WO1991011404A1 - Simulated colored granite and process - Google Patents

Simulated colored granite and process Download PDF

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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
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WO
WIPO (PCT)
Prior art keywords
weight
article
methyl methacrylate
particles
microns
Prior art date
Application number
PCT/US1990/000383
Other languages
French (fr)
Inventor
Gin Guei Huang Ebnesajjad
Original Assignee
E.I. Du Pont De Nemours And Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by E.I. Du Pont De Nemours And Company filed Critical E.I. Du Pont De Nemours And Company
Priority to PCT/US1990/000383 priority Critical patent/WO1991011404A1/en
Priority to JP2503106A priority patent/JP2888632B2/en
Publication of WO1991011404A1 publication Critical patent/WO1991011404A1/en
Priority to GB9117988A priority patent/GB2245581B/en

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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
Figure imgf000003_0001
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
Figure imgf000004_0001
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
Figure imgf000004_0002
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.
Figure imgf000005_0001
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
Figure imgf000006_0001
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
Figure imgf000006_0002
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
Figure imgf000007_0001
Figure imgf000008_0001
Thixotrope -
Kane ACE-B22 (Kaneka Texas Corporation) 1.0
Figure imgf000009_0001

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.
PCT/US1990/000383 1990-01-29 1990-01-29 Simulated colored granite and process WO1991011404A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
PCT/US1990/000383 WO1991011404A1 (en) 1990-01-29 1990-01-29 Simulated colored granite and process
JP2503106A JP2888632B2 (en) 1990-01-29 1990-01-29 Colored artificial granite and manufacturing method
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

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Cited By (4)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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

Patent Citations (8)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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
GB2245581B (en) 1993-12-08
JP2888632B2 (en) 1999-05-10
JPH04504402A (en) 1992-08-06
GB9117988D0 (en) 1991-10-09
GB2245581A (en) 1992-01-08

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