WO1990001470A1 - Simulated colored granite and process - Google Patents
Simulated colored granite and process Download PDFInfo
- Publication number
- WO1990001470A1 WO1990001470A1 PCT/US1989/003146 US8903146W WO9001470A1 WO 1990001470 A1 WO1990001470 A1 WO 1990001470A1 US 8903146 W US8903146 W US 8903146W WO 9001470 A1 WO9001470 A1 WO 9001470A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- weight
- methyl methacrylate
- article
- particles
- matrix
- Prior art date
Links
- 239000010438 granite Substances 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 title claims abstract description 7
- 239000002245 particle Substances 0.000 claims abstract description 37
- 229920000642 polymer Polymers 0.000 claims abstract description 16
- 239000003086 colorant Substances 0.000 claims abstract description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000004684 trihydrates Chemical class 0.000 claims abstract description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 38
- 239000011159 matrix material Substances 0.000 claims description 22
- 239000000049 pigment Substances 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 12
- 229920001519 homopolymer Polymers 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 5
- 239000006188 syrup Substances 0.000 claims description 5
- 235000020357 syrup Nutrition 0.000 claims description 5
- 241000220317 Rosa Species 0.000 claims description 3
- 238000005266 casting Methods 0.000 claims description 2
- 239000004576 sand Substances 0.000 claims description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 4
- 239000005083 Zinc sulfide Substances 0.000 claims 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims 4
- 239000012463 white pigment Substances 0.000 claims 4
- 239000011787 zinc oxide Substances 0.000 claims 4
- 229910052984 zinc sulfide Inorganic materials 0.000 claims 4
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims 4
- 239000004408 titanium dioxide Substances 0.000 claims 2
- 239000000470 constituent Substances 0.000 claims 1
- 239000003999 initiator Substances 0.000 claims 1
- 239000000178 monomer Substances 0.000 claims 1
- 230000003247 decreasing effect Effects 0.000 abstract description 2
- 239000000945 filler Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/36—Inorganic materials not provided for in groups C04B14/022 and C04B14/04 - C04B14/34
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44F—SPECIAL DESIGNS OR PICTURES
- B44F9/00—Designs imitating natural patterns
- B44F9/04—Designs imitating natural patterns of stone surfaces, e.g. marble
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B26/06—Acrylates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/54—Substitutes for natural stone, artistic materials or the like
- C04B2111/542—Artificial natural stone
Definitions
- This invention relates to simulated colored granite and its production, using filler of alumina trihydrate (ATH) in syrup and pre-ground particles of ATH-filled polymer.
- ATH alumina trihydrate
- the present invention provides a preparative process and a simulated granite article comprising
- methyl methacrylate polymer selected from the group consisting of methyl methacrylate homopolymers and copolymers of methyl methacrylate with alpha-beta-ethylenically unsaturated compounds, and
- Desirable sand-colored simulated granite can be made using brown and yellow pigmented particles, and pink to rose colored simulated granite can be made using red pigments in the particles. Similar pigments can be used in the matrix.
- the comparative test gave acceptable results but in different color families, black and white rather than sand or rose.
- the present invention is particularly useful.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Civil Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
Simulated granite in selected colors with increased levels of alumina trihydrate (ATH) and decreased amounts of pre-ground ATH-filled polymer particles of selected colors, and preparative process.
Description
SIMULATED COLORED GRANITE AND PROCESS Background of the Invention
This invention relates to simulated colored granite and its production, using filler of alumina trihydrate (ATH) in syrup and pre-ground particles of ATH-filled polymer.
This is an improvement for making simulated granite articles with colors other than black and white over U.S. Patents 4,085,246 (1978) and 4,159,301 (1979), both to Buser, Roedel and Vasilliou. U.S. Patent 3,775,364 (1973) - Duggins, describes casting and polymerization systems useful in the present invention. All three of these patents are hereby incorporated herein by reference.
U.S. Patent 4,544,584 - Ross (1985) describes technology for making simulated stone products including colorants. Summary of the Invention
The present invention provides a preparative process and a simulated granite article comprising
A. 60 to 99% by weight (based on weight of the article) of a matrix comprising
(1) 30 to 45% by weight (based on weight of the article) of methyl methacrylate polymer selected from the group consisting of methyl methacrylate homopolymers and copolymers of methyl methacrylate with alpha-beta-ethylenically unsaturated compounds, and
(2) 30 to 60% by weight (based on weight of the article) of alumina trihydrate particles having a maximum particle size less than
about 100 microns in the longest dimension;
B. 0.8 to 20% by weight (based on weight of the article) particles in the size range of 100 to 800 or 2000 microns comprising a matrix of methyl methacrylate polymer selected from the group consisting of methyl methacrylate homopolymers and copolymers of methyl methacrylate with alpha-beta- ethylenically unsaturated compounds, filled with (based on the weight of the particles) 50 to 70% by weight alumina trihydrate and up to 2.5% by weight pigment, having a clear to white color;
C. 0.1-10% by weight (based on weight of the article) of particles in the size range of 100 to 2000 microns comprising a matrix of methyl methacrylate polymer selected from the group consisting of methyl methacrylate homopolymers and copolymers of methyl methacrylate with alpha-beta-ethylenically unsaturated compounds, filled with (based on the weight of the particles) 0.1-2.5% pigment having a black color;
D. 0.1-10.0% by weight (based on weight of the article) of particles in the size range of 100 to 2000 microns comprising a matrix of methyl methacrylate polymer selected from the group consisting of methyl methacrylate homopolymers and copolymers of methyl methacrylate with alpha-beta-ethylenically unsaturated compounds, filled with (based on the weight of the particles) 0.1-2.5% pigment of selected color other than black and white; and
E. 0-1% by weight (based on the weight of the article) of pigments of selected colors in at least the matrix of A.
Detailed Description
In order to provide simulated granite articles with colors other than black and white and desirable aesthetics more economically, it has been discovered that the ATH content of the matrix should be increased above that normally used and to a particular narrow range within the general teachings of related art, while the content of ATH-filled particles should be decreased and appropriate pigments added to the particles. Optionally, the matrix can be pigmented at low levels. Since the particles can be more costly than the matrix resin, this permits cost savings.
Desirable sand-colored simulated granite can be made using brown and yellow pigmented particles, and pink to rose colored simulated granite can be made using red pigments in the particles. Similar pigments can be used in the matrix.
The content of ATH in the matrix is increased from a normal level near 30% to the range of 30 to 60%, preferably 45 to 55%. All parts, percentages and proportions are by weight, based on the weight of the article, except where indicated otherwise. Percentages of filler in pre-ground particles are by weight based on the weight of the particles themselves.
The content of pre-ground particles in the article preferably is down from a normally used 33% to 5-20%, more preferably at least about 10%. These changes, surprisingly, permit significant improvement in aesthetics with sustained physical, chemical and mechanical properties.
In the following examples and comparative test, formulations are presented which are processed as in the above-cited Buser et al patents and others known in the art to produce useful end product in the
form of flat sheet and shape such as kitchen sinks and bowls. The seive size series used are in the American Standard Sieve Series in which 25-50 mesh is 700-300 microns and 50-100 mesh is 300 to 150 microns.
The particles are preformed methyl methacrylate polymer (PMMA) filled with about 62 to 65% by weight ATH particles and comminuted by techniques known in the art, preferably cryogenically, to the indicated mesh sizes, which are all in the range of 100 to 800 microns. The total filler level is also indicated, showing how much ATH plus pre-ground particles are in the matrix syrup. Suitable pigments known in the art can be used.
The comparative test gave acceptable results but in different color families, black and white rather than sand or rose. For obtaining the colors other than black and white, the present invention is particularly useful.
Example 1
Claims
Claims 1. A simulated granite article comprising
A. 60 to 99% by weight (based on weight of the article) of a matrix comprising
(1) 30 to 45% by weight (based on weight of the article) of methyl methacrylate polymer selected from the group consisting of methyl methacrylate homopolymers and copolymers of methyl methacrylate with alpha-beta-ethylenically unsaturated compounds, and
(2) 30 to 60% by weight (based on weight of the article) of alumina trihydrate particles having a maximum particle size less than about 100 microns in the longest dimension;
B. 0.8 to 20% by weight (based on weight of the article) particles in the size range of 100 to 2000 microns comprising a matrix of methyl methacrylate polymer selected from the group consisting of methyl methacrylate homopolymers and copolymers of methyl methacrylate with alpha-beta-ethylenically unsaturated compounds, filled with (based on the weight of the particles) 50 to 70% by weight alumina trihydrate and up to 2.5% by weight pigment having a clear to white color;
C. 0.1-10% by weight (based on weight of the article) of particles in the size range of 100 to 2000 microns comprising a matrix of such methyl methacrylate polymer selected from the group consisting of methyl methacrylate homopolymers and copolymers of methyl methacrylate with alpha-beta-ethylenically unsaturated compounds, filled with (based on the weight of the particles) 0.1-2.5% pigment having a black color;
D. 0.1-10.0% by weight (based on weight of the article) of particles in the size range of 100 to 2000 microns comprising a matrix of such methyl methacrylate polymer selected from the group consisting of methyl methacrylate homopolymers and copolymers of methyl methacrylate with alpha-beta-ethylenically unsaturated compounds, filled with (based on the weight of the particles) 0.1-2.5% pigment of selected color other than black and white; and
E. 0-1% by weight (based on the weight of the article) of pigments of selected colors in at least the matrix of A.
2. The article of claim 1 in which the selected colors of the pigments of (D) are brown and yellow, and the article has an overall color similar to sand.
3. The article of claim 1 in which the selected color of the pigments of (D) is red and the article has an overall color in the range of pink to rose.
4. The article of claim 1 wherein the white pigment of B is selected from the group consisting of titanium dioxide, barium sulfate, zinc sulfide and zinc oxide.
5. The article of claim 4 wherein the white pigment includes zinc oxide or zinc sulfide.
6. A process of preparing a simulated granite article of claim 1 by:
A. preparing a matrix wet mix comprising about 60 to 99% by weight (based on the weight of the article) comprising about: (1) 30-45% by weight (based on the weight of the article) of a syrup of 10 to 35% by weight (based on the weight of the syrup) of methyl methacrylate polymer selected from the group consisting of methyl methacrylate homopolymers and copolymers of methyl methacrylate with alpha-beta- ethylenically unsaturated compound, the balance of said syrup being monomer of such methyl methacrylate polymer, and
(2) 30 to 60% by weight (based on the weight of the article) of alumina trihydrate particles having a maximum particle size less than about 100 microns in the longest dimension;
B. mixing with said matrix wet mix about:
(1) 0.8 to 20% by weight (based on weight of the article) particles in the size range of 100 to 800 microns comprising a matrix of methyl methacrylate polymer selected from the group consisting of methyl methacrylate homopolymers and copolymers of methyl methacrylate with alpha-beta- ethylenically unsaturated compounds, filled with (based on the weight of the particles) 50 to 70% by weight alumina trihydrate and up to 2.5% by weight pigment having a clear to white color;
(2) 0.1-10% by weight (based on weight of the article) of particles in the size range of 100 to 2000 microns comprising a matrix of such methyl methacrylate polymer selected from the group consisting of methyl methacrylate homopolymers and copolymers of methyl methacrylate with alpha-beta-ethylenically unsaturated compounds, filled with (based on the weight of the particles) 0.1-2.5% pigment having a black color;
(3) 0.1-10.0% by weight (based on weight of the article) of particles in the size range of 100 to 2000 microns comprising a matrix of such methyl methacrylate polymer selected from the group consisting of methyl methacrylate homopolymers and copolymers of methyl methacrylate with alpha-beta-ethylenically unsaturated compounds, filled with (based on the weight of the particles) 0.1-2.5% pigment of selected color other than black and white; and (4) 0-1% by weight (based on the weight of the article) of pigments of selected colors in at least the matrix of A;
C. adding an initiator system for the polymerizable constituent;
D. introducing the composition from (C) onto a casting surface or into a mold; and
E. curing the composition to form the article.
7. The process of claim 6 wherein the white pigment of B is selected from the group consisting of titanium dioxide, barium sulfate, zinc sulfide and zinc oxide.
8. The article of claim 4 wherein the white pigment includes zinc oxide or zinc sulfide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9006478A GB2230529B (en) | 1988-07-29 | 1990-03-16 | "simulated colored granite and process" |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US22624788A | 1988-07-29 | 1988-07-29 | |
| US22598988A | 1988-07-29 | 1988-07-29 | |
| US225,989 | 1988-07-29 | ||
| US226,247 | 1988-07-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1990001470A1 true WO1990001470A1 (en) | 1990-02-22 |
Family
ID=26920115
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US1989/003146 WO1990001470A1 (en) | 1988-07-29 | 1989-07-21 | Simulated colored granite and process |
Country Status (2)
| Country | Link |
|---|---|
| GB (1) | GB2230529B (en) |
| WO (1) | WO1990001470A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2233640A (en) * | 1989-01-11 | 1991-01-16 | Frank Brendan Devlin | Mineral composition |
| EP0639539A1 (en) * | 1993-08-17 | 1995-02-22 | Röhm Gmbh | Process for manufacturing of highly filled mouldings from polymethylmethacrylnate |
| EP0734828A1 (en) * | 1995-03-27 | 1996-10-02 | Atohaas Holding C.V. | Process for producing a thermoformable acrylic resin sheet, thermoformable acrylic resin sheet and shaped article having a granit-like appearance which has been obtained by thermoforming such a sheet |
| EP0731116A3 (en) * | 1995-03-07 | 1998-05-13 | Röhm Gmbh | Process for the preparation of highly filled polymers |
| US7247667B2 (en) * | 2004-03-23 | 2007-07-24 | E. I. Du Pont De Nemours And Company | Particle containing solid surface material |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991011404A1 (en) * | 1990-01-29 | 1991-08-08 | E.I. Du Pont De Nemours And Company | Simulated colored granite and process |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3488246A (en) * | 1966-08-31 | 1970-01-06 | Du Pont | Cast plastic simulated marble building product |
| FR2179022A1 (en) * | 1972-04-03 | 1973-11-16 | Du Pont | |
| US3847865A (en) * | 1972-04-28 | 1974-11-12 | Du Pont | Use of alumina trihydrate in a polymethyl methacrylate article |
| US4544584A (en) * | 1980-05-05 | 1985-10-01 | Ross Gilbert B | Cultured onyx products and methods therefor |
| EP0211657A2 (en) * | 1985-08-07 | 1987-02-25 | Nippon Shokubai Co., Ltd. | Curable composition, method for manufacture thereof and articles made therefrom |
-
1989
- 1989-07-21 WO PCT/US1989/003146 patent/WO1990001470A1/en active Application Filing
-
1990
- 1990-03-16 GB GB9006478A patent/GB2230529B/en not_active Expired - Lifetime
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3488246A (en) * | 1966-08-31 | 1970-01-06 | Du Pont | Cast plastic simulated marble building product |
| FR2179022A1 (en) * | 1972-04-03 | 1973-11-16 | Du Pont | |
| US3847865A (en) * | 1972-04-28 | 1974-11-12 | Du Pont | Use of alumina trihydrate in a polymethyl methacrylate article |
| US4544584A (en) * | 1980-05-05 | 1985-10-01 | Ross Gilbert B | Cultured onyx products and methods therefor |
| US4544584B1 (en) * | 1980-05-05 | 1991-07-02 | Cultured onyx products and methods therefor | |
| US4544584B2 (en) * | 1980-05-05 | 1998-06-30 | Spectrum 21 Licensing Corp | Cultured onyx products and methods therefor |
| EP0211657A2 (en) * | 1985-08-07 | 1987-02-25 | Nippon Shokubai Co., Ltd. | Curable composition, method for manufacture thereof and articles made therefrom |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2233640A (en) * | 1989-01-11 | 1991-01-16 | Frank Brendan Devlin | Mineral composition |
| EP0639539A1 (en) * | 1993-08-17 | 1995-02-22 | Röhm Gmbh | Process for manufacturing of highly filled mouldings from polymethylmethacrylnate |
| EP0731116A3 (en) * | 1995-03-07 | 1998-05-13 | Röhm Gmbh | Process for the preparation of highly filled polymers |
| EP0734828A1 (en) * | 1995-03-27 | 1996-10-02 | Atohaas Holding C.V. | Process for producing a thermoformable acrylic resin sheet, thermoformable acrylic resin sheet and shaped article having a granit-like appearance which has been obtained by thermoforming such a sheet |
| US5851606A (en) * | 1995-03-27 | 1998-12-22 | Atohaas Holding C.V. | Thermoformable acrylic resin sheet |
| US7247667B2 (en) * | 2004-03-23 | 2007-07-24 | E. I. Du Pont De Nemours And Company | Particle containing solid surface material |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2230529A (en) | 1990-10-24 |
| GB9006478D0 (en) | 1990-07-25 |
| GB2230529B (en) | 1992-01-15 |
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