JPH07501566A - Pigments with improved gloss - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] The present invention is doped with metal oxide particles and has high hiding power and improved optical Concerning flaky pigments with luster.

Flaky pigments that exhibit high gloss as well as satisfactory interference and moderate hiding power are often Until now, its manufacture has been difficult. In particular, colored pigments that are commonly produced by co-precipitation In the case of flaky pigments, the gloss and/or hiding power are often satisfactory. It wasn't. Similarly, flakes coated with one or more metal oxide layers The substrate exhibits interference and gloss, but due to the transparency of the material it is unsuitable. It only shows serious concealment ability.

It is true that hiding power is enhanced by precipitating a relatively coarse metal oxide layer. True, but this dramatically reduces the luster. flaky carrier material The use of metal substrates as well allows achieving high hiding power, but mostly It also gives rise to a metallic luster which is highly undesirable for use in.

Therefore, it has a high gloss with high hiding power and is particularly aesthetically appealing and yet usable. for flake pigments that extend and complement the range of pigments that can be used in flake form, especially colored pigments. There is a strong desire to do so.

Materials that have favorable properties, meet the above requirements, and are useful for industrial use. It is an object of the present invention to provide a novel pigment having the following properties.

It has been found that this object is achieved by the flaky pigments according to the invention.

Surprisingly, high gloss and improved pigments compared to pigments produced by conventional co-precipitation methods flake-like pigments with a high hiding power are combined with small metal oxide particles and/or dye particles. by hydrolyzing a metal salt solution in the presence of a metal oxide layer to precipitate the metal oxide layer. It became possible to manufacture.

The present invention therefore provides submicron sized metal oxide particles and/or dye particles. It consists of a flaky carrier material coated with an inorganic matrix containing , and its coating is extremely uniform, giving it a flaky coating with high gloss and hiding power. Provide pigments.

The present invention also provides a method for producing flaky pigments with improved gloss and hiding power. Ru. The method involves metal oxidation by hydrolysis of metal salts on a flaky substrate in an aqueous suspension. coated with a metal oxide or metal oxide hydrate layer and then separated; When cleaning, drying, and firing, (a) carrying out the hydrolysis in the presence of metal oxide particles and/or dye particles; ,and (b) The particle size is less than a micron.

The invention also provides an improved method for producing the pigment according to the invention and an improved use thereof. A method is also provided.

The pigments according to the invention can be applied to flaky inorganic carrier materials such as glass, kaolin, musk, etc. It consists of covite, ilmenite or particularly preferably mica. this The flaky material is a metal containing metal oxide particles and/or organic dye particles. coating by precipitation with a hydroxide layer, but the metal oxide Particles and/or organic dye particles are entrained during the precipitation of the hydroxide layer and are This is not coprecipitation in the usual sense.

The thickness of the flaky substrate is preferably between 0.1 and 5 μm, in particular between 0.2 and 4.5 μm. It is between. The dimensions in the other two directions are typically between l and 250 μm, particularly preferably The diameter is between 2 and 200 μm.

Suitable matrix oxides include, for example, silicon dioxide, silicates, boron dioxide, boron acid salts, aluminum oxides, aluminates or other, particularly preferably diacids. titanium chloride, as well as for the production of other flaky pearlescent pigments and colored luster pigments. All materials known to the public.

These materials generally contain suitable soluble metal salts, preferably halides, sulfuric acid, etc. Starting from salts or nitrates, particularly preferably chlorides, hydrolysis at appropriate pH Manufactured by

Size of metal oxide particles and/or organic dye particles included in the matrix The diameter is 110-40n, therefore, flaky pigment or obtained by co-precipitation Much smaller than metal oxides and dragged during matrix oxide precipitation and is housed in the interstices of the matrix filling, thereby increasing the A high packing density is achieved, thus also resulting in high hiding power and high gloss.

Metal oxide particles and/or organic dye particles are generally encapsulated in a random arrangement. and is preferably amorphous or spherical.

Suitable metal oxide particles are used as precursor elements of the matrix during the preparation of the pigment according to the invention. All stable inorganic oxides known per se that do not react with materials. metal oxidation The particles may be colored or colorless and are preferably in pure form. It is added in the form of However, mixtures of different metal oxides and/or organic pigments I am also considering using it. Some particularly suitable metal oxides are titanium dioxide (Ti O2), aluminum oxide (AlzOs), silicon dioxide (SiO2), tin oxide (SnOz), magnesium oxide (MgO), zinc oxide (ZnO), iron oxide , for example, Fe, O, or Fe-0, chromium oxide (Cr, 03), dioxide Cerium (CeO2), tungsten oxide (W○, ), molybdenum oxide (MOO) zirconium oxide (Zr02), but for example CrzFeO4, C.

It can also be a mixed oxide such as A1aO4 or N1A1tC1.

In addition to inorganic pigment particles, it is also possible to use organic pigment particles, in which case Particularly preferred are thermally stable organic pigments, which in many cases produce the pigments according to the invention. The conditions for By increasing the drying or baking time, you can reduce the stability of the Organic pigments can also be modified using other means in a manner that is also fully usable and durable. It is Noh.

Furthermore, the stability of organic pigment particles is increased by their encapsulation in the matrix. It is often acknowledged that it is a big deal. The organic pigment particles used are preferably For example, phthalocyanine, products made of basic dyes made into lakes with heteropolyacids, anthraquinone, phenazine, phenoxazine, diketopyrrolobirol or It is perylene.

The pigment particles exemplified here are known as well as their manufacturing methods (for example, H, chirachi, etc.). Written by xtttel Villasenschattrihier Fairaxgesellschaft (Wissengchaftliche Verlagagesellscha ft) Stuttgart, 1960, by G. Benzig. Pigments for coating agents Expert Verlag), and is generally commercially available.

However, these pigment particles are only described by way of example and do not merely reflect the invention. For the purpose of illustrating only and not limiting this in any way, clearly Beyond these aspects mentioned, a variety of other pigment particles can be utilized. Ru.

In many cases, for a better dispersion of pigment particles, e.g. non-ionic or ionic It is advantageous to mix the precursor solution with an onic commercial grade wetting agent. example For example, polyethylene glycol or polypropylene glycol are highly preferred. Although neither the type nor the amount of wetting agent added is critical, generally The proportion of lubricant is not more than 2% by weight of the dispersion.

In an advantageous embodiment of the pigment according to the invention, a flaky carrier material, preferably of the rutile type, is used. i. A titanium salt solution, preferably a titanium tetrachloride solution, also containing O2 particles. Coating mica by hydrolysis. These rutile-type particles are formed during precipitation. It is dragged into the interstices of the matrix. These serve as the nucleus for rutilation. Moreover, it also causes partial rutilization of the titanium dioxide coating.

The proportion of the amount of rutile in the matrix is generally from 0.5 to 40% by weight. Ru.

Rutile particles have an average diameter between 1 and 40 nm. As a result, high light A flaky pigment with brightness and high hiding power is obtained. In that pigment, the proportion of rutile type varies greatly depending on the firing temperature. Firing preferably at 700 and 1000℃ , particularly preferably between 800 and 900"C. Do not use other layers that cause silting, such as SnO layers.

Metal oxide coating of fine metal oxide particles with an average size of 110-40n The encapsulation into the internal voids is accompanied by a highly uniform coating and is obtained by co-precipitation. This results in a significant increase in hiding power and gloss compared to colored pigments.

In the case of the hiding power and colored pigments according to the invention, the pigment's ability to remain unchanged with viewing angle The absorption color can be changed over a wide range by changing the concentration of the pigment particles contained in it. It is possible to The ratio of encapsulated pigment particles to the matrix is typically Typically between 0.5 and 30%, especially between 2 and 20%.

Invention containing one or more encapsulated organic and/or especially inorganic colored pigments Pigments according to are preferred. Especially iron oxides, chromium oxides, cobalt oxides and Colored spinel, such as cobalt aluminum oxide (COA 1 * 04) ) is preferably used.

The pigment according to the invention is therefore an optical system with excellent optical properties and furthermore Its relative excellence is widely variable and optimal for specialized applications. This optimization is based on the 0 descriptions that can be It can be carried out routinely by those skilled in the art without any need.

Therefore, the pigment according to the present invention can be favorably evaluated in the range of industrially usable pigments. It shows that it has expanded in a number of ways, and it also has definite economic importance. It is.

The pigments according to the invention are described, for example, in US Pat. No. 3,087,328, DE 20 09 56 6, DE22 14545, DE25 22 572, DE25 22573, DE31 37 809, DE31 51354, DE31 51 355, D E32 11602 or DE 32 35 017, and coprecipitation can be synthesized by wet chemical reactions such as those used during pigment production by method. Wear.

A preferred method is to make an aqueous suspension of flaky substrate and apply it to 5 and 9. This suspension is then heated in the submicron range by heating to a temperature between 5°C and 0°C. The dissolution of metal salts in the presence of metal oxide and/or organic dye particles having a particle size of Add liquid. The particles are finely dispersed in a substrate suspension or in a metal salt solution. Gold may be added separately as an aqueous dispersion, but simultaneously added to the substrate suspension. Added as a genus salt solution. The pH of the substrate suspension simultaneously increases the hydrolysis of specific metal salts. by simultaneous addition of a base suitable for and within the range which results in precipitation of the corresponding hydroxide. maintain. During precipitation, previously added metal oxide and/or organic dye particles It becomes trapped in the voids in the oxide layer containing precipitated water. Ru. The coated substrates are separated, washed, dried and then heated to 400 and 1200°C. , preferably between 600 and 1000°C.

However, the substrate to be coated, the submicron particles to be encapsulated, producing a suspension containing metal salts and heating and/or bases; It is also possible to cause hydrolysis of metal salts by adding .

The following examples are intended to explain the invention in more detail and are not intended to limit it. All temperatures up to now and since then are expressed in degrees Celsius.

Example 1 100 g of mica are suspended in 2000 ml of water and heated to 75°C. Then acid with hydrochloric acid A solution of 1.6 g of 5nC14,.5Hz dissolved in 50ml of water was added to this reaction. Add to the suspension. Furthermore, at the same time, TiCl4 aqueous solution (TiC14280g / 1) 355 ml, Aerosil (Aeros + 1) 200 (Registered Trademark) (Degussa) Highly Dispersible Pyrogenic Silica, Particle Size 1O-2 0 nm) and Texopon Kl 2 (registered trademark) Hen From Henkel (wetting agent whose main ingredient is lauryl sulfate) 355 ml of the dispersion consisting of 355 ml of the following are added to the reaction mixture. Keep the pH constant during this addition. Maintain the value at 1.8. After the above chemical additions are completed, the desired end point of the coating is Mix the aqueous solution of TiC14 until a silver finish is reached. after that The mixture is stirred for 15 minutes to complete the reaction. Filters pigments and eliminates chlorides and dry at 120° C. for 16 hours. The dried pigment is then baked for 30 minutes. to be accomplished.

Pigment composition: 51% mica, 1% 5nai, 6% Aerosil 200 (registered trademark) , Tie, about 42%.

Example 2 Aerosil 200 (registered trademark) 12% was precipitated into a layer of TiO instead of 6%. Example 1 was repeated except that

Pigment composition: Mica 44%, SnO*12%, Aerosil 200 (registered trademark) 12 %, TiO□approximately 43%.

Example 3 Suspend 100 mg of mica in 2000 ml of water and heat to 75°C. this reaction Gradually add 5 g of micro titanium oxide MT 100-3 (registered trademark) to the mixture. Mixed with 300ml of titanium chloride aqueous solution (TiC14280g/l) mix into a suspended suspension. During the addition the pH is kept at a constant value of 1.8. After addition The reaction mixture is stirred for an additional 15 minutes to complete the reaction. then pigment Filter, wash free of chloride and dry at 120'C for 16 hours. drying After completion, the pigment is calcined at 80° C. for 30 minutes. The TiO2 layer is 20% rutile type and It consists of 80% anatase and anatase types.

Example 4 Example 3 was repeated except that the final firing temperature was increased to 850'C. 40 TiOz coating consisting of % rutile type and 60% anatase type. A flaky pigment having the following properties is obtained.

Example 5 Example 3 is repeated to coat the mica with a TiO2 layer by precipitation.

The dried product is fired at 900°C. Tie, rutile type with 30% layer, 70% layer Obtain flaky T i O2 coated pigment with anatase type composition .

Submission of translation of written amendment (Article 184-8 of the Patent Law) June 3, 1994

Claims (1)

[Claims] 1. High gloss and made of flaky carrier material coated with an inorganic matrix. A flaky pigment with concealing ability, whose matrix is in the range of microns or less. characterized by containing metal oxide particles and/or dye particles with a size of A flaky pigment with high gloss and hiding power. 2. Pigment according to claim 1, characterized in that the flaky substrate is mica. 3 The average size of the encapsulated metal oxide particles and/or dye particles is 10-4 Pigment according to claim 1, characterized in that it has a particle diameter of 0 nm. 4. The metal oxide particles added are rutile-type TiO2 particles. Pigment according to claim 1. 5 Metal oxides or gold are formed by hydrolysis of metal salts on flaky substrates in aqueous suspension. coating with a hydrated oxide layer, followed by separation, optionally washing, and drying A method for producing flaky pigments having improved gloss and hiding power upon firing. The hydrolysis of gold scrap oxide particles having a size in the submicron range and/or the above manufacturing method, characterized in that it is carried out in the presence of dye particles. . 6. Process according to claim 5, characterized in that the flaky substrate used is mica. 7 The average size of the metal oxide particles and/or dye particles is 10-40 nm. 6. A method according to claim 5, characterized in that: 6. Process according to claim 5, characterized in that TiO2 particles of the rutile type are added. 9. In formulations such as paints, dyes, plastics and cosmetics Use of pigments according to 6.