CN101208396A - 可喷涂的涂料组合物 - Google Patents
可喷涂的涂料组合物 Download PDFInfo
- Publication number
- CN101208396A CN101208396A CNA2006800179439A CN200680017943A CN101208396A CN 101208396 A CN101208396 A CN 101208396A CN A2006800179439 A CNA2006800179439 A CN A2006800179439A CN 200680017943 A CN200680017943 A CN 200680017943A CN 101208396 A CN101208396 A CN 101208396A
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- Prior art keywords
- resin
- composition
- matrix resin
- particle
- accelerator
- 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.)
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- -1 alkali metal carboxylate Chemical class 0.000 claims description 23
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 150000004684 trihydrates Chemical class 0.000 claims description 9
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 8
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- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
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- 239000007788 liquid Substances 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- BYKRNSHANADUFY-UHFFFAOYSA-M sodium octanoate Chemical compound [Na+].CCCCCCCC([O-])=O BYKRNSHANADUFY-UHFFFAOYSA-M 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- YPEWWOUWRRQBAX-UHFFFAOYSA-N n,n-dimethyl-3-oxobutanamide Chemical compound CN(C)C(=O)CC(C)=O YPEWWOUWRRQBAX-UHFFFAOYSA-N 0.000 claims description 2
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- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
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- 229940102838 methylmethacrylate Drugs 0.000 description 3
- 229940059574 pentaerithrityl Drugs 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 238000007761 roller coating Methods 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- KJJUCWRQGZGUFX-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 2-methylprop-2-enoate 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C.CC(=C)C(=O)OCCOC(=O)C(C)=C KJJUCWRQGZGUFX-UHFFFAOYSA-N 0.000 description 2
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
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- 229920005992 thermoplastic resin Polymers 0.000 description 2
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- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- SCBKKGZZWVHHOC-UHFFFAOYSA-N 2,2-bis(sulfanyl)propanoic acid Chemical compound CC(S)(S)C(O)=O SCBKKGZZWVHHOC-UHFFFAOYSA-N 0.000 description 1
- PSYGHMBJXWRQFD-UHFFFAOYSA-N 2-(2-sulfanylacetyl)oxyethyl 2-sulfanylacetate Chemical compound SCC(=O)OCCOC(=O)CS PSYGHMBJXWRQFD-UHFFFAOYSA-N 0.000 description 1
- MMEDJBFVJUFIDD-UHFFFAOYSA-N 2-[2-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC=C1CC(O)=O MMEDJBFVJUFIDD-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 241001251094 Formica Species 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- UQKKDJWFQBNZBJ-UHFFFAOYSA-N Polydin Natural products OC1C(O)C(O)COC1OC1=CC(O)=C(CC(O)C(O2)C=3C=C(O)C(O)=CC=3)C2=C1 UQKKDJWFQBNZBJ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- RSOILICUEWXSLA-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 RSOILICUEWXSLA-UHFFFAOYSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- NDWWLJQHOLSEHX-UHFFFAOYSA-L calcium;octanoate Chemical compound [Ca+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O NDWWLJQHOLSEHX-UHFFFAOYSA-L 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 229940120693 copper naphthenate Drugs 0.000 description 1
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
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- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- GYVGXEWAOAAJEU-UHFFFAOYSA-N n,n,4-trimethylaniline Chemical compound CN(C)C1=CC=C(C)C=C1 GYVGXEWAOAAJEU-UHFFFAOYSA-N 0.000 description 1
- NTMXFHGYWJIAAE-UHFFFAOYSA-N n,n-diethyl-3-oxobutanamide Chemical compound CCN(CC)C(=O)CC(C)=O NTMXFHGYWJIAAE-UHFFFAOYSA-N 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- ZVUVJTQITHFYHV-UHFFFAOYSA-M potassium;naphthalene-1-carboxylate Chemical compound [K+].C1=CC=C2C(C(=O)[O-])=CC=CC2=C1 ZVUVJTQITHFYHV-UHFFFAOYSA-M 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000010125 resin casting Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 description 1
- 229940082004 sodium laurate Drugs 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000012905 visible particle Substances 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/28—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for wrinkle, crackle, orange-peel, or similar decorative effects
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
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Abstract
可喷涂的花岗石样涂料组合物,其可用于形成模拟的石材表面,比如抛光的花岗石,这样的表面具有高的冲击强度、优良的硬度和美学上令人愉悦的外观。该涂料组合物包括基于不饱和可交联的聚酯或丙烯酸类树脂的凝胶树脂基质、固化加速剂组合物和包括热固性树脂或者热塑性树脂与热固性树脂的混合物的颗粒。凝胶涂料树脂和颗粒在视觉上可区分,两者基本不相混溶并且密度基本相同。该组合物的特征在于形成了厚度均一并快速固化的涂层,该涂层即使在厚度薄时也可提供均一的花岗石外观。
Description
发明背景
本发明通常涉及用于形成模拟各种天然石物质例如卵石、花岗石、大理石等的合成表面的组合物,并且更特别地,涉及包括能够喷涂到水平和直立固体表面的有机树脂材料的组合物,当该组合物固化时,可模拟各种天然物质,例如花岗石。
目前存在形成合成材料和表面的方法,该方法可以模拟各种天然物质如石材、大理石等的外观。这样的材料通常用于制造地板和其他类型的瓷砖、浴室隔板、工作台面、水槽、建筑饰面(architectural facings)、装饰物(ornamental object),并且通常用于任何其他使用大理石、石材等的用途。
一个这样的实例是利用市售商标为FORMICA的层压板材料的方法。把这样的材料形成大的板材(sheets),然后将其切割并通过粘合剂等将其应用于期望的表面。这样的板材可以制造成单色或者各种图案,其中的一些模拟了各种石材或其他纹理材料。
另一个实例是用于制备通常称作“人造大理石(Cultured Marble)”的材料的方法。通过首先制造所需形状的模具,并将凝胶涂料喷涂到模具的内表面,然后用常规的铸模树脂来填充模具而形成“人造大理石”。向树脂中添加颜料以使其具有期望的颜色或图案。在树脂固化后,将模具移出,面向该模具的表面形成最终产品的外表面。
虽然许多用于制造模拟石材等的合成表面的现有技术方法一般是可接受的,但是仍不断地努力开发可以提供更加均一、更加光滑的涂层以及更加精密地模拟各种天然材料的表面(例如抛光的卵石、大理石或花岗石等)的组合物,。因此,不断地需要并且希望改善现存的方法。
适合的凝胶涂料的实例可以在以下专利中找到:1985年9月24日授予Smith的美国专利第4,543,366号,1991年7月2日授予Lathrop的美国专利第5,028,459号以及1987年5月12日授予Genovese等人的美国专利第4,664,982号,每篇专利的内容通过引用结合入本文。为了获得模拟石材涂层,基体树脂必须含有提供石材外观的固体填充剂。这样的石材填充剂具有的密度比基体树脂的密度高很多,因此易于沉降而使得涂层无法提供期望的模拟石材外观。已经开发了各种方法以解决这个问题。例如,Lathrop使用了密度基本上大于凝胶涂料的碎石集料(crushed stoneaggregate)。因此,为了获得三维的展示,必须应用连续多层的凝胶涂料和基质。本发明通过使用密度基本上与基体树脂组合物相等的颗粒和通过控制交联反应以预防沉降而克服了这个问题。
在1991年8月27日授予Nogi等人的、美国专利第5,043,377号关于浇铸模制花岗石样人造石的内容中,解决了相似的问题。Nogi等人将固化的、含有大比例填充剂的热塑片悬浮在热塑性树脂浇铸组合物中,并指出热塑片与液体基质的比重应彼此相近。但是在喷涂组合物中,通过使用热固性树脂作为基体树脂并通过控制交联和固化的速率来获得没有沉降的更加均一的结果。
授予Akbar Ghahary的美国专利第5,476,895号公开了基于使用热固性基体树脂和含有无机填充剂的交联树脂颗粒的概念的可喷涂涂料组合物。该颗粒和基质基本上具有相同的密度。虽然这样的组合物可用于喷涂应用,但是它们对粘度变化极为敏感并且在其充分交联以固定之前使该涂料流动的过程中经常无法提供均一的厚度,尤其是当将涂料组合物喷涂到直立的表面时。
本发明提供了在室温下喷涂时提高基体树脂聚合速率而不会使基体树脂基体脱色的方法,以便形成更加均一的模拟石材的涂层。可以将本涂料组合物直接喷涂、刷涂、滚涂或幕墙涂布(curtain walled)到作为最终覆盖喷涂(over spray)的表面上,或者将其喷涂、刷涂、滚涂或幕墙涂布到模具的内表面上,然后用基质(例如玻璃纤维或树脂)加衬。
发明概述
本发明提供用于形成具有模拟抛光的石材(例如花岗石)表面的涂层的物质组合物。该涂料组合物包括可交联的液体基体树脂、细粒交联的树脂填充剂(在下文中也称为颗粒)以及聚合加速剂系统。基体树脂和颗粒具有基本相同的密度,其意味着所述颗粒在喷涂和固化步骤中不会由于重力而出现可见的沉降。术语细粒预期表征所述颗粒在基体树脂中是基本上不相混的。
可以通过使用商业可获得的喷涂设备来使涂料组合物与基材接触而将本发明的涂料组合物喷涂到任何固体基材上。显然,尽管该涂料组合物被设计用于喷涂应用,但是其也可以用于其他的应用涂料的方法,例如涂漆或浇铸。这与许多现有技术的组合物不同,现有技术的组合物适合作为浇铸树脂,但是不能提供在基体树脂交联中需要更高反应速率的喷涂组合物。此外,其与可得的涂料组合物不同,本发明的组合物可用来喷涂到直立的表面上,并且还能在这样的表面上形成均一的涂层。
发明详述
本发明可喷涂的涂料组合物包括基体树脂、颗粒和加速剂系统的三组分系统,其关键特征是在喷涂和固化步骤期间没有可见的颗粒沉降并且在喷涂和固化步骤期间涂层无实质性流动,从而提供了均一的厚度。本发明组合物的另一个关键特征是它们可以在室温喷涂和固化。
优选的可交联的基体树脂是工业上已知的、作为凝胶涂料树脂的不饱和聚酯树脂。它们一般包括低分子量的直链树脂,该直链树脂通过苯二甲酸组分与二醇的缩合以及与不饱和组分(诸如马来酐)的缩合获得,从而提供交联性能。通常将聚酯溶解于诸如苯乙烯的芳香族单体中,所述单体在聚酯树脂的聚合开始时起该聚酯树脂的交联剂的作用。除苯乙烯外,可以通过加入其他单体(例如丙烯酸或丙烯酸酯)使聚酯改性以获得特定的性能。还可将直链的二羧酸(例如己二酸)或其他的脂肪酸加入苯二甲酸组分中以增加柔韧性。优选的不饱和聚酯树脂是间苯二酸酐和新戊二醇(NPG)的缩合产物。这些树脂可以作为凝胶涂料树脂从多种来源商购获得,例如Reichhold、Ashland、Lilly Industries、Valspar和Polydine。另一种可采用的基体树脂是基于如下单体的丙烯酸类树脂:悬浮在现有技术已知为浆的丙烯酸酯单体中的甲基丙烯酸甲酯、丙烯酸乙酯。为了交联丙烯酸类树脂,向所述浆中加入二不饱和丙烯酸酯单体。这样的二不饱和单体包括异丁烯酸缩水甘油酯和乙二醇二甲基丙烯酸酯二丙烯酸乙二醇酯(ethylene dimethacrylate ethylene glycol diacrylate)、二乙烯基苯、邻苯二甲酸二烯丙酯和丙烯酸烯丙酯或异丁烯酸烯丙酯。丙烯酸酯树脂可以被进一步改性以含有附加至或取代所述低分子量丙烯酸类树脂的聚氨酯。
通常通过加入自由基引发剂,且优选为过氧偶氮化合物,来引发可喷涂的基体树脂的聚合反应,所述过氧偶氮化合物如过氧化甲乙酮、过苯甲酸叔丁酯和2,2′偶氮二异丁腈月桂酰过氧化物。
通常期望在基体树脂中包括无机填充剂或填料,以部分提供模拟石材外观的细粒背景颜色,以及部分获得与有待加入的颗粒基本上相等的密度。为了改善喷涂组合物的喷涂性和均一性,另一种优选的添加剂是触变剂,如火成二氧化硅。同样地,可加入其他增加氧化稳定性、紫外线抵抗阻燃性(fire retardency)或温度稳定性的成分。
将第二种组分、颗粒混入液体基体树脂以便形成可喷涂的组合物并提供复合物的模拟石材外观。如此处所用,术语“颗粒”包括经常被本领域技术人员提及的术语“碎屑(chips)”和“细粒”。颗粒可由基体树脂中采用的相同的树脂获得。因此,可以采用不饱和聚酯和丙烯酸类树脂来形成颗粒。可以将树脂与无机填充剂、颜料和任何其他需要的添加剂混合,以便在以细粒形式与基体树脂交联后混合时,提供模拟石材的性能。可以通过使用具有不同密度的填充剂组合来调整颗粒树脂的密度。虽然无机填充剂通常比树脂更重并且因此增加了颗粒的密度,但是这种增加可以通过使用较轻的填充剂(例如玻璃微泡或火成二氧化硅)来抵消。通过将树脂浇铸进敞口的模具,交联该树脂,且随后将该树脂粉碎成范围在10至200U.S.目径之间的期望的粒径来形成颗粒。优选的平均粒径范围为200微米至500微米。虽然该颗粒提供了“花岗石样”的石材外观,但是它们并不显著降低凝胶涂层完全透明的特征。在颗粒的形成中使用的优选填充剂是三水氧化铝,其通常使用的浓度是颗粒重量的10%至60%。其他可使用的填充剂包括碱土金属碳酸盐和硅酸盐,例如碳酸钙或石灰石、滑石、粘土、石膏、白垩或大理石。由于天然的石材具有含有不同着色颗粒的外观,因此一般需要向颗粒树脂中加入颜料,例如加入二氧化钛以便获得白色的颗粒,以及加入碳黑以便获得黑色的颗粒。
颗粒还优选含有热塑性树脂组分,该组分的存在增加了颗粒与基体树脂之间的界面粘合。这样的热塑性组分可以通过加入过量的上述单体获得,过量的单体是交联形成热塑性组分所需要的。因此,在不饱和聚酯树脂的情况下,提供过量的苯乙烯以使该颗粒除了交联的聚酯外,还含有一些热塑性聚苯乙烯。在文献例如美国专利5,476,895中描述了如本发明所使用的颗粒的制备,其通过引用结合入本文。
本发明的可喷涂组合物的第三种组分是加速剂,其通过加速基体树脂的交联来使有待喷涂的组合物不产生流动或变薄并且不形成颜色,特别是在室温喷涂条件下。本发明的加速剂至少为两组分并且优选为三组分的混合物,其包括:(a)碱金属羧酸盐或氢氧化钙或羧酸钙,其中羧酸盐具有6至22个碳原子,(b)包括二氮取代的酰胺、三氮取代的胺或硫取代的硫醇的杂有机化合物,和(c)任选的重金属化合物,所述重金属化合物选自铜、钴和锌的羧酸盐类,其中该羧酸盐具有6至22个碳原子。适合的碱金属羧酸盐的实例一般包括辛酸钠、苯甲酸钠、环烷酸钠、月桂酸钠以及钠和钾的脂肪酸羧酸盐。叔酰胺化合物包括N,N′-二甲基乙酰乙酰胺和N,N′二乙基乙酰乙酰胺。在加速剂组合物中有用的叔胺包括二甲基对甲苯胺、二乙苯胺、二甲苯胺、N,N-双(2-羟乙基)对甲苯胺和N,N-双-(2-羟丙基)甲苯胺。在加速剂中有用的硫醇包括乙二醇二硫醇基乙酸酯、乙二醇二巯基丙酸酯、3-巯基丙酸异辛酯、季戊四醇四-(3-巯基丙酸酯)和三羟甲基丙烷三-(3-巯基丙酸酯)。各组分通常的使用范围为基体树脂重量的0.1%至5%。在不饱和聚酯树脂的情况中,优选采用确定的、取代的氮化合物和碱金属羧酸盐,而在丙烯酸类树酯的情况中,优选采用取代的硫醇与碱土金属羧酸盐的组合。在基体树脂组合物中,本发明的加速剂是获得期望的涂层性能的必需组分,但是其在颗粒的制备中也可以任选地使用。
所制得的涂层一般为透明或高度透明的涂层,其中具有足量的三水氧化铝以遮盖被涂布物体的颜色。这样的涂层在常规凝胶涂层分解的温度下往往更稳定。这种稳定性的增加可归因于由三水氧化铝提供的导热性和热耗散。本涂料一般比目前市场上可得的涂料具有更高的冲击强度。在迄今为止进行的测试中,已显示本涂料与目前可得的涂料相比,展示出两倍的冲击强度和更大的硬度。
将本物质组合物正常混合,然后通过常规的喷涂装置进行喷涂。尽管此处未对这样的喷涂装置进行详细的描述,但是其对于涂料领域的技术人员而言是公知的。可选地,该组合物可以被刷涂、滚涂、幕墙涂布或通过其他方式应用。
以下的实施例显示了在本发明的涂料组合物中使用的颗粒的制备。
实施例A
使用以下成分来制备100lbs.的白色颗粒聚酯组合物
40lbs. 商购获得的、含有苯乙烯单体的间苯二酸酯/新戊
二醇树脂(Reichhold 32168-20)
40lbs. 填充剂-三水氧化铝
4lbs. 颜料-二氧化钛
15lbs. 轻质填充剂-3M玻璃微泡(glass microbubbles)
1lb. 催化剂-“Triganox KSM”
将前述聚酯组合物在除去空气的真空混合器中混合。然后将材料转移到封闭的金属模具中,并在炉中于300_加热一(1)小时。将所得的固化交联树脂从模具中取出并在制粒机中压碎到不超过1/4″的直径。然后将颗粒状材料转移至粉碎机(pulverizing machinery)以制造最终在树脂A中悬浮的各种粒径。然后将粉碎的材料转移至分粒机(classificationmachinery)以分离各种粒径并除去不能在U.S.140目筛上保留的颗粒。比U.S.140目筛更细的颗粒能够增加最终可喷涂的表面材料的粘度并改变其颜色。通过使用碳黑代替二氧化钛来制备黑色的颗粒。
实施例B
以下100lbs的白色丙烯酸类树脂颗粒由下述组分制成
40lbs. 商购获得的、含有MMA单体的聚甲基丙烯酸甲酯
(polymethylmetharylate)浆(Degussa Corp)
40lbs. 填充剂-三水氧化铝
4lbs. 颜料-二氧化钛
15lbs. 轻质填充剂-3M玻璃微泡
0.25lbs. 硫醇
1lb. 催化剂-Experox 41-25
将丙烯酸组合物在除去空气的真空混合器中混合。然后将材料转移到封闭的金属模具中,并在室温下于炉中固化一(1)小时,然后在212_后固化30分钟。然后按照实施例A所述的方法将所得的交联丙烯酸类树脂粉碎成颗粒。通过使用碳黑代替二氧化钛来制备黑色的丙烯酸类树脂颗粒。
以下对本发明可喷涂的涂料组合物进行了举例说明。
实施例I
含有以下组分(以重量计)的可喷涂聚酯涂料材料的制备:
60% 商购获得的、含有苯乙烯单体的可交联的聚甲基丙烯酸甲酯/
新戊二醇树脂(Reichhold 32168-20)
5% “3M”玻璃微泡
10%* 表面处理的三水氧化铝(ATH),平均粒径15微米,用于增
强表面硬化性能和阻燃性
25% 按实施例A方法制备的白色颗粒和黑色颗粒的50/50混合物
0.5% 辛酸钠
0.25% N,N″-二甲基乙酰乙酰胺
0.15% 辛酸钴
*ATH优选用硅烷偶合剂处理以改善基体树脂与填充剂之间的接触。
将组合物的各组分在轻微搅动下混合,直到不溶组分均匀分布于基体树脂,得到粘度为大约4,000cps(4号转子)的组合物。当与过氧化物引发剂混合时,这种组合物在喷涂到硬表面上时可迅速交联。
实施例II
含有以下组分(以重量计)的、可喷涂的丙烯酸类树脂涂料组合物的制备:
40% 甲基丙烯酸甲酯树脂(Degament 1004)
5% 丙烯酸氨基甲酸乙酯(Sartomer CN-991)
5% 甲基丙烯酸丁酯
10% 甲基丙烯酸甲酯
14% 表面处理的三水氧化铝(ATH)
25% 按实施例B方法制备的白色颗粒和黑色颗粒的50/50混合物
1% 火成二氧化硅
0.25% 辛酸钙
0.1% 季戊四醇四-(3-巯基丙酸酯)
0.1% 环烷酸钴
将组合物的各组分在轻微搅动下混合,直到不溶组分均匀分布于基体树脂,得到粘度为大约4,000cps(4号转子)的组合物。当与过氧化物引发剂——可商购获得的过氧化物“Eperox 41-25”混合时,这种组合物在喷涂到硬表面上时可迅速交联。
实施例III
可喷涂的聚酯组合物的组分
材料 %重量
含有苯乙烯的间苯二酸NPG树脂 聚酯树脂 37
含有己二酸/苯乙烯的间苯二酸NPG 聚酯树脂 8
树脂
苯乙烯 单体 8
甲基丙烯酸甲酯 单体 4
丙烯酸 树脂改性剂 0.5
Aerosil 200 火成二氧化硅 1
Silquest A-174NT 硅烷偶合剂 0.25
BYK R605 粘度调节添加剂 0.15
Tinuvin 328 UV吸收剂 0.25
Tinuvin 292 光稳定剂 0.25
GC04 加速剂 0.6
三水合氧化铝 填充剂- 15
实施例A的白色颗粒和黑色
颗粒 25
颗粒的50/50混合物
加速剂GC04组合物
材料 %重量
异丙醇溶剂 44
辛酸钠溶液(8%的钠) 36
环烷酸钾 0.15
环烷酸钴溶液(12%的钴) 5.75
N,N’-二甲基乙酰乙酰胺 14
环烷酸铜溶液(8%的钴) 0.1
将组合物的各组分在轻微搅动下混合,直到不溶组分均匀分布于基体树脂,得到粘度为大约4,000cps(4号转子)的组合物。当与过氧化物引发剂例如浓度为大约2%的过氧化甲乙酮混合时,这种组合物在喷涂到硬表面上时可迅速交联。
实施例IV
可喷涂的丙烯酸类树脂组合物的制备
%重量 材料 类型
24 Degament 1004 丙烯酸类树脂
5 CN991 丙烯酸氨基甲酸乙酯树脂
二甲基丙烯酸乙烯缩水甘油酯
1 交联单体
(Ethylenglycidyl dimethacrylate)
8 甲基丙烯酸丁酯 单体
10 甲基丙烯酸甲酯 单体
0.75 Aerosil 200 火成二氧化硅
0.25 SN-1000 HEMA-磷酸酯偶合剂
0.25 BYK 501 消泡剂
0.25 氢氧化钙 加速剂
0.25 辛酸锌 加速剂
0.25 季戊四醇四-(3-巯基丙酸酯) 加速剂
30 三水氧化铝 填充剂
实施例A的白色颗粒
20 颗粒
和黑色颗粒的50/50混合物
将组合物的各组分在轻微搅动下混合,直到不溶组分均匀分布于基体树脂,得到粘度为大约4,000cps(4号转子)的组合物。当与过氧化物引发剂例如浓度为大约2%的叔丁基单过氧化马来酸盐混合时,这种组合物在喷涂到硬表面上时可迅速交联。
制造实施例1
使用准备好的玻璃纤维模具来制备浴室隔板部件(shower enclosureunit)。将实施例I的聚酯喷涂组合物与1%重量的MEK过氧化物混合,并在室温下使用商购获得的喷涂设备将其喷涂到模具的表面,从而得到20毫寸(mil)的厚度。被喷涂的涂料快速地交联,即使是在直立的表面该组合物也没有任何显著的流动。被喷涂的材料在75_下于25分钟后完全固化。使用玻璃纤维加强的聚酯来给喷涂的材料加衬并固化。在两小时内由模具取出的成形片材(piece)具有灰色花岗石外观的华丽表面。
制造实施例2
制造具有后挡板(backsplash)的厨房工作台面的1.5″外圆角形的预加工碎料板。将实施例I的聚酯组合物喷涂到加工好的厨房工作台面上,确保该组合物覆盖全部水平和垂直的表面以及外圆角边缘。使喷涂的片材在75_下于20-30分钟内完全固化。固化的工作台面具有喷涂时可使用的纹理表面。但是,为了模拟高度抛光的天然花岗石的纹理和外观,将该片材砂磨至外观与固体表面材料例如DUPONT CORIAN相似的缎光面,然后抛光获得光亮的表面。之间的硬度差异。此外,基质和颗粒之间的比重同一性在透亮的基质中产生了三维外观。
制造实施例3
制备透亮的丙烯酸板并真空形成浴缸形状。向实施例I的丙烯酸类树脂喷涂组合物中加入该组合物重量的1%的PMA催化剂。然后使用商购获得的喷涂设备将以上描述的涂料材料垂直地喷涂到其外表面上。将板上的涂层在75_下固化25-30分钟。由于在其成为交联的一部分以前,组合物中的丙烯酸与丙烯酸基材具有化学键合作用,因此该涂层永久地附着于丙烯酸片材(sheet)。将玻璃纤维与树脂的组合应用于外部以强化该浴缸。浴缸内表面看起来像玻璃覆盖的花岗石。
认为前述实施例是说明性的并且不应解释为限制。
Claims (13)
1.一种涂布物品以形成模拟石材涂层的方法,其包括:
(1)制备流体组合物,该流体组合物包括:(a)可交联的液体基体树脂,其中所述树脂是分布在其中的不饱和聚酯或不饱和丙烯酸类树脂,(b)含有无机填充剂的交联的细粒树脂颗粒,该细粒树脂颗粒与所述基体树脂在视觉上可区分并且与所述基体树脂具有大致相同的密度,和(c)交联加速剂,该交联加速剂包括:(i)组合物总重量0.1%至2.5%的碱金属羧酸盐或氢氧化钙或羧酸钙,其中所述羧酸盐部分具有6至22个碳原子,(ii)组合物总重量0%至2.5%的重金属羧酸盐,其中所述羧酸盐部分具有6至22个碳原子,并且其中所述金属是钴、铜或锌,和(iii)0.1%至2.5%的氮三取代的胺或氮二取代的酰胺或硫取代的硫醇,和
(2)加入引发剂,并在室温下将所得到的组合物应用于基材。
2.根据权利要求1所述的方法,其中所述基体树脂和所述颗粒由不饱和聚酯树脂制成。
3.根据权利要求2所述的方法,其中所述聚酯树脂是含有苯乙烯的新戊二醇间苯二酸酯树脂。
4.根据权利要求1所述的方法,其中所述基体树脂是丙烯酸类树脂。
5.根据权利要求2所述的方法,其中所述加速剂是碱金属羧酸盐和三取代的胺或二取代的酰胺的组合。
6.根据权利要求3所述的方法,其中所述加速剂是碱金属羧酸盐和硫醇。
7.一种流体涂料组合物,其包括:(a)可交联的液体基体树脂,其中所述树脂是均匀分布地包含在其中的不饱和聚酯或不饱和丙烯酸类树脂,(b)含有无机填充剂的交联的细粒树脂颗粒,该细粒树脂颗粒与所述基体树脂在视觉上可区分并且与所述基体树脂具有大致相同的密度,和(c)交联加速剂,该交联加速剂包括:以组合物总重量计,(i)0.1%至2.5%的碱金属羧酸盐或碱土金属羧酸盐,其中所述羧酸盐部分具有6至22个碳原子,(ii)组合物总重量0%至2.5%的重金属羧酸盐,其中所述羧酸盐部分具有6至22个碳原子,并且其中所述金属是钴、铜、或锌,和(iii)0.1%至2.5%的氮三取代的胺或氮二取代的酰胺或取代的硫醇。
8.根据权利要求7所述的组合物,其中所述基体树脂是不饱和新戊二醇间苯二酸酯树脂,并且所述加速剂包括羧酸钠和三取代的胺或二取代的酰胺。
9.根据权利要求7所述的组合物,其中所述基体树脂是丙烯酸类树脂,并且所述加速剂包括碱土金属羧酸盐和硫醇。
10.根据权利要求7所述的组合物,其中所述颗粒和所述基体树脂含有三水氧化铝。
11.根据权利要求8所述的组合物,其中所述加速剂还包括羧酸钴。
12.根据权利要求9所述的组合物,其中所述丙烯酸类树脂是可交联的聚甲基丙烯酸甲酯树脂浆。
13.根据权利要求8所述的涂料组合物,其中所述羧酸钠是辛酸钠,且所述酰胺是N,N′二甲基乙酰乙酰胺。
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US8128999B2 (en) * | 2005-12-06 | 2012-03-06 | Safas Corporation | Fire resistant sprayable coating composition |
BRPI0815847A2 (pt) | 2007-08-30 | 2015-08-25 | Ashland Licensing & Intellectu | Composição de revestimento em gel, processo para fabricar uma composição de revestimento em gel, e, método para fabricar uma embarcação. |
US9457375B2 (en) * | 2010-02-01 | 2016-10-04 | Chips Unlimited, Inc. | Decorative colored particle dispersion for use in surface coating compositions and method for making same |
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US9260344B1 (en) * | 2014-09-04 | 2016-02-16 | Safas Corporation | Moldable engineered stone |
CA3008905C (en) * | 2016-01-06 | 2020-07-07 | Oren Technologies, Llc | Conveyor with integrated dust collector system |
CN111286244A (zh) * | 2020-03-26 | 2020-06-16 | 达利塑胶制品(深圳)有限公司 | 一种高光洁度abs塑料粉盒喷漆及其制备工艺 |
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US505327A (en) * | 1893-09-19 | Charles william pinkney | ||
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US4664982A (en) | 1983-07-15 | 1987-05-12 | American Standard Inc. | Multi-layer composite structure |
US4678819A (en) * | 1984-08-30 | 1987-07-07 | Mitsubishi Rayon Co., Ltd. | Compositions for artificial marbles and process for producing artificial marbles therefrom |
US4543366A (en) | 1984-09-10 | 1985-09-24 | Thermocell Development, Ltd. | Sprayable urethane resin composition and method |
US4734452A (en) * | 1985-08-07 | 1988-03-29 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Curable composition, method for manufacturing thereof, and uses thereof |
US4664954A (en) * | 1986-08-07 | 1987-05-12 | Mountain West Marble & Onyx, Inc. | Process for forming simulated ornamental stone and product thereof |
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US5043377A (en) * | 1988-10-07 | 1991-08-27 | Nippon Shokubai Kagaku Kogyo Company, Ltd. | Granite-like artificial stone |
US5028459A (en) | 1989-06-07 | 1991-07-02 | Bayliner Marine Corporation | Imitation stone counter material and method of making the same |
US5244941A (en) * | 1989-11-02 | 1993-09-14 | Ralph Wilson Plastics Company | Artificial stone compositions, process of producing the same, and apparatus employed in the production thereof |
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US5286290A (en) * | 1992-04-16 | 1994-02-15 | Avonite, Inc. | Filler and artificial stone made therewith |
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US20040197551A1 (en) * | 2003-04-01 | 2004-10-07 | Simmons John Paul | Sprayable hardtop coating |
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