# US 11,441,008 B2 · Composite powder containing calcium carbonate and having microstructured particles

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- Number: US 11,441,008 B2
- Document ID: US11441008B2
- Status: Granted
- Kind: B2
- Application number: 16/330,668
- Filed: 2017-09-07
- Published: 2019-07-11
- Granted: 2022-09-13
- Earliest claimed: 2016-09-08
- Assignees: Schaefer Kalk GmbH & Co. KG
- Applicants: Schaefer Kalk GmbH & Co. KG
- Inventors: Marijan Vucak
- Web page: https://patentgrep.com/patent/US11441008B2

## CPC

- B33Y 70/00: Materials specially adapted for additive manufacturing
- C08K 3/26: Carbonates; Bicarbonates
- A61L 27/446: {with other specific inorganic fillers other than those covered by A61L27/443 or A61L27/46}
- A61L 27/58: Materials at least partially resorbable by the body
- A61P 19/00: Drugs for skeletal disorders
- C01F 11/181: {Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by control of the carbonation conditions}
- C01F 11/183: {the additive being an organic compound}
- C08J 3/124: {Treatment for improving the free-flowing characteristics}
- C08J 3/203: {Solid polymers with solid and/or liquid additives}
- C08K 7/18: inorganic
- C09C 1/0081: {Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound (C09C1/0015, C09C1/0078 take precedence)}
- C09C 1/021: {Calcium carbonates}
- C01P 2004/01: depicted by an image
- C01P 2004/32: Spheres
- C01P 2004/61: Micrometer sized, i.e. from 1-100 micrometer
- C01P 2004/62: Submicrometer sized, i.e. from 0.1-1 micrometer
- C08J 2367/04: Polyesters derived from hydroxy carboxylic acids, e.g. lactones (C08J2367/06 takes precedence)
- C08K 2003/265: {Calcium, strontium or barium carbonate}
- C08K 2201/005: Additives being defined by their particle size in general
- B33Y: ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- A61L: METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES (preservation of bodies or disinfecting characterised by the agents employed A01N; preserving, e.g. sterilising, food or foodstuffs A23; preparations for medical, dental or toiletry purposes A61K)
- A61P: SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- C01F: COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS (metal hydrides {monoborane, diborane or addition complexes thereof} C01B6/00; salts of oxyacids of halogens C01B11/00; peroxides, salts of peroxyacids C01B15/00; sulfides or polysulfides of magnesium, calcium, strontium, or barium C01B17/42; thiosulfates, dithionites, polythionates C01B17/64; compounds containing selenium or tellurium C01B19/00; binary compounds of nitrogen with metals C01B21/06; azides C01B21/08; {compounds other than ammonia or cyanogen containing nitrogen and non-metals and optionally metals C01B21/082; amides or imides of silicon C01B21/087}; metal {imides or} amides C01B21/092, {C01B21/0923}; nitrites C01B21/50; {compounds of noble gases C01B23/0005}; phosphides C01B25/08; salts of oxyacids of phosphorus C01B25/16; carbides C01B32/90; compounds containing silicon C01B33/00; compounds containing boron C01B35/00; compounds having molecular sieve properties but not having base-exchange properties C01B37/00; compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites, C01B39/00; cyanides C01C3/08; salts of cyanic acid C01C3/14; salts of cyanamide C01C3/16; thiocyanates C01C3/20; {double sulfates of magnesium with sodium or potassium C01D5/12; with other alkali metals C01D15/00, C01D17/00})
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)
- C09C: TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES (treatment of materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone C04B14/00, C04B18/00, C04B20/00); PREPARATION OF CARBON BLACK {; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS}
- C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS

## Abstract

A composite powder containing microstructured particles obtainable by means of a method in which large particles are combined with small particles, wherein the large particles have an average particle diameter within the range from 0.1 μm to 10 mm, the large particles comprise at least one polymer, the small particles are arranged on the surface of the large particles and/or distributed inhomogeneously within the large particles, the small particles comprise sphere-shaped precipitated calcium carbonate particles having an average diameter within the range from 0.05 μm to 50.0 μm, wherein the sphere-shaped calcium carbonate particles are obtainable by means of a method in which a. a calcium hydroxide suspension is initially charged, b. carbon dioxide or a carbon dioxide-containing gas mixture is introduced into the suspension from step a. and c. resultant calcium carbonate particles are separated off, with 0.3% by weight to 0.7% by weight of at least one aminotrisalkylenephosphonic acid being further added. Preferred application areas of the composite powder encompass its use as additive, especially as polymer additive, as additive substance or starting material for compounding, for the production of components, for applications in medical technology and/or in microtechnology and/or for the production of foamed articles. The invention therefore also provides components obtainable by selective laser sintering of a composition comprising a composite powder according to the invention, except for implants for uses in the field of neurosurgery, oral surgery, jaw surgery, facial surgery, neck surgery, nose surgery and ear surgery as well as hand surgery, foot surgery, thorax surgery, rib surgery and shoulder surgery. The invention also provides the sphere-shaped calcium carbonate particles which can advantageously be used to produce the composite particles according to the invention, and the use thereof.

## Claims

### Claim 1

A composite powder containing microstructured particles in which large particles are combined with small particles, wherein
the large particles have an average particle diameter within the range from 0.1 μm to 10 mm,
the large particles comprise at least one polymer,
the small particles are arranged on the surface of the large particles and/or distributed inhomogeneously within the large particles,
the small particles comprise sphere-shaped precipitated calcium carbonate particles having an average diameter within the range from 0.05 μm to 50.0 μm,
characterized in that
the sphere-shaped calcium carbonate particles are obtained by a method in which
a. a calcium hydroxide suspension is initially charged,
b. carbon dioxide or a carbon dioxide-containing gas mixture is introduced into the suspension from step a. and
c. resultant calcium carbonate particles are separated off,
with 0.3% by weight to 0.7% by weight of at least one aminotrisalkylenephosphonic acid being further added, and
the particles of the composite powder have an average particle size d50 within the range from 10 μm to less than 200 μm.

### Claim 2 (depends on 1)

The composite powder as claimed in claim 1, comprising calcium carbonate particles obtained by a method in which aminotrismethylenephosphonic acid, aminotrisethylenephosphonic acid, aminotrispropylenephosphonic acid and/or aminotrisbutylenephosphonic acid are added.

### Claim 3 (depends on 1)

The composite powder as claimed in claim 1, comprising calcium carbonate particles obtainable by a method in which the carbon dioxide or the carbon dioxide-containing gas mixture is introduced until the reaction mixture has a pH less than 9.

### Claim 4 (depends on 1)

The composite powder as claimed in claim 1, comprising calcium carbonate particles obtainable by a method in which the conversion of the calcium hydroxide suspension with the carbon dioxide or the carbon dioxide-containing gas mixture is carried out at a temperature less than 25° C.

### Claim 5 (depends on 1)

The composite powder as claimed in claim 1, comprising calcium carbonate particles obtainable by a method in which carbon dioxide or a carbon dioxide-containing gas mixture is introduced into the calcium hydroxide suspension at a gas flow rate within the range from 0.02 L CO2/(h*g Ca(OH)2) to 2.0 L CO2/(h*g Ca(OH)2).

### Claim 6 (depends on 1)

The composite powder as claimed in claim 1, characterized in that the sphere-shaped calcium carbonate particles have an average diameter less than 30.0 μm.

### Claim 7 (depends on 1)

The composite powder as claimed in claim 1, characterized in that the sphere-shaped calcium carbonate particles have a size distribution in which at least 90.0% by weight of all calcium carbonate particles have a particle diameter within the range of average particle diameter −30% to average particle diameter +30%.

### Claim 8 (depends on 1)

The composite powder as claimed in claim 1, characterized in that the sphere-shaped calcium carbonate particles have a shape factor, defined as the quotient formed from minimum particle diameter and maximum particle diameter, greater than 0.90.

### Claim 9 (depends on 1)

The composite powder as claimed in claim 1, characterized in that the large particles comprise at least one thermoplastic polymer.

### Claim 10 (depends on 1)

The composite powder as claimed in claim 1, characterized in that the large particles comprise at least one resorbable polymer.

### Claim 11 (depends on 10)

The composite powder as claimed in claim 10, characterized in that the resorbable polymer has an inherent viscosity, measured in chloroform at 25° C. and 0.1% polymer concentration, within the range from 0.3 dL/g to 8.0 dL/g.

### Claim 12 (depends on 1)

The composite powder as claimed in claim 1, characterized in that the large particles comprise poly-D-, poly-L- and/or poly-D,L-lactic acid.

### Claim 13 (depends on 1)

The composite powder as claimed in claim 1, characterized in that the large particles comprise at least one resorbable polyester having a number-average molecular weight within the range from 500 g/mol to 1 000 000 g/mol.

### Claim 14 (depends on 1)

The composite powder as claimed in claim 1, characterized in that the large particles comprise at least one polyamide.

### Claim 15 (depends on 1)

The composite powder as claimed in claim 1, characterized in that the large particles comprise at least one polyurethane.

### Claim 16 (depends on 1)

The composite powder as claimed in claim 1, characterized in that the proportion by weight of the precipitated calcium carbonate particles, based on the total weight of the composite powder, is at least 0.1% by weight.

### Claim 17 (depends on 1)

The composite powder as claimed in claim 1, characterized in that the composite powder comprise, based on the total weight of the composite powder, 40.0% by weight to 80.0% by weight of a poly-L-lactic acid (PLLA) and 20.0% by weight to 60.0% by weight of precipitated calcium carbonate particles.

### Claim 18 (depends on 1)

A method comprising adding a composite powder as claimed in claim 1 as additive, as additive substance or starting material for compounding, for the production of components, for applications in medical technology and/or in microtechnology and/or for the production of foamed articles.

### Claim 19 (depends on 1)

A component obtainable by selective laser sintering of a composition comprising a composite powder as claimed in claim 1, except for implants for uses in the field of neurosurgery, oral surgery, jaw surgery, facial surgery, neck surgery, nose surgery, ear surgery, hand surgery, foot surgery, thorax surgery, rib surgery and shoulder surgery.

### Claim 20

Sphere-shaped calcium carbonate particles obtained by a method in which
a. a calcium hydroxide suspension is initially charged,
b. carbon dioxide or a carbon dioxide-containing gas mixture is introduced into the suspension from step a. and
c. resultant calcium carbonate particles are separated off,
with 0.3% by weight to 0.7% by weight of at least one aminotrisalkylenephosphonic acid being further added.

### Claim 21 (depends on 20)

A method comprising adding the sphere-shaped calcium carbonate particles as claimed in claim 20 as additive for paper, plastics, paints, varnishes, elastomers, adhesives, sealants, in construction chemistry, in dry mortar and in medical technology, or in resorbable polymers.

### Claim 22 (depends on 1)

The composite powder as claimed in claim 1, characterized in that the sphere-shaped calcium carbonate particles have an average diameter less than 20.0 μm.

### Claim 23 (depends on 1)

A method comprising adding a composite powder as claimed in claim 1 as polymer additive, as additive substance or starting material for compounding, for the production of components, for applications in medical technology and/or in microtechnology and/or for the production of foamed articles.