ES2351468B1 - PROCEDURE FOR THE PREPARATION OF AN ORGANIC NANOCRISTALINE-COLORING CALCIUM HYBRID CERAMIC MATERIAL. - Google Patents

Abstract

Procedure for the preparation of a ceramic hybrid nanocrystalline calcium phosphate-organic dye material. # The prepared hybrid pigment is formed by an organic dye that functionalizes and directs the structure of a nanocrystalline calcium phosphate ceramic. The organic dye is obtained by condensation of a substituted nitrobenzaldehyde and is covalently and / or electrostatically bound to the nanocrystalline calcium phosphate matrix also forming microspheres that are located in the calcium phosphate matrix. # Both the hybrid pigment and the organic dye do not contain metals and are water resistant and can be used in numerous applications such as cement dyes, textile dyes and dyes of other consumer products.

Description

Procedure for the preparation of a hybrid ceramic nanocrystalline phosphate-organic dye material.

Technical sector

The present invention falls within the technical field of manufacturing pigments and dyes. More specifically, the invention relates to the preparation of hybrid pigments consisting of an organic dye that functionalizes a nanocrystalline calcium phosphate and can be applied as a dye from cements, textiles, general consumer products, dental implants or solar cells sensitive to dyes.

State of the art

Pigments based on ceramic materials are widely used to induce color and / or opacity to many synthetic items and are generally incorporated as small particles into paints, plastics and other materials.

There are different documents describing ceramic pigments for a wide variety of applications obtained by different procedures.

EP02014451 describes a compound of general formula M5 (AO) 4X3 where M is Ba, Sr, Ca or mixture of both, A is P, V or mixture thereof and X represents a mixture of Cu, O, OH -, F, Cl, Br, and / or I. The compound has apatite structure with Xsituated in the hexagonal channels and including C atoms. To prepare the compound, precursors of the elements M, AyXy are then mixed, a thermal treatment is mixed between 200 and 1700 ° C. The tone of the desired color is regulated using elements My and Different. The presence of copper is a Essential characteristic of the pigment because it brings brightness to the color. The compound can be used as a pigment in paints, plastics and other materials.

US 6630019 refers to non-toxic calcium phosphate dyes for use in food, pharmaceuticals and cosmetics, including calcium phosphate, aluminum hydroxide and nitrates. Calcium phosphate is in the form of particles coated with aluminum hydroxide that fixes the dye.

Other ceramic pigments obtained by the sol-gel method based on CoO-ZnO-SiO2 systems (Djambazov et al. Ceramics International 24, 1998) are also described in the literature. Starting from solutions of precursors of ZnyCoyde dissolution of SiO2, the gel is formed by gelation. Crystalline heat treatment is necessary above 500ºC.

Yuanet al. (J. Phys. Chem. B, 2006, 110, 388-394) have described a method for coating organic pigment particles with titanium, through a sol-gel process, to improve their weather resistance and dispersibility in alagua systems.

Although there are many compounds on the market that are effectively applied as pigments, it would be desirable to find new compounds and mixtures that have bright colors and are relatively cheap, stable to heating and light, water resistant, chemically compatible with the desired materials, not Toxic and harmless to the environment.

For this, the present invention is inorganic-inorganic hybrid rerefigments based on calcium phosphates. The dye by itself or the hybrid pigment could be an alternative to the existing dyes based on the azo group (-N = N-). Azo compounds can produce unwanted effects (such as allergic reactions or have a carcinogenic nature) and therefore many of them have been banned.

The dye object of the present invention does not contain any azo group and the hybrid pigment dye-apatite does not contain metal ions with possible harmful effects for living things such as aluminum or chromium, usually present in other dyes, which is an advantage from the environmental point of view.

Description

The hybrid material referred to in the present invention is a calcium phosphate nanocomposite (with apatite structure) -organic color obtained by a simple sol-gel method. The process is carried out at temperatures between 30 and 120 ° C and the final hybrid material has a uniform matrix at a nanometric scale.

In a first stage, an aqueous solution of a phosphate precursor salt is heated to a temperature of 30120 ° C and in the presence of a cationic surfactant. This cationic surfactant can be a quaternary ammonium surfactant such as decyltrimethyl ammonium bromide [CH3 (CH2) 9N (CH3) 3Br], dodecyltrimethyl ammonium bromide [CH3 (CH2) 11N (CH3) 3Br], dodecyltrimethyl ammonium chloride [CH3 (CH2 (CH2 (CH2) ) 11N (CH3) 3Cl], tetradecyltrimethyl ammonium bromide [CH3 (CH2) 13N (Br) (CH3) 3], tetradecyltrimethyl ammonium chloride [CH3 (CH2) 13N (Cl) (CH3) 3], hexadecyltrimethyl ammonium bromide [CH3 (CH2) 15N (Br) (CH3) 3] or chloridedehexadecyltrimethylammonium [CH3 (CH2) 15N (Cl) (CH3) 3].

Next, a substituted nitrobenzaldehyde dissolved in a low molecular weight alcohol (such as methanol or ethanol) is added and the mixture is stirred. Once this stage is completed, the temperature is lowered to 40-80 ° C and the mixture is brought to a basic level near 10. In this basic medium, a condensation process begins where a polymeric organic dye is formed mainly in the form of spheres and also as dissolved polymeric entities.

A calcium precursor salt is added to the resulting mixture.

A gel is thus obtained from which the nanocrystalline calcium phosphate hybrid pigment -organic organic pigment is recovered.

The dye is covalently and / or electrostatically bonded to the nanocrystalline calcium phosphate matrix and also forms microspheres.The pigment microspheres are homogeneously distributed in a matrix and will allow to obtain a uniform macroporosity in the material (pore diameter between 2.5 and 4.7 µm) after their extraction.

The resulting hybrid pigment does not contain any metallic bond that induces color. The dye has a melting point of about 230 ° C but withstands temperatures of 250 ° C without decomposing.

Lapatita can be demolished with clay or clay (calcium sulfate) according to its application. The hybrid organic-colored clay could also be used in other composite materials, resins, porcelain and metals. Ordinary cement is gray but there is also white cement. The dye or the organic apatite-dye hybrid system could be used as a durable dye (water resistant) for cement systems (general-purpose cement and clinkers).

In addition, since the organic dye appears to be thermally stable up to 230 ° C, it could be applied in other fields, such as the textile industry, which requires stable dyes up to 220 ° C-245 ° C.

On the other hand, both the organic dye and the hybrid pigment can be used in general consumer products, such as food, drug or cosmetic pigments.

The hybrid pigment can also be applied as a colored dental implant to coat the gingival part of the tooth.

The organic dye or hybrid pigment can be applied in the field of "dye-sensitizied solar cells" (DSSCs).

Brief description of the fi gures

Figure 1 shows a micrograph obtained by electron microscopy of the nanocrystalline calcium phosphate hybrid phosphate.

Embodiment of the invention

The invention is illustrated by the following example, which is not intended to limit its scope.

Example 1

An aqueous solution of a 0.26M concentration phosphate salt (precursor: sodium hydrogen phosphate dihydrate, Na2HPO4 * 2H2O) and bromide dehexadecyltrimethyl ammonium (CTAB) or trimethyl ammonium chloride (CTAC) are mixed at a temperature of 80 ° C for a time between 10 and 12 hours. 0.955g of 4-nitro benzaldehyde in 80mL of methanol (or ethanol) and stir for a time between 1 and 10 hours.Then the temperature is lowered to 60 ° C and ammonium hydroxide is added between 10 and 20mL until reaching a higher pH of 10 ° C. Continuation of the concentration of water is added at a concentration of 60m. : calcium chloride dihydrate CaCl2 * 2H2O) and stir between 1 and 4 hours.

The gel formed is fi ltered to obtain a hybrid nanocrystalline calcium phosphate hybrid dye - an intense red color. If it is allowed to age before filtering, keeping it in a solution for 5 days at 40 ° C, the hybrid material obtained darkens into a deep purple color.

The filtered calcium phosphate-colorarite gel hydride is washed with distilled and deionized water. The material obtained is dried at room temperature under pressure or at a lower temperature under vacuum conditions.

If the hybrid phosphate of calcium-filtrate dye is dried at a temperature between 30 and 90 ° C, the color changes from deep red to orange. But if the material is submerged in water at room temperature it returns to show the original red color.

After extraction and drying, the collected organic dye can be heated to temperatures up to 250 ° C without losing its color.

Claims (16)

1. Procedure for the preparation of a ceramic calcium phosphate pigment-organic dye comprising: (a) preparing a solution of a phosphate precursor salt in the presence of a surfactant and heating with stirring, (b) adding to the previous solution a Substituted nitrobenzaldehyde dissolved in a low molecular weight alcohol while stirring, then cool to room temperature and rise to an alkaline medium, (c) add a calcium precursor and stir the mixture until you obtain a (d) recover hybrid pigment.

2.

Process for the preparation of a ceramic calcium phosphate pigment-organic dye according to claim 1, wherein the calcium phosphate precursor salts are sodium hydrogen phosphate dihydrate and calcium dihydrate chloride forming a crystalline calcium phosphate.

3.

Process for the preparation of a calcium phosphate ceramic dye-organic dye according to previous claims, wherein the low molecular weight alcohol is methanol or ethanol.

Four.

Process for the preparation of a ceramic calcium phosphate pigment-organic dye according to previous claims, wherein the substituted nitrobenzaldehyde is meta-, ortho-para-nitrobenzaldehyde substituted and the surfactant is a cationic surfactant.

5.

Process for the preparation of a ceramic calcium phosphate pigment-organic dye according to previous claims, wherein the cationic surfactant is a quaternary ammonium surfactant such as decyltrimethyl ammonium bromide [CH3 (CH2) 9N (CH3) 3Br], dodecyltrimethyl bromide ammonium [CH3 (CH2) 11N (CH3) 3Br], dodecyltrimethyl ammonium chloride [CH3 (CH2) 11N (CH3) 3Cl], tetradecyltrimethyl ammonium bromide [CH3 (CH2) 13N (Br) (CH3) 3], tetradecyltrimethylammonium chloride [CH3 (CH2) 13N (Cl) (CH3) 3], hexadecyltrimethyl ammonium bromide [CH3 (CH2) 15N (Br) (CH3) 3] or chloridedehexadecyltrimethylammonium [CH3 (CH2) 15N (Cl) (CH3) 3].

6.

Process for the preparation of a ceramic calcium phosphate pigment-organic dye according to previous claims, wherein the pH is raised to a value close to 10 by adding ammonium hydroxide or sodium hydroxide.

7.

Process for the preparation of a ceramic calcium phosphate pigment-organic dye according to previous claims, wherein the hybrid pigment is recovered by filtration

8. Ceramic pigment calcium phosphate-organic dye obtainable through the claimed process.

9.

Use of the hybrid pigment claimed to provide color in composite materials, clays, resins, porcelains, metals and cement.

10.

Use of the hybrid pigment claimed to color textile materials.

eleven.

Use of the hybrid pigment claimed as a dye in general consumer products.

12.

Use of the hybrid pigment claimed in obtaining the solar cells of the DSSC type.

13.

Procedure for the preparation of an organic dye comprising the condensation of 4-nitrobenzaldehyde in methanol or methanol and in the absence or absence of a cone quaternary surfactant without addition of water at a temperature between 30 and 120 ° C and subsequent cooling below 80 ° C and addition of sodium hydroxide or ammonium hydroxide to reach a pH greater than 10.

14.

Process for the preparation of an organic dye according to claim 13, wherein the quaternary surfactant is a quaternary ammonium surfactant such as decyltrimethyl ammonium bromide [CH3 (CH2) 9N (CH3) 3Br], dodecyltrimethyl ammonium bromide [CH3 (CH2) 11N (CH3) 3Br], dodecyltrimethyl ammonium chloride [CH3 (CH2) 11N (CH3) 3Cl], tetradecyltrimethyl ammonium bromide [CH3 (CH2) 13N (Br) (CH3) 3], tetradecyltrimethyl ammonium chloride [CH3 (CH2) 13N (Cl) (CH3) 3], hexadecyltrimethyl ammonium bromide [CH3 (CH2) 15N (Br) (CH3) 3] or hexadecyltrimethyl ammonium chloride [CH3 (CH2) 15N (Cl) (CH3) 3].

15. Organic dye obtainable through the process claimed according to claims 13 and 14. SPANISH OFFICE OF THE PATENTS AND BRAND Application no .: 200901633 SPAIN Date of submission of the application: 23.07.2009 Priority Date: REPORT ON THE STATE OF THE TECHNIQUE 51 Int. Cl.: C09B67 / 20 (01.01.2006) C01B25 / 32 (01.01.2006) RELEVANT DOCUMENTS

Category

Documents cited Claims Affected

TO

US 2003129149 A1 (PIKE KATHLEEN S ET AL.) 07/10/2003 the whole document. 1-15

TO

JP 9328623 A (MARUO CALCIUM) 12/22/1997 summary; 1-15

TO

WO 0032700 A1 (ENGELHARD CORP) 06/08/2000 the whole document. 1-15

TO

HOFACKER, S., et al., Hybrid pigments via sol-gel processing, Journal of Sol-Gel Science and Technology, 1998, Vol. 13, pp. 479-484. Whole document. 1-15

Category of the documents cited X: of particular relevance Y: of particular relevance combined with other / s of the same category A: reflects the state of the art O: refers to unwritten disclosure P: published between the priority date and the date of priority submission of the application E: previous document, but published after the date of submission of the application

This report has been prepared • for all claims □ for claims no:

Date of realization of the report 07.12.2010

Examiner M. García Poza Page 1/4

REPORT OF THE STATE OF THE TECHNIQUE Application number: 200901633 Minimum documentation sought (classification system followed by classification symbols) C09B, C01B Electronic databases consulted during the search (name of the database and, if possible, terms of search used) INVENES, EPODOC, WPI, XPESP, CAPLUS State of the Art Report Page 2/4  WRITTEN OPINION Application number: 200901633 Date of Written Opinion: 07.12.2010 Statement

Novelty (Art. 6.1 LP 11/1986)

Claims Claims 1-15 IF NOT

Inventive activity (Art. 8.1 LP11 / 1986)

Claims Claims 1-15 IF NOT

The application is considered to comply with the industrial application requirement. This requirement was evaluated during the formal and technical examination phase of the application (Article 31.2 Law 11/1986).  Opinion Base.- This opinion has been made on the basis of the patent application as published. State of the Art Report Page 3/4  WRITTEN OPINION Application number: 200901633 1. Documents considered.- The documents belonging to the state of the art taken into consideration for the realization of this opinion are listed below.

Document

Publication or Identification Number publication date

D01

US 2003 129149 A1 (PIKE KATHLEEN S ET AL.) 10.07.2003

D02

JP 9328623 A (MARUO CALCIUM) 22.12.1997

D03

WO 0032700 A1 (ENGELHARD CORP) 08.06.2000

D04

HOFACKER, S., et al., Hybrid pigments via sol-gel processing, Journal of Sol-Gel Science and Technology, 1998, Vol. 13, pp. 479-484. Whole document.

2. Statement motivated according to articles 29.6 and 29.7 of the Regulations for the execution of Law 11/1986, of March 20, on Patents on novelty and inventive activity; quotes and explanations in support of this statement The object of the invention is a process for the preparation of a ceramic calcium phosphate pigment-organic dye. Document D01 discloses a process for preparing dyes of calcium phosphate particles that are coated with dye that is fixed to calcium phosphate with aluminum hydroxide. It starts from a suspension of calcium phosphate particles to which aluminum hydroxide is added. This suspension is colored by the addition of a dye. Document D02 discloses a process for preparing lacquers containing calcium phosphate as a dye carrier, in which the dye is deposited in calcium phosphate particles that have been prepared from calcium carbonate and orthophosphoric acid. Document D03 discloses hybrid pigments comprising a clay (kaolinite) and oxides or precursors of transition or post-transition metal oxides and combinations thereof. Document D04 discloses hybrid pigments prepared by a sol-gel process. These are organic pigments within inorganic matrices. None of the aforementioned documents, which are considered to be the closest state of the art, disclose a process for preparing an organic calcium phosphate-dye ceramic pigment comprising preparing a solution of a calcium phosphate precursor salt in the presence of a surfactant and heat with stirring; add to the solution a substituted nitrobenzaldehyde dissolved in a low molecular weight alcohool while stirring; add a calcium precursor salt and stir the mixture until a gel is obtained and the hybrid pigment is recovered. Therefore, in view of the state of the art, it is considered that the object of the invention set forth in claims 1 to 15 is new and has inventive activity (Arts. 6.1 and 8.1 LP). State of the Art Report Page 4/4