トピー工業(株)製PDM-20L:合成カリウム金雲母、粒子径約20μm、アスペクト比約70)を比較例1と同様にFe3O4で均一に被覆した。
具体的には、マイカ10質量%濃度の水スラリーを80℃にて混合攪拌しながら、内割でFe3O4換算で50質量%になるように塩化第二鉄(FeCl3)水溶液を滴下した。このとき、NaOH水溶液を滴下してスラリーをpH=3.0に保持し、黄色酸化鉄(FeOOH)をマイカ粒子表面全体に一様に被覆した。その後脱水、105℃で乾燥し、H210%N290%混合ガスを流した還元雰囲気にて530℃で30分焼成し、マイカ粒子表面に被覆したFeOOHをFe3O4に変化させ黒赤色光沢顔料を得た。電子顕微鏡写真を図6に示す。
製造例1又は2で用いた合成マイカ粉体(トピー工業(株)製PDM-20L:合成カリウム金雲母、粒子径約20μm、アスペクト比約70)を比較例2と同様にFe3O4とTiO2で被覆した。構成比率(質量比)もFe3O4:TiO2:マイカ=50:7:43になるように調整した。
具体的には、マイカの水スラリーを70℃に加温し、四塩化チタン水溶液と、スラリーをpH=1.5に保持するためのNaOH水溶液とを適宜用いて滴下し、アナターゼ型TiO2をマイカ粒子全体に緻密に被覆後、脱水乾燥し、700℃で30分焼成して、TiO2被覆マイカを得た。
無色透明のアクリル樹脂塗料(Nアクリルオートクリヤースーパー、日本ペイント(株)製、固形分約50質量%)に被験試料が塗料中で10質量%になるように添加し、よく混合攪拌した後、隠蔽率測定紙に100μm隙間のアプリケータで塗布し、乾燥させた。その塗膜をミノルタ製色彩色差計CR300を用いてL,a,bを測定した。L値が低く、a,b値がゼロに近いほど黒いことを意味する。また、目視でも塗膜の色を判断した。
白色厚紙に紙両面テープ(ナイスタック(R)、ニチバン(株)製)を貼り、はくり紙を剥がした後、被験試料の粉体をふりかけ、ハケで一方向に均一になるまでならし、粉体を紙両面テープの上に付着させ、最後に余分な粉体を払い落とし試験片を作製した。多角度分光測色計(MA-68II、X-rite社製)を使用して、試験片に対して45°で光を入射し、45°正反射から試験片に対して15°垂直方向に反射したL値(輝度:L15値)を測定した。L15値が高いほど輝度が高く光沢が強いことを意味する。
上記光沢測定のために作成した試験片について、目視観察により干渉色の有無を調べた。
同様に、比較例3のFe3O4を被覆した合成マイカ粉体も、図6のように、マイカ板状粒子の面部及び端部全体が約95nm程度のFe3O4層でほぼ均一に被覆された黒赤色光沢顔料であり、光沢には優れているが、赤色の干渉色を有しており黒さに劣る。
同様に、比較例4のFe3O4とTiO2で被覆した合成マイカ粉体も、図7のように、TiO2で面部及び端部が均一に被覆された合成マイカ板状粒子の面部及び端部に100~300nm程度のFe3O4粒子が非選択的に散在した黒色顔料であり、黒さにおいては十分である反面、光沢に劣る。
その理由は明らかではないが、一つには次のように考えられる。
しかし、板状粒子の端部においては、光の乱反射により散乱光を生じ、この散乱光は光沢を減じる要因となる。
なお、製造例2の方が製造例1よりも光沢が高い理由としては、マイカ板状粒子の端部が厚い酸化鉄層で被覆されていることに加えて、板状粒子面部全体が干渉色が出ない程度(約60nm以下)の均一な酸化鉄層で被覆されているため、製造例1では透過していた面部での光が、面部でのマイカとFe3O4との界面で発生する規則的反射光、即ち光沢に変換されるためと考えられる。
従来の酸化鉄被覆層状ケイ酸塩顔料は、基板板状粒子の面部及び端部の全体がほぼ均一に酸化鉄層で被覆されたものか、あるいは板状粒子の面部及び端部の全体にわたって非選択的に酸化鉄粒子が散在(部分被覆)しているものであり、本発明のような酸化鉄被覆層状ケイ酸塩顔料はこれまで報告されていない。
製造例1又は製造例2で得られた酸化鉄被覆層状ケイ酸塩顔料を配合したこれら化粧料は何れも、黒色の発色及び光沢に優れるものであった。酸化鉄被覆層状ケイ酸塩顔料の代わりに比較例1~4の何れかの顔料を用いた場合には、本発明の化粧料に比べて黒色の発色あるいは光沢において劣るものであった。
<パーツA>
水 51.90 質量%
ヒドロキシエチルセルロース 0.70
トリエタノールアミン 2.00
<パーツB>
バイキュサン(R)C1000 11.60
(バイエル マテリアルサイエンス(株)製、水性ポリウレタン分散液)
<パーツC>
ステアリン酸グリセリル 2.50
カルナウバロウ 10.00
ステアリン酸 5.00
フェノキシエタノール 0.50
メチルパラベン 0.20
プロピルパラベン 0.10
<パーツD>
酸化鉄被覆層状ケイ酸塩顔料 15.00
<パーツE>
メチルポリシロキサン 0.50
(信越化学工業(株)製、KF-96A-350cs)
ヒドロキシエチルセルロースが完全に水和してパーツAが均一になるように分散し、その後パーツAを80℃に加熱した。このパーツAに、パーツBを撹拌しながら添加した(相I)。
別の容器でパーツCを80℃に加熱して完全に溶解した後、このパーツCを撹拌しながらパーツEを添加した(相II)。
相IIを相Iにゆっくり添加して80℃で15分間乳化した後、冷却し、途中45℃においてパーツDをエマルジョンに添加混合し、さらに25℃まで冷却してO/W型のクリームマスカラを得た。
<パーツA>
酸化鉄被覆層状ケイ酸塩顔料 34.00質量%
タルク 50.00
ステアリン酸マグネシウム 2.02
エチルパラベン 0.08
<パーツB>
BELSIL(R) CDM3526VP 1.50
(旭化成ワッカーシリコーン(株)製、アルキル(C26-28)ジメチコン)
BELSIL(R) RG90 5.00
(旭化成ワッカーシリコーン(株)製、イソドデカン及び(ビニルジメチル/トリメチルシロキシケイ酸ステアリルジメチコン)コポリマー)の混合物)
BELSIL(R) PDM350VP 3.00
(旭化成ワッカーシリコーン(株)製、トリメチルシロキシフェニルジメチコン)
イソドデカン 4.00
パーツAの全成分をミキサーで均一混合した。
別容器でパーツBのイソドデカンにBELSIL(R) RG90を溶解し、BELSIL(R) PDM350VP、及びBELSIL(R) CDM3526VPを加え、40℃に加熱してパーツBを完全に溶解した。
その後、パーツBにパーツAを投入し、ディスパーで均一に混合した後、金型容器に流し込んで圧力30barで1分30秒加圧し、アイシャドーを得た。
<パーツA>
ニトロセルロース 18.00質量%
トルエンスルホンアミド樹脂 6.00
クエン酸アセチルトリブチル 6.00
アクリル酸アルキル共重合体 2.00
<パーツB>
イソプロパノール 5.00
ベンジルジメチルアンモニウムヘクトライト 2.00
酢酸エチル 20.00
酢酸ブチル 31.00
<パーツC>
酸化鉄被覆層状ケイ酸塩顔料 10.00
パーツAをローラーミルで混練し均一化後、パーツBを添加し、ディスパーで均一分散した。その後、パーツCを投入し、再度ディスパーで均一分散した後、所定の容器に充填してネイルカラーを得た。
Claims (14)
- 基板である層状ケイ酸塩の板状粒子と、前記板状粒子を被覆する酸化鉄とを含む酸化鉄被覆層状ケイ酸塩顔料であって、前記酸化鉄は前記板状粒子の面部を被覆していないか、あるいは、前記板状粒子の面部よりも端部に偏在していることを特徴とする酸化鉄被覆層状ケイ酸塩顔料。
- 請求項1記載の顔料において、基板板状粒子の面に平行な方向の酸化鉄被覆層の厚さである端部酸化鉄厚さが、基板板状粒子の厚さに平行な方向の酸化鉄被覆層の厚さである面部酸化鉄厚さよりも大きいことを特徴とする酸化鉄被覆層状ケイ酸塩顔料。
- 請求項2記載の顔料において、端部酸化鉄厚さが面部酸化鉄厚さの1.5倍以上であることを特徴とする酸化鉄被覆層状ケイ酸塩顔料。
- 請求項1~3の何れかに記載の顔料において、基板板状粒子の端部全体が酸化鉄で被覆されていることを特徴とする酸化鉄被覆層状ケイ酸塩顔料。
- 請求項1~4の何れかに記載の顔料において、基板板状粒子の面部が酸化鉄で被覆されていないことを特徴とする酸化鉄被覆層状ケイ酸塩顔料。
- 請求項1~4の何れかに記載の顔料において、基板板状粒子の面部の一部が酸化鉄で被覆されていることを特徴とする酸化鉄被覆層状ケイ酸塩顔料。
- 請求項1~4の何れかに記載の顔料において、基板板状粒子の面部全体が酸化鉄で被覆されていることを特徴とする酸化鉄被覆層状ケイ酸塩顔料。
- 請求項1~7の何れかに記載の顔料において、層状ケイ酸塩がマイカ族層状ケイ酸塩であることを特徴とする酸化鉄被覆層状ケイ酸塩顔料。
- 請求項8記載の顔料において、層状ケイ酸塩が合成マイカであることを特徴とする酸化鉄被覆層状ケイ酸塩顔料。
- 請求項1~9の何れかに記載の顔料において、酸化鉄が黒酸化鉄(Fe3O4)及び赤酸化鉄(Fe2O3)から選ばれる少なくとも1種であることを特徴とする酸化鉄被覆層状ケイ酸塩顔料。
- 請求項1~9の何れかに記載の顔料において、酸化鉄が黒酸化鉄(Fe3O4)であることを特徴とする酸化鉄被覆層状ケイ酸塩顔料。
- 酸化鉄が黒酸化鉄(Fe3O4)である請求項1~9の何れかに記載の顔料を酸化し、黒酸化鉄(Fe3O4)の少なくとも一部を赤酸化鉄(Fe2O3)に変換したことを特徴とする酸化鉄被覆層状ケイ酸塩顔料。
- 請求項1~12の何れかに記載の顔料において、干渉色を持たないことを特徴とする酸化鉄被覆層状ケイ酸塩顔料。
- 請求項1~13の何れかに記載の酸化鉄被覆層状ケイ酸塩顔料を含有することを特徴とする化粧料。
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EP13741230.0A EP2808363B1 (en) | 2012-01-23 | 2013-01-23 | Iron oxide-coated layered silicate pigment |
JP2013549441A JP5769820B2 (ja) | 2012-01-23 | 2013-01-23 | 酸化鉄被覆層状ケイ酸塩顔料 |
US14/373,422 US9637638B2 (en) | 2012-01-23 | 2013-01-23 | Iron oxide-coated layered silicate pigment |
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JP2012011283 | 2012-01-23 | ||
JP2012-011283 | 2012-01-23 |
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US (1) | US9637638B2 (ja) |
EP (1) | EP2808363B1 (ja) |
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WO (1) | WO2013111771A1 (ja) |
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WO2020040169A1 (ja) | 2018-08-22 | 2020-02-27 | トピー工業株式会社 | ケイ酸塩被覆体 |
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JP2017529689A (ja) * | 2014-07-29 | 2017-10-05 | ローム・アンド・ハース・エレクトロニック・マテリアルズ・コリア・リミテッド | 電子緩衝材及び有機エレクトロルミネセントデバイス |
EP3357981A4 (en) * | 2015-09-30 | 2018-08-08 | FUJI-FILM Corporation | Iron oxide dispersion for ink jet recording, method for producing same, and ink jet recording method |
WO2017148533A1 (en) * | 2016-03-04 | 2017-09-08 | Hp Indigo B.V. | Security liquid electrostatic ink composition |
JP2022017652A (ja) * | 2020-07-14 | 2022-01-26 | 東洋アルミニウム株式会社 | 被覆顔料 |
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Also Published As
Publication number | Publication date |
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US9637638B2 (en) | 2017-05-02 |
EP2808363A4 (en) | 2015-10-14 |
EP2808363B1 (en) | 2018-11-21 |
US20150005393A1 (en) | 2015-01-01 |
JPWO2013111771A1 (ja) | 2015-05-11 |
JP6116602B2 (ja) | 2017-04-19 |
JP5769820B2 (ja) | 2015-08-26 |
EP2808363A1 (en) | 2014-12-03 |
JP2015120927A (ja) | 2015-07-02 |
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