EP1824916A1 - Compositions resineuse durcissable et revetements de comptoirs resistants aux egratignures derives de ces compositions - Google Patents

Compositions resineuse durcissable et revetements de comptoirs resistants aux egratignures derives de ces compositions

Info

Publication number
EP1824916A1
EP1824916A1 EP04800941A EP04800941A EP1824916A1 EP 1824916 A1 EP1824916 A1 EP 1824916A1 EP 04800941 A EP04800941 A EP 04800941A EP 04800941 A EP04800941 A EP 04800941A EP 1824916 A1 EP1824916 A1 EP 1824916A1
Authority
EP
European Patent Office
Prior art keywords
anhydride
resinous composition
curable resinous
acid
sand
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP04800941A
Other languages
German (de)
English (en)
Inventor
James Michael Quackenbush
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Laboratory Tops Inc
Original Assignee
Laboratory Tops Inc
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 Laboratory Tops Inc filed Critical Laboratory Tops Inc
Publication of EP1824916A1 publication Critical patent/EP1824916A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B26/14—Polyepoxides
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • 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
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/2038—Resistance against physical degradation
    • 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
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K

Definitions

  • the invention relates to a curable resinous composition containing an epoxy resin and hardened scratch resistant countertops derived from such curable compositions.
  • the surfaces from these materials are generally designed for residential and light commercial use. They are not as durable physically or chemically as some applications require for long-term use. Further, some more expensive materials at about two to three times the price of the above materials can offer durability but again are priced at a range that limits many persons from enjoying such surfaces.
  • Some additional examples include an epoxy thermosetting material as part of a resin matrix and fill materials of metal or stone particles.
  • U.S. Patent No. 6,365,662 to Sakai discloses an artificial stone comprising an inorganic particle component of 82-93% by weight of a mixture of small and large particles of specific size ranges and a resin component of 7-18%.
  • the resin component can include thermosetting resins such as acrylics, methacrylics, unsaturated polyesters, and epoxies.
  • WO 99/00235 discloses a resin matrix bound to a substrate where the resin matrix contains a curable liquid resin, metal or stone particles, and a catalyst.
  • the curable resin can be acrylates, methacrylates, styrenes, methylstyrenes, allys, diallylphthalates, unsaturated polyesters, vinyl esters, urethanes and epoxies.
  • the catalyst can include aliphatic amines, aromatic amines, catalytic curing agents and acid anhydrides.
  • Other known efforts include using an epoxy resin in conjunction with an anhydride and silica as the fill material to form a mixture and then catalyzing the mixture with an amine.
  • the industry is still lacking in a particular process and corresponding product that combines the benefits of an epoxy resin with mineral fill materials in a particular manner to produce a commercially viable and relatively inexpensive manufactured structural synthetic surface.
  • the synthetic surface needs the combination of scratch resistance and hardness while being durable and impact resistant at a moderate costs. Therefore, there remains a need in the industry for such a material.
  • the invention relates to a resinous curable composition and hardened surfaces derived therefrom.
  • the resinous curable composition contains an epoxy resin and at least one carboxylic acid anhydride, along with multiple sized inorganic filler materials which serve to increase the loading capacity of the composition.
  • the composition is hardened in the presence of a heat-activated catalyst.
  • the resulting product is harder and more scratch resistant than other known commercially available materials and, further, is cheaper to produce.
  • the hardened surface may be a countertop such as a kitchen countertop, laboratory bench countertop and other type of working surface.
  • the curable resinous composition of the invention comprises:
  • the resinous composition of the invention employs dramatically less epoxy resin and more fillers than the formulations of the prior art. As such, the resinous compositions of the invention can be more economically produced than the compositions of the prior art. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
  • the curable resinous composition of the invention contains an epoxy resin.
  • the amount of epoxy resin in the resinous curable composition is less than 15 weight percent, typically less than 13 weight percent. In some cases, the amount of epoxy resin in the resinous curable composition may be as low as 6 weight percent. For instance, where granite chips and/or sand are used as the inorganic filler (D) of the curable resinous composition, the amount of requisite epoxy resin is generally half of that required in the more traditional epoxy resin formulations.
  • the epoxide resin may be a cycloaliphatic epoxide resin, i.e. a resin that has a least one epoxide group in which the oxygen atom is attached to carbon atoms in a cycloaliphatic ring, a N-glycidylamine, a polyglycidyl ester of a polycarboxylic acid or a polyglycidyl ether of a polyhydric alcohol or phenol.
  • epoxy resins contain aliphatic, cycloaliphatic or aromatic backbones.
  • One type of epoxy resin preferred for use in accordance with the invention is a polyfunctional epoxy composition containing at least three epoxide groups.
  • Preferred resin compositions include those comprising at least one glycidyl ether of a polyhydric phenol such as 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), bis(4- hydroxyphenyl)methane (bisphenol F), a phenol formaldehyde novolak or a cresol- formaldehyde novolak.
  • a polyhydric phenol such as 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), bis(4- hydroxyphenyl)methane (bisphenol F), a phenol formaldehyde novolak or a cresol- formaldehyde novolak.
  • epoxy resins preferred for this invention include 2,2- bis[4-(2,3-epoxypropoxy)phenyl]propane (diglycidyl ether of bisphenol A) and materials under the trade designation "Epon 828", “Epon 1004" and “Epon 1001F”, commercially available from Resolution Performance Polymers, "DER-331 ", “DER-332” and “DER-334”, commercially available from Dow Chemical Co.
  • Other suitable epoxy resins include glycidyl ethers of phenol formaldehyde novolac (e.g., "DEN-43 " and "DEN-428”, commercially available from Dow Chemical Co.). Such resins preferably have a weight average molecular weight less than about 20,000, most preferably less than 14,000.
  • Epoxy resins may further include monomeric epoxy resins as well as polymeric epoxy resins. These resins can vary greatly in the nature of their backbones and substituent groups.
  • the backbone may be of any type normally associated with epoxy resins and substituent groups thereon can be any group free of an active hydrogen atom that is reactive with an oxirane ring at room temperature.
  • substituent groups for epoxy resins include halogens, ester groups, ether groups, sulfonate groups, siloxane groups, nitro groups, and phosphate groups.
  • the polyfunctional epoxy compounds of the invention may be derived from any number of sources, including the reaction product of chlorohydrin compounds such as epichlorohydrin, glycerol dichlorohydrin, and beta-methylepichlorohydrin with polycarboxylic acid compounds including aromatic and aliphatic polycarboxylic acids such as tri and tetra carboxylic acids; with polyhydroxyl compounds such as alcoholic and phenolic polyhydroxyl compounds; with amine compounds comprising three or more amino hydrogen atoms including aliphatic, cycloaliphatic, and aromatic amines; with polythiol compounds; and with polyene type unsaturated cycloaliphatic compounds.
  • chlorohydrin compounds such as epichlorohydrin, glycerol dichlorohydrin, and beta-methylepichlorohydrin
  • polycarboxylic acid compounds including aromatic and aliphatic polycarboxylic acids such as tri and tetra carboxylic acids
  • polyhydroxyl compounds such as alcoholic and phenolic
  • desirable epoxy resins include those derived from saturated and unsaturated polyfunctional alcohols such as tetritols, pentitols, and hexitols such as sorbitol, and maltitol.
  • polyfunctional epoxies are aliphatic epoxy resins of hexitol polyglycidyl ethers such as sorbitols and maltitols.
  • Polyfunctional epoxy resins are available from suppliers such as Dow Chemical, Ciba Geigy, Rhone-Poulenc, Resolution Performance Polymers as well as from Dixie Chemical Company of Houston, Tex. which offers the sorbitol polyglycidyl ether as Dixie DCE 358.
  • the carboxylic acid anhydride for use in the invention typically comprises from about 4 to about 15, preferably from about 6 to about 10, weight percent of the curable composition.
  • Preferred as the carboxylic acid anhydride are aromatic acid anhydrides such as phthalic acid anhydride, isophthalic acid anhydride, terephthalic acid anhydride, pyromellitic acid and benzophenone-3,3',4,4'-tetracarboxylic acid as well as alicyclic aromatic acid anhydrides such as tetrahydrophthalic acid anhydride, methyltetrahydrophthalic acid anhydride, hexahydrophthalic acid anhydride, methylhexahydrophthalic acid anhydride, methylendomethylenetetrahydrophthalic acid anhydride, hexahydroterephthalic acid anhydride, 4-methyltetrahydrophthalic acid anhydride, tetrahydroisophthalic acid anhydride, endomethylenetetrahydrophthalic
  • More preferred blends include methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride and methylhexahydrophtahlic anhydride and especially preferred is a 45:55 to 55:45 weight ratio blend of hexahydrophthalic acid anhydride: methylhexahydrophthalic acid anhydride.
  • two or more carboxylic acid anhydrides are used; most preferably at least one carboxylic acid anhydride is an aromatic acid anhydride and the second is an alicyclic aromatic acid anhydride.
  • the aromatic acid anhydride is a flake material.
  • the molar ratio of aromatic acid anhydride:alicyclic aromatic acid anhydride is generally from about 1.2:0.8 to 0.8: 1.2.
  • the composition of the invention further contains as high as 75, and may be as high as 89, weight percent of inorganic filler.
  • inorganic filler loadings are higher than the permissible inorganic filler loadings of the compositions of the prior art formulations.
  • the amount of epoxy resin employed in the composition is reduced.
  • One of the inorganic fillers defined as “inorganic filler (D)" are particulates having high particle diameter sizes. For instance, 80% of the particulates of such inorganic fillers are typically characterized by a particle size greater than about 90 microns.
  • Such particulates are typically sand or chips of natural stone, such as granite, tuff, marble, sandstone and the like or a combination thereof.
  • the sand in addition to containing silica, may contain trace amounts of iron oxide, aluminum oxide, titanium dioxide, calcium oxide, and magnesium oxide as well as other oxides.
  • the use of natural stone chips is most preferred because the amount of epoxy resin required to be employed, when such chips are used as the inorganic filler, is almost half of that required in the epoxy resin formulations of the prior art. In a most preferred mode, at least 80% of the chips of natural stone have a particle size diameter greater than 1/8 inch.
  • the curable composition of the invention further contains a second inorganic filler, defined as "inorganic filler (C)".
  • inorganic fillers have much smaller average particle size diameter than inorganic fillers (D); typically, at least about 80% of the particles of inorganic filler (C) have a particle diameter size of from between about 10 to about 40 microns.
  • Exemplary of such inorganic fillers are naturally occurring inorganic materials such as silica stone, silica sand, diatomaceous earth, kaolin, halloysite, montmorillonite, bentonite, zeolite, phosphorite, diaspore, gibbsite, bauxite, Japanese acid clay, porcelain stone, pyrophyllite rock, feldspars, limestone, wollastonite, gypsum, dolomite, magnesite and talc.
  • the (second) inorganic filler is sand.
  • inorganic filler (C) is sand and inorganic filler (D) is sand and/or granite chips.
  • the weight ratio of the sand of inorganic filler C:inorganic filler D is typically 7:1 to about 1 :1.5. Particularly desirous results have been obtained where the inorganic filler D is a combination of sand and granite chips. In such instances, the weight ratio of the sand of inorganic filler C to the sand of inorganic filler D is approximately 1 :1 and the weight ratio of total sand (of inorganic filler (C) and inorganic filler (D)) to the granite chips is about 1 : 1.
  • the resinous composition of the further invention may be cured by heating, preferably in the presence of a heat activated catalyst.
  • Typical heat activated catalysts include cycloaliphatic and aromatic polyamiiies, polyhydric phenols or an imidazole.
  • 200 Sand refers to Unimin No. 200 sieve silica sand (80% of the particulates having a particle diameter size range of 10 to 40 microns);
  • 325 Sand refers to Unimin No. 325 sieve silica sand (80% of the particulates having a particle diameter size range of about 10 to 25 microns); 7010 Sand refers to Unimin No. 7010 sieve silica sand (80% of the particulates having a particle diameter size range of about 90 to 150 microns);
  • Epon 828 is a commercially available epoxy resin from Resolution Performance Polymers.
  • Liquid Anhydride Mix refers to ECA 10OH, available from Dixie Chemical Company of Houston, Tex., is a mixture of from about 0-5% by weight methyltetrahydrophthalic anhydride, 45-50% by weight hexahydrophthalic anhydride and 45 -50% by weight methylhexahydrophthalic anhydride; flake phthalic anhydride refers to melted flake phthalic anhydride, available from Koppers; and LINDAX 1 is l-(2 hydroxypropyl) imidazole heat activated catalyst, available from

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition résineuse durcissable comprenant (A) une résine époxyde, (B) au moins un anhydride d'acide carboxylique, (C) au moins une charge inorganique, au moins 80 % des particules de la charge possédant un diamètre compris entre 10 et 40 microns environ, et (D) au moins une charge inorganique, au moins 80 % des particules de la charge possédant un diamètre supérieur à 90 microns environ et étant constituées de sable et/ou de fragments de granite. La composition durcissable peut être durcie en présence d'un catalyseur pouvant être activé à la chaleur pour obtenir une surface dure résistante aux égratignures. Cette surface peut être utilisée comme surface de comptoir ou comme dessus de table de laboratoire. La composition peut contenir jusqu'à 89 % de charge inorganique.
EP04800941A 2004-11-10 2004-11-10 Compositions resineuse durcissable et revetements de comptoirs resistants aux egratignures derives de ces compositions Withdrawn EP1824916A1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2004/037419 WO2006052253A1 (fr) 2004-11-10 2004-11-10 Compositions resineuse durcissable et revetements de comptoirs resistants aux egratignures derives de ces compositions

Publications (1)

Publication Number Publication Date
EP1824916A1 true EP1824916A1 (fr) 2007-08-29

Family

ID=34959513

Family Applications (1)

Application Number Title Priority Date Filing Date
EP04800941A Withdrawn EP1824916A1 (fr) 2004-11-10 2004-11-10 Compositions resineuse durcissable et revetements de comptoirs resistants aux egratignures derives de ces compositions

Country Status (4)

Country Link
EP (1) EP1824916A1 (fr)
CA (1) CA2584418A1 (fr)
MX (1) MX2007005334A (fr)
WO (1) WO2006052253A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2098561A3 (fr) 2008-03-05 2011-03-09 Weatherford/Lamb, Inc. Formulation de matériau composite
US8383243B2 (en) 2008-12-10 2013-02-26 Xerox Corporation Composite containing polymer, filler and metal plating catalyst, method of making same, and article manufactured therefrom
PL218580B1 (pl) 2012-05-06 2014-12-31 Przedsiębiorstwo Amepox Spółka Z Ograniczoną Odpowiedzialnością Sposób wytwarzania żywicowanych płyt kamiennych
CN104583296A (zh) * 2012-07-02 2015-04-29 纳幕尔杜邦公司 改性的填料颗粒
GB201320831D0 (en) * 2013-11-26 2014-01-08 Friel Shaun High friction surface coating
IT201700102110A1 (it) * 2017-09-12 2019-03-12 Rosa Riccardo Salvatore La Composto, lapideorinforzato a basso peso, ottenuto da scarti di fanghi e polveri delle lavorazioni lapidee, processo di recupero dalle lavorazioni e metodo per l'utilizzo di detti materiali di risulta all'interno dello stabilimento di produzione o presso strutture esterne
CN117486533B (zh) * 2023-10-30 2026-04-28 泉州市新兴石材工艺有限公司 一种环保人造石英石制备工艺

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3594460A (en) * 1968-08-05 1971-07-20 Sheldon & Co E H Method for preparing a laboratory counter top
JPH10330647A (ja) * 1997-06-02 1998-12-15 Nippon Shokubai Co Ltd 透明性塗料組成物およびその硬化方法
CA2318122C (fr) * 1998-01-16 2007-10-23 Doppel Co., Ltd. Pierre reconstituee antiderapante
JP2000063679A (ja) * 1998-08-17 2000-02-29 Yamaha Ribingutetsuku Kk 熱硬化性樹脂組成物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2006052253A1 *

Also Published As

Publication number Publication date
MX2007005334A (es) 2007-09-11
WO2006052253A1 (fr) 2006-05-18
CA2584418A1 (fr) 2006-05-18

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