WO1991011404A1 - Simulated colored granite and process - Google Patents
Simulated colored granite and process Download PDFInfo
- Publication number
- WO1991011404A1 WO1991011404A1 PCT/US1990/000383 US9000383W WO9111404A1 WO 1991011404 A1 WO1991011404 A1 WO 1991011404A1 US 9000383 W US9000383 W US 9000383W WO 9111404 A1 WO9111404 A1 WO 9111404A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- weight
- article
- methyl methacrylate
- particles
- microns
- Prior art date
Links
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
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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 5 granite and its production, using filler of alumina trihydrate (ATH) in syrup and pre-ground particles of ATH-filled polymer.
- ATH alumina trihydrate
- methyl methacrylate polymer selected from the group consisting of methyl methacrylate homopolymers and copolymers of methyl methacrylate with alpha-beta-ethylenically unsaturated compounds, and 30 (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;
- i i l h 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
- rheological additive such ' as core-shell particles of butadiene-styrene core grafted with polymethyl methacrylate to form the shell.
- the preferred particle size for B, C and D is between 2000 and 5000 microns.
- 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.
- 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 cajT ⁇ be used in the matrix.
- 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 permit significant improvement in aesthetics with sustained physical, chemical and mechanical properties.
- the problem of particle segregation as a result of the wide range of particles size preferably is prevented by the use of a thixotrope, using rheological additives, especially for the use of larger ground up particles above 2000 microns.
- the thixotrope can be organic or inorganic in nature. Without the thixotrope, the large particles tend to settle to the bottom and the smaller particles tend to float on the top during the polymerization process. As a result, the appearance of the surface is undesirable and uncontrollable due to the
- PMMA-butadiene styrene shell-core particles of about preferably in the range of 0.1-2 micron particle size, such as 0.2 microns manufactured by Kaneka Texas Corporation.
- 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.
- Kane ACE-B22 (Kaneka Texas Corporation) 1.0
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
TITLE SIMULATED COLORED GRANITE AND PROCESS Background of the Invention
This invention relates to simulated colored 5 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 10 white over U.S. Patents 4,085,246 (1978) and 4,159,301 (1979), both to Buser, Roedel and Vasilliou. U.S. Patent 3,7,75,,364"*:(-19 3) - Duggins, describes casting --~~ andTpolymerization systems useful in the present invention. All three of these patents are hereby 15 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 provides a preparative 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 25 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 30 (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 35 the article) particles in the size range of 100 to
5000 (preferably less than 2000 or less than 800) microns comprising a particle 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
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
i i l h 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 welght of the article) of pigments of selected colors in at least the matrix of A.
F. 0-5% by weight (based on the weight of the article) of rheological additive such' as core-shell particles of butadiene-styrene core grafted with polymethyl methacrylate to form the shell.
In some situations, the preferred particle size for B, C and D is between 2000 and 5000 microns. 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 cajT^be used in the matrix.
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.
The problem of particle segregation as a result of the wide range of particles size preferably is prevented by the use of a thixotrope, using rheological additives, especially for the use of larger ground up particles above 2000 microns. The thixotrope can be organic or inorganic in nature. Without the thixotrope, the large particles tend to settle to the bottom and the smaller particles tend to float on the top during the polymerization process. As a result, the appearance of the surface is undesirable and uncontrollable due to the
to eliminate the segregation by building the mix viscosity were unsuccessful. It is only when a thixotrope is used that the settling is eliminated. As a result of such additive, the appearance is greatly improved, a three-dimensional appearance is
contains PMMA-butadiene styrene shell-core particles of about preferably in the range of 0.1-2 micron particle size, such as 0.2 microns manufactured by Kaneka Texas Corporation.
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 sieve 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 to the indicated mesh sizes, which are all in the range of 100 to 5000 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 including metallic particles for a glittering appearance 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.
Exam le 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 5000 microns comprising a particle 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 5000 microns comprising a particle 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 5000 microns comprising a particle 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% igmen of selected color other than black and white;
E. 0-1% by weight (based on the weight of the article) of pigments of selected colors in at least the matrix of A; and
F. 0-5% by weight (based on the weight of the article) of rheological additive.
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. The article of claim 1 wherein the particles of B, C and O have a maximum size no larger than 2000 microns.
7. 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 5000 microns comprising a particle 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 5000 microns comprising a particle 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 5000 microns comprising a particle 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;
E. curing the composition to form the article; and F. 0-5% by weight (based on the weight of the article) of rheological additive.
8. The process of claim 7 wherein the white pigment of B is selected from the group consisting of titanium dioxide, barium sulfate, zinc sulfide and zinc oxide.
9. The process of claim 8 wherein the white pigment includes zinc oxide or zinc sulfide.
10. The process of claim 7 wherein the particles of B, -C and D have a maximum size no larger than 2000 microns.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2503106A JP2888632B2 (en) | 1990-01-29 | 1990-01-29 | Colored artificial granite and manufacturing method |
PCT/US1990/000383 WO1991011404A1 (en) | 1990-01-29 | 1990-01-29 | Simulated colored granite and process |
GB9117988A GB2245581B (en) | 1990-01-29 | 1991-08-20 | Simulated colored granite and process |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/US1990/000383 WO1991011404A1 (en) | 1990-01-29 | 1990-01-29 | Simulated colored granite and process |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1991011404A1 true WO1991011404A1 (en) | 1991-08-08 |
Family
ID=22220634
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1990/000383 WO1991011404A1 (en) | 1990-01-29 | 1990-01-29 | Simulated colored granite and process |
Country Status (3)
Country | Link |
---|---|
JP (1) | JP2888632B2 (en) |
GB (1) | GB2245581B (en) |
WO (1) | WO1991011404A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1993008993A1 (en) * | 1991-11-07 | 1993-05-13 | Akbar Ghahary | Mineral-like plastics |
EP0640651A1 (en) * | 1993-08-25 | 1995-03-01 | Röhm GmbH | Granite-like shaped body made of highly filled plastic material |
EP0731116A2 (en) * | 1995-03-07 | 1996-09-11 | Röhm Gmbh | Process for the preparation of highly filled polymers |
EP0781732A1 (en) * | 1995-12-29 | 1997-07-02 | Remmers Bauchemie GmbH | Resin/filler system for making coatings, plastic floors obtained therefrom and preparation thereof |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3192955B2 (en) * | 1996-01-09 | 2001-07-30 | エムアールシー・デュポン株式会社 | Composition for artificial granite and artificial granite |
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 |
US3775364A (en) * | 1971-11-11 | 1973-11-27 | R Duggins | Process for curing methyl methacrylate in the presence of peroxy catalysts |
US3847865A (en) * | 1972-04-28 | 1974-11-12 | Du Pont | Use of alumina trihydrate in a polymethyl methacrylate article |
US4085246A (en) * | 1975-06-18 | 1978-04-18 | E. I. Du Pont De Nemours And Company | Simulated granite and its preparation |
US4544584A (en) * | 1980-05-05 | 1985-10-01 | Ross Gilbert B | Cultured onyx products and methods therefor |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1990001470A1 (en) * | 1988-07-29 | 1990-02-22 | E.I. Du Pont De Nemours And Company | Simulated colored granite and process |
-
1990
- 1990-01-29 WO PCT/US1990/000383 patent/WO1991011404A1/en active Application Filing
- 1990-01-29 JP JP2503106A patent/JP2888632B2/en not_active Expired - Lifetime
-
1991
- 1991-08-20 GB GB9117988A patent/GB2245581B/en not_active Expired - Lifetime
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3488246A (en) * | 1966-08-31 | 1970-01-06 | Du Pont | Cast plastic simulated marble building product |
US3775364A (en) * | 1971-11-11 | 1973-11-27 | R Duggins | Process for curing methyl methacrylate in the presence of peroxy catalysts |
US3847865A (en) * | 1972-04-28 | 1974-11-12 | Du Pont | Use of alumina trihydrate in a polymethyl methacrylate article |
US4085246A (en) * | 1975-06-18 | 1978-04-18 | E. I. Du Pont De Nemours And Company | Simulated granite and its preparation |
US4159301A (en) * | 1975-06-18 | 1979-06-26 | E. I. Du Pont De Nemours And Company | Simulated granite and its preparation |
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 |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1993008993A1 (en) * | 1991-11-07 | 1993-05-13 | Akbar Ghahary | Mineral-like plastics |
EP0640651A1 (en) * | 1993-08-25 | 1995-03-01 | Röhm GmbH | Granite-like shaped body made of highly filled plastic material |
US5882560A (en) * | 1993-08-25 | 1999-03-16 | Roehm Gmbh Chemische Fabrik | Method for producing high filler content plastic molded articles which resemble granite |
EP0731116A2 (en) * | 1995-03-07 | 1996-09-11 | Röhm Gmbh | Process for the preparation of highly filled polymers |
EP0731116A3 (en) * | 1995-03-07 | 1998-05-13 | Röhm Gmbh | Process for the preparation of highly filled polymers |
EP0781732A1 (en) * | 1995-12-29 | 1997-07-02 | Remmers Bauchemie GmbH | Resin/filler system for making coatings, plastic floors obtained therefrom and preparation thereof |
Also Published As
Publication number | Publication date |
---|---|
JP2888632B2 (en) | 1999-05-10 |
JPH04504402A (en) | 1992-08-06 |
GB2245581B (en) | 1993-12-08 |
GB9117988D0 (en) | 1991-10-09 |
GB2245581A (en) | 1992-01-08 |
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