ITTO940338A1 - POLYMERIC SHAPED ARTICLES OF RESIN FOR CASTING WITH METALLIC GLOSS SURFACES IF ANY COLORED. - Google Patents
POLYMERIC SHAPED ARTICLES OF RESIN FOR CASTING WITH METALLIC GLOSS SURFACES IF ANY COLORED. Download PDFInfo
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- ITTO940338A1 ITTO940338A1 IT94TO000338A ITTO940338A ITTO940338A1 IT TO940338 A1 ITTO940338 A1 IT TO940338A1 IT 94TO000338 A IT94TO000338 A IT 94TO000338A IT TO940338 A ITTO940338 A IT TO940338A IT TO940338 A1 ITTO940338 A1 IT TO940338A1
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- Italy
- Prior art keywords
- process according
- resin
- paint
- casting
- pigment
- Prior art date
Links
- 238000005266 casting Methods 0.000 title claims description 34
- 229920005989 resin Polymers 0.000 claims description 44
- 239000011347 resin Substances 0.000 claims description 44
- 239000002932 luster Substances 0.000 claims description 35
- 239000000049 pigment Substances 0.000 claims description 33
- 239000003973 paint Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 28
- 239000011230 binding agent Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 15
- 239000000945 filler Substances 0.000 claims description 13
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 9
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- -1 methyl methyl methyl methyl methyl Chemical group 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 229920005596 polymer binder Polymers 0.000 claims description 7
- 239000002491 polymer binding agent Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000010422 painting Methods 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 229920003002 synthetic resin Polymers 0.000 claims description 3
- 239000000057 synthetic resin Substances 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 2
- 125000005907 alkyl ester group Chemical group 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 229920001519 homopolymer Polymers 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 230000000694 effects Effects 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 229920000180 alkyd Polymers 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000003086 colorant Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 229920003180 amino resin Polymers 0.000 description 3
- 235000013339 cereals Nutrition 0.000 description 3
- 239000013065 commercial product Substances 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920001228 polyisocyanate Polymers 0.000 description 3
- 239000005056 polyisocyanate Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229940116336 glycol dimethacrylate Drugs 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- NOBYOEQUFMGXBP-UHFFFAOYSA-N (4-tert-butylcyclohexyl) (4-tert-butylcyclohexyl)oxycarbonyloxy carbonate Chemical compound C1CC(C(C)(C)C)CCC1OC(=O)OOC(=O)OC1CCC(C(C)(C)C)CC1 NOBYOEQUFMGXBP-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- PLXMOAALOJOTIY-FPTXNFDTSA-N Aesculin Natural products OC[C@@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@H](O)[C@H]1Oc2cc3C=CC(=O)Oc3cc2O PLXMOAALOJOTIY-FPTXNFDTSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 239000010428 baryte Substances 0.000 description 1
- 229910052601 baryte Inorganic materials 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical class C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- 150000002976 peresters Chemical class 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000002444 silanisation Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 235000014101 wine Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C37/00—Component parts, details, accessories or auxiliary operations, not covered by group B29C33/00 or B29C35/00
- B29C37/0025—Applying surface layers, e.g. coatings, decorative layers, printed layers, to articles during shaping, e.g. in-mould printing
- B29C37/0028—In-mould coating, e.g. by introducing the coating material into the mould after forming the article
- B29C37/0032—In-mould coating, e.g. by introducing the coating material into the mould after forming the article the coating being applied upon the mould surface before introducing the moulding compound, e.g. applying a gelcoat
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
- B29C67/0007—Manufacturing coloured articles not otherwise provided for, e.g. by colour change
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C37/00—Component parts, details, accessories or auxiliary operations, not covered by group B29C33/00 or B29C35/00
- B29C37/0025—Applying surface layers, e.g. coatings, decorative layers, printed layers, to articles during shaping, e.g. in-mould printing
- B29C37/0028—In-mould coating, e.g. by introducing the coating material into the mould after forming the article
- B29C2037/0035—In-mould coating, e.g. by introducing the coating material into the mould after forming the article the coating being applied as liquid, gel, paste or the like
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2033/00—Use of polymers of unsaturated acids or derivatives thereof as moulding material
- B29K2033/04—Polymers of esters
- B29K2033/12—Polymers of methacrylic acid esters, e.g. PMMA, i.e. polymethylmethacrylate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
- B29K2105/0032—Pigments, colouring agents or opacifiyng agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
- B29K2105/16—Fillers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/769—Sanitary equipment
Description
DESCRIZIONE dell'invenzione industriale dal titolo: DESCRIPTION of the industrial invention entitled:
"Articoli sagomati polimerici di resine per colata "Polymeric shaped articles of casting resins
con superfici di lucentezza metallica eventualmente colorata" with metallic luster surfaces possibly colored "
D E S C R I Z I O N E DESCRIPTION
Oggetto dell 'invenzione Object of the invention
La presente invenzione concerne articoli sagomati polimerici di resine pericolata molto caricate con superfici di lucentezza metallica eventualmente colorate, l'effetto di superficie venendo prodotto e fissato mediante vernicia tura. The present invention relates to polymeric shaped articles of highly charged hazardous resins with possibly colored metallic luster surfaces, the surface effect being produced and fixed by painting.
Livello della tecnica Level of technique
Già nel brevetto germanico 693824 viene descritto, che si possono incassare strati contenenti colorante in ar ticoli sagomati polimerici, che vengono prodotti per polimerizzazione nello stampo, appena sotto la superficie, applicando tali strati contenenti pigmento, che contengono un legante praticamente insolubile nei composti da polimerizzare sulla parete dello stampo e quindi dopo l'introduzione dei composti fluidi da polimerizzare effettuando la polimerizzazione in modo noto. Already in the Germanic patent 693824 it is described that it is possible to embed layers containing dye in polymeric shaped articles, which are produced by polymerization in the mold, just below the surface, by applying such pigment-containing layers, which contain a practically insoluble binder in the compounds to be polymerized. on the mold wall and then after the introduction of the fluid compounds to be polymerized by carrying out the polymerization in a known way.
Gli strati contenenti pigmento possono essere distribuiti uniformemente o in modo non uniforme e per impiego di diver si strati contenenti pigmento essere policromi. E' previsto tra l'altro anche l'impiego di solventi (organici) per i leganti impiegati. Un trattamento successivo come l'applica zione di uno strato di copertura é per contro non indispensabile. The pigment-containing layers can be uniformly or non-uniformly distributed and by use of different pigment-containing layers be polychrome. Among other things, the use of (organic) solvents is also envisaged for the binders used. On the other hand, a subsequent treatment such as the application of a covering layer is not essential.
Il DE-A 3023964 descrive un procedimento per la produzione di zone contenenti pigmenti in resine acriliche e metaacriliche in vicinanza della superficie nel corso della polimerizzazione dei monomeri e prepolimeri in camere di poli merizzazione di sagomatura, che é caratterizzato dal fatto che anzitutto si applica sulla parete della camera dì polimerizzazione di formatura come strato pigmento distribuito in modo omogeneo in un legante, il legante essendo solubile o almeno rigonfiabile nella resina liquida ovvero suoi sta di preliminari, e che dopo introduzione dei monomeri e/o prepolimeri da polimerizzare si poliraerizza a resine in mo do per sé noto. DE-A 3023964 describes a process for the production of areas containing pigments in acrylic and meta-acrylic resins in the vicinity of the surface during the polymerization of monomers and prepolymers in shaping polymerization chambers, which is characterized in that it is first applied on the wall of the forming polymerization chamber as a homogeneously distributed pigment layer in a binder, the binder being soluble or at least swellable in the liquid resin or its preliminary stages, and which, after introduction of the monomers and / or prepolymers to be polymerized, polymerizes to resins in a way known per se.
Dal EP 06l 245 é noto un procedimento per la formazio ne di un oggetto sagomato, nel quale la composizione viene indurita in uno stampo, che presenta almeno due parti di stampo, che definiscono una cavità, e nel quale prima della introduzione della composizione induritine nella cavità del o stampo almeno una parte della superficie che forma la ca vita dello stampo viene munita di una deposizione di un materiale che con la composizione induritile fornisce un contrasto di colore, la deposizione venendo prestabilita su superfici dello stampo, che corrispondono alle superfici sull'oggetto sagomato indurito, sulle quali deve venire for mato un contrasto di colore, e e che é caratterizzato dal fatto che la deposizione consiste di almeno un pigmento fi nemente suddiviso in miscela con almeno una carica finemen te suddivisa di una dimensione media di particelle di 100 μm o meno e che la miscela viene applicata come sospensione in un veicolo volatile. From EP 06l 245 a process for forming a shaped object is known, in which the composition is hardened in a mold, which has at least two parts of the mold, which define a cavity, and in which, before the introduction of the hardened composition into the cavity of the mold at least a part of the surface that forms the cavity of the mold is provided with a deposition of a material which with the hardened composition provides a color contrast, the deposition being pre-established on surfaces of the mold, which correspond to the surfaces on the hardened shaped object, on which a color contrast is to be formed, and which is characterized in that the deposition consists of at least one finely divided pigment in a mixture with at least one finely divided filler of an average particle size of 100 μm or not and that the mixture is applied as a suspension in a volatile vehicle.
Il EP-A 0217 544 descrive un procedimento per la pro duzione di pezzi sagomati di composizioni induritili con zone di superficie ohe presentano contrasti di colore, una superficie di stampo prima dell'introduzione della composizione induritile venendo rivestita con un agente coloran te, costituito da a) almeno 25 % in peso di un veicolo li quido di 0 - 100 parti in peso di un liquido polimerizzabi le e 100 - 0 parti di un liquido organ. non poiimerizzatile b) 0,1 - 10 % in peso di un pigmento inorganico o 0,0001 — 1 % in peso di coloranti organ. c) 0,1 - 50 % di una resina alchidica solubile in un veicolo a) essiccante e e) un polimero solubile nel liquido. EP-A 0217 544 discloses a process for the production of shaped pieces of cured compositions with surface areas which exhibit color contrasts, a mold surface prior to the introduction of the cured composition by being coated with a coloring agent, consisting of a) at least 25% by weight of a liquid carrier of 0 - 100 parts by weight of a polymerizable liquid and 100 - 0 parts of an organic liquid. not polymerizable b) 0.1 - 10% by weight of an inorganic pigment or 0.0001 - 1% by weight of organic dyes. c) 0.1 - 50% of an alkyd resin soluble in a vehicle a) desiccant and e) a liquid soluble polymer.
Dal EP-A 0526 818 é noto un procedimento per la produ zione di articoli sagomati polimerici di resine per colata molto caricate con zone di superficie cromaticamente diffe ronziate, nel quale una superficie dello stampo di formatu ra prima del riempimento con la resina per colata viene ri vestita con un rivestimento induritile di una composizione contenente agente colorante in modo tale che risulta diffe renziazione cromatica, il rivestimento venendo applicato in almeno due stadi di verniciatura sulle zone di superfi eie previste per questo dello stampo e dopo l'essiccazione degli strati di vernice, lo stampo venendo riempito con la resina per colata e polimerizzata per riscaldamento ed infine sformata. From EP-A 0526 818 a process is known for the production of polymer shaped articles of heavily loaded casting resins with chromatically differentiated surface areas, in which a surface of the forming mold before filling with the casting resin is coated with a hardening coating of a composition containing coloring agent in such a way that chromatic differentiation results, the coating being applied in at least two painting stages on the surface areas provided for this of the mold and after drying of the paint layers , the mold being filled with the casting resin and polymerized by heating and finally demoulded.
Una particolare colorazione con pigmento, ad esempio colori a stampa o vernici, si può conseguire con pigmenti a lucentezza perlacea, i cosiddetti pigmenti ad effetto. L'effetto di lucentezza perlacea, una lucentezza metallica é molto preferito per scopi decorativi. A particular pigment coloring, for example printed colors or varnishes, can be achieved with pearly luster pigments, so-called effect pigments. The pearly sheen effect, a metallic sheen is much preferred for decorative purposes.
Vetro acrilico con effetto di lucentezza può venire realizzato mediante usuale aggiunta, ad esempio mediante miscelazione di pigmento a lucentezza perlacea nella raasea di meti'lmetacrilato da polimerizzare. In questo modo di pro cedere usuale non si possono però produrre da sistemi molto caricati oggetti induriti con superfici a lucentezza metallica causata da pigmento a lucentezza perlacea. Gloss effect acrylic glass can be made by the usual addition, for example by mixing pearly sheen pigment in the methylmethacrylate raase to be polymerized. In this usual procedure, however, it is not possible to produce from heavily loaded systems hardened objects with metallic luster surfaces caused by a pearly luster pigment.
Compito e soluzione Task and solution
Oggetti che presentano lucentezza metallica provocata da pigmento a lucentezza perlacea da sistemi induriti molto caricati si potevano approntare dopo scoperta di un procedimento di produzione adatto a ciò. Tali oggetti di resina per colata hanno interesse in particolare nel campo sanitario. Per questo essi devono essere provvisti di uno strato di superficie uniforme ad aspetto metallico lucente sufficiente profondità di colore ovvero di pigmento, per potersi opporre efficacemente allo sbiadimento sotto l'influenza di umidità ""Water-Whitening"). Items exhibiting metallic luster caused by pearly luster pigment from highly charged hardened systems could be made after discovery of a suitable manufacturing process. Such casting resin objects are of particular interest in the sanitary field. For this they must be provided with a uniform surface layer with a shiny metallic appearance sufficient depth of color or pigment, to be able to effectively resist fading under the influence of humidity "" Water-Whitening ").
Secondo la .presente invenzione possono venire appronta ti oggetti di nuovo genere di resine per colata indurite, molto caricate con superfici colorate superficialmente con pigmento a lucentezza perlacea e a lucentezza metallica. In loro proprietà esse soddisfano le esigenze poste molto ampiamente. Sorprendentemente venne trovato, che i nuovi oggetti colorati superficialmente in modo uniforme, si possono produrre in "base al procedimento noto dal EP-A 05268l8 per la produzione di articoli sagomati polimerici da resine per colata con zone di superficie differenziate cromaticamente. According to the present invention, objects of a new kind of hardened casting resins, heavily loaded with superficially colored surfaces with pearly luster and metallic luster pigment, can be prepared. In their properties they meet the demands placed very widely. Surprisingly it was found that the new objects colored in a uniform manner on the surface can be produced according to the process known from EP-A 0526818 for the production of shaped polymeric articles from casting resins with chromatically differentiated surface areas.
L'invenzione concerne The invention concerns
Articoli sagomati polimerici da resine per colata mol to caricate con superfici a lucentezza metallica, caratterizzati dal fatto che la superficie a lucentezza metallica é un rivestimento contenente pigmento a lucentezza perlacea. Polymeric shaped articles from heavily loaded casting resins with metallic luster surfaces, characterized in that the metallic luster surface is a coating containing pearly luster pigment.
Il pigmento a lucentezza perlacea può essere colorato. The pearly luster pigment can be tinted.
Inoltre la presente invenzione concerne un procedimento per la produzione dei nuovi articoli sagomati polimerici da resina per colata molto caricate con superfici a lucentezza metallica, eventualmente colorate, caratterizzato dal fatto che una superficie dello stampo di formatura prima del riempimento con la resina per colatura viene rivestita superficialmente con una composizione di vernice L induribi le contenente pigmento a lucentezza perlacea e dopo avvenuta essiccazione dello strato di vernice si riempie lo Btam po con la resina per colata e per riscaldamento viene poli merizzata ed infine sformata. Come resine per colatura ven gono impiegate preferibilmente quelle della classe delle resine acriliche. Furthermore, the present invention relates to a process for the production of new polymeric shaped articles from casting resin heavily loaded with metallic luster surfaces, possibly colored, characterized in that a surface of the forming mold is coated before filling with the casting resin. superficially with a hardenable paint composition L containing pearly luster pigment and after drying of the paint layer the Btam po is filled with the resin by casting and by heating it is polymerized and finally demoulded. As casting resins, those of the class of acrylic resins are preferably used.
Eventualmente oltre alla vernice L contenente pigmento a lucentezza perlacea viene ancora coimpiegata un'ulteriore vernice L' esente da pigmento a lucentezza perlacea, ma con tenente carica per la preparazione di superficie. If necessary, in addition to the lacquer L containing pearly sheen pigment, a further pigment-free lacquer with pearly sheen, but containing filler, is also used for surface preparation.
Attuazione dell'invenzione Implementation of the invention
Il procedimento secondo la presente invenzione per ot tenere le superfici a lucentezza metallica - come già espo sto - si serve almeno di una verniciatura ad uno stadio -eventualmente a due stadi. Nello stadio di verniciatura so stanziale giunge ad impiego una dispersione di vernice L con l'aggiunta di pigmento a lucentezza perlacea. Alla struttura delle dispersioni di vernice L ed eventualmente di L', prendono parte inoltre legante B e veicoli componen ti liquidi T. The process according to the present invention in order to obtain metallic luster surfaces - as already explained - uses at least a one-stage-possibly two-stage painting. In the substantial painting stage, a dispersion of paint L is used with the addition of a pigment with a pearly luster. In addition, binder B and liquid component vehicles T take part in the structure of the paint dispersions L and possibly L '.
I pigmenti a lucentezza perlacea da impiegare nel prò cedimento secondo la presente invenzione per la formazione delle superfici a lucentezza metallica dei nuovi articoli sagomati polimerici, sono pigmenti a lucentezza perlacea bianchi e colorati a base di mica o diossido di titanio ovvero ossido di ferro(III) con dimensioni di grana nello intervallo di 0,1 a circa 50μm. Pigmenti a lucentezza per lacea noti vengono ad esempio impiegati tecnicamente sotto il nome depositato Iriodin .Essi vengono impiegati in in chiostri da stampa, tinture di materia plastica e vernici, come ad esempio vernici per auto. Gli effetti cromatici di questi pigmenti si realizzano mediante assorbimento della luce ed interferenza. Pigmenti a lucentezza perlacea di determinato spessore di particelle soddisfano le condizioni d'interferenza e mostrano colori iridescenti The pearly luster pigments to be used in the process according to the present invention for the formation of the metallic luster surfaces of the new polymeric shaped articles, are white and colored pearly luster pigments based on mica or titanium dioxide or iron oxide (III ) with grain sizes in the range of 0.1 to approximately 50μm. Known gloss pigments for lacea are, for example, technically used under the trade name Iriodin. They are used in printing kiosks, plastic dyes and paints, such as car paints. The chromatic effects of these pigments are achieved through light absorption and interference. Pearly luster pigments of certain particle thickness meet the interference conditions and exhibit iridescent colors
Con Iriodin<® >rutilo satin fine WR secondo la presente invenzione viene ottenuto un articolo sagomato polimerico con una lucentezza molto uniforme ed una superficie che mostra un effetto metallico color argento. Nell'impiego di Iriodin rosso 9514 Silkrot WR II dopo la sformatura del corpo di polimerizzazione un corpo con una superficie che mostra effetto metallico molto lucido rosso scuro. With Iriodin <®> rutile satin fine WR according to the present invention a polymeric shaped article with a very uniform luster and a surface showing a silver metallic effect is obtained. When using Iriodin red 9514 Silkrot WR II after demoulding the polymerization body a body with a surface showing a very shiny dark red metallic effect.
In generale vengono impiegati pigmenti a lucentezza perlacea G o carica F e legante B nel rapporto 1 : 1 a 20 : 1 parti in peso, preferibilmente 2 : 1 a 10 : 1 parti in peso. In prima approssimazione si possono suddividere gli agenti leganti in questione B in leganti polimeri (B-P) e sistemi reattivi-legante (B-R) (cfr. H. Wagner & H.F. Sarx, Lackkunstharze (Resine per vernici), Carl Hanser Verlag, MELnchen 1959), che sono solubili nel componente di supporto T. I leganti polimeri B-P possono opportunamente appartene re alla stessa classe di polimeri come le resine per colata stesse. Ad esempio esse sono scelte dal gruppo dei poli'(-met) acrilati, in particolare del polimetilmetacrilato e suoi co polimeri. In general, pigments with pearly luster G or filler F and binder B in the ratio 1: 1 to 20: 1 parts by weight, preferably 2: 1 to 10: 1 parts by weight, are used. As a first approximation, the binding agents in question B can be divided into polymer binders (B-P) and reactive-binder systems (B-R) (see H. Wagner & H.F. Sarx, Lackkunstharze (Resins for paints), Carl Hanser Verlag, MELnchen 1959) , which are soluble in the support component T. The polymer binders B-P may suitably belong to the same class of polymers as the casting resins themselves. For example, they are selected from the group of poly (- meth) acrylates, in particular of polymethylmethacrylate and its copolymers.
In generale il peso molecolare MW dei leganti polimeri sta nell'intervallo 10000 - 1000000, preferibilmente nell'intervallo di 100000 - 500000 Dalton, il criterio della solubilità nel componente di supporto T dovendo essere soddisfatto . Il legante B-P giunge ad impiego sciolto in un solvente adatto, preferibilmente nel componente di supporto T. In general, the molecular weight MW of the polymer binders lies in the range 10000 - 1000000, preferably in the range of 100000 - 500000 Dalton, the criterion of solubility in the support component T having to be satisfied. The B-P binder can be used dissolved in a suitable solvent, preferably in the support component T.
La presenza dei leganti polimeri B-P non é forzatamente necessaria, per contro per l'indurimento occorre almeno un sistema-reattivo B-R. Questi sistemi possono essere forma ti solo da un legante reattivo, ad esempio una resina alchi dica, come ad esempio Alkidal<® >F26, o da due o più componenti , che induriscono sotto le condizioni dominanti (Cfr. H. Wagner, H.F. Sarx, Lackkunstharze (Resine per vernici ) loc. cit : Kirk-Othmer, Encyclopedia of Chemical Technology, (Enciclopedia di tecnologia chimica) , 3a. Ed. , Voi . 6, pagg. The presence of the B-P polymer binders is not necessarily necessary, on the other hand at least one B-R reactive system is required for hardening. These systems can be formed only from a reactive binder, for example an alkyd resin, such as Alkidal <®> F26, or from two or more components, which cure under the dominant conditions (See H. Wagner, H.F. Sarx , Lackkunstharze (Resins for paints) loc.cit: Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd Ed., Vol. 6, pp.
4-27 - 445, J. Wiley 1979). 4-27 - 445, J. Wiley 1979).
Leganti impiegabili possono essere scelti dalla classe delle resine di poiicondensazione, delle resine di poliaddizione e delle resine di polimerizzazione. Siano citate a titolo d'esempio i gruppi di Usable binders can be selected from the class of polycondensation resins, polyaddition resins and polymerization resins. The groups of
Resine alchidiche, in particolare oleomodificate ad esempio delle resine alchidiche ossidate Alkyd resins, in particular oil-modified, for example oxidized alkyd resins
Resine alchidiche più diisocianato Alkyd resins plus diisocyanate
" più materie plastiche clorurate "more chlorinated plastics
" più polistirolo "more polystyrene
” più nitrocellulosa ”Plus nitrocellulose
" più resina vinilica ed epossidica " più aminoplasti (più resina epossidica) " più silicone "more vinyl and epoxy" more aminoplasts (more epoxy) "more silicone
Resine epossidiche oleomodificate più axninoplaati.il contenuto d'olio può qui essere 20 - 80 % in peso. Oil-modified epoxy resins plus axninoplaates. The oil content can here be 20 - 80% by weight.
Fenoplasti (con o senza componenti epossidici, vinilacetalici o aminoplasti) Phenoplasts (with or without epoxy, vinyl acetal or aminoplast components)
vinilacetali con o senza componenti fenolici allilaminoplastici vinyl acetals with or without allylaminoplastic phenolic components
Resine poliestere e triaziniche Polyester and triazine resins
Allilpoliestere Allylpolyester
Aminoresine complesse Complex aminoresins
Resine indeniche e cumaroniche Indenic and coumaronic resins
Siano citati ad esempio leganti B-R, formati ad esempio da un poliisocianato aromatico (ad esempio prodotti del commercio del tipo DESMODURC <® >, prodotti della Ditta Bayer AG) e poliesteri o polieteri con gruppi ossidrile liberi (ad esempio prodotti del commercio del tipo DESMOPHEN <® >della Bayer AG) o quelli che vengono ottenuti mediante rea zione di poliisocianati con resine acriliche contenenti gruppi ossidrile (ad esempio prodotto del commercio JAGOTEX <® >F232, prodotto della Ditta,.Jäger, Fabrik chemischer Rohstoffe (Fabbrica di materia prime chimiche). For example, B-R ligands are mentioned, formed for example by an aromatic polyisocyanate (for example commercial products of the DESMODURC <®> type, products of the Company Bayer AG) and polyesters or polyethers with free hydroxyl groups (for example commercial products of the DESMOPHEN type <®> of Bayer AG) or those obtained by reacting polyisocyanates with acrylic resins containing hydroxyl groups (e.g. commercial product JAGOTEX <®> F232, product of the Company, Jäger, Fabrik chemischer Rohstoffe (Raw material factory chemicals).
Per una reticolazione tridimensionale almeno uno dei partners di reazione deve presentare tre o più gruppi reattivi nella molecola. For a three-dimensional cross-linking at least one of the reaction partners must have three or more reactive groups in the molecule.
Le vernici L ed eventualmente L' possono ancora contenere monomeri funzionalizzati come acido (met)acrilico per il miglioramento dell'adesione in porzioni da 0 a 50 %° in pe so riferito ai leganti B-P B-R, inoltre monomeri reticolanti per sé noti (cfr. Rauch-Puntigam, Acryl- und Methaacrylverbindungen (Composti acrilici e metacrilici)f Sprin ger —Verlag 1967), ad esempio esteri di acido (met)acrili co di alcoli polivalenti (polioli) come glicoldimetacrilarto e simili usualmente in quantità inferiori a 15 % in peso. Siano citati come leganti ad esempio combinazioni di leganti B-P come polimetilmetacrilato, eventualmente con ma quota di comonomero - perlopiù < 15 % in peso - ad esempio metilacrilato, 2-etilesil(met)acrilato e simili con un legante B-R, formato ad esempio da un poliisocianato aro matico (ad esempio prodotto del commercio BESMDDUR <® >N 75) ed un poliacrilato contenente gruppi ossidrile (prodotto del commercio JAGOTEX <®>F 232). Come appoggio per l'impiego siano indicati rapporto in peso B-P a B-R di.(3 — l) : 1. The paints L and possibly L 'may still contain functionalized monomers such as (meth) acrylic acid for the improvement of adhesion in portions from 0 to 50% by weight referred to the binders B-P B-R, furthermore known cross-linking monomers (cf. Rauch-Puntigam, Acryl- und Methaacrylverbindungen (Acrylic and methacrylic compounds) f Sprin ger - Verlag 1967), e.g. esters of (meth) acryl acid of polyvalent alcohols (polyols) such as glycoldimethacrylate and the like usually in amounts less than 15% in weight. For example, combinations of B-P ligands such as polymethyl methacrylate, optionally with but a share of comonomer - mostly <15% by weight - for example methyl acrylate, 2-ethylhexyl (meth) acrylate and the like with a B-R binder, formed for example by a aromatic polyisocyanate (for example commercial product BESMDDUR <®> N 75) and a polyacrylate containing hydroxyl groups (commercial product JAGOTEX <®> F 232). As a support for use, the weight ratio B-P to B-R of. (3 - l): 1 is indicated.
Il componente di supporto liquido T nella vernice L garantisce la spruzzatilità per volatilizzarsi dopo un certo tempo(d'essiccazione) opportunamente scelto. Il componen te di supporto 7 ha pertanto come Base un punto d'ebollizio ne (in condizioni normali) nell'intervallo di 50 - 220 gra di C, preferibilmente nell'intervallo di 75 - 170 gradi C. (Tuttavia può condurre allo scopo eventualmente anche la combinazione di un componente più alto bollente ed uno bassoboilente). The liquid support component T in the paint L guarantees the sprayability to volatilize after a certain (drying) time suitably chosen. The carrier component 7 therefore has as a base a boiling point (under normal conditions) in the range of 50 - 220 degrees C, preferably in the range of 75 - 170 degrees C. (However, it may eventually lead to the purpose also the combination of a higher boiling component and a low-boiling component).
Il componente di supporto T può quindi venire scelto convenientemente dal gruppo costituito da: The support component T can therefore be conveniently chosen from the group consisting of:
— Monomeri, specialmente polimerizzabili a radicali, ad esempio del tipo di esteri di acido (met)acrilico, in particolare con radicali alchile-Cl-C6, assai in particolare esteri CI o C2 (= T—M) - Monomers, especially polymerizable to radicals, for example of the type of esters of (meth) acrylic acid, in particular with alkyl-Cl-C6 radicals, very particularly esters CI or C2 (= T-M)
- Solventi, ad esempio del tipo di idrocarburi (aromat.), dei chetoni (= T-L) - Solvents, for example of the type of hydrocarbons (aromat.), Ketones (= T-L)
Come criterio di scelta supplementare per i componenti di supporto T-L può venire adibito un indice d'evaporazione (riferito a etere = 1) di 2 - 100, specialmente di 2,5 - 50· L'indice d'evaporazione (indice di evaporazione lenta é co sì definito come il tempo, nel quale una determinata quantità di solvente (usualmente 0,3 mi entro 5 sec. applicata da 10 mm di distanza su carta da filtro) é evaporata in con fronto a etiletere. (Cfr. DIN 53170; Ullmanns Encyclopädie der Techn. Chemie (Enciclopedia della chimica tecnica); 4·a Edizione Voi. 16, pag. 289,V.C. 1978). As an additional selection criterion for the T-L carrier components, an evaporation index (referred to ether = 1) of 2 - 100, especially 2.5 - 50 The evaporation index (slow evaporation index it is thus defined as the time in which a determined quantity of solvent (usually 0.3 ml within 5 sec. applied from 10 mm distance on filter paper) is evaporated in comparison with ethyl ether (cf. DIN 53170; Ullmanns Encyclopädie der Techn. Chemie (Encyclopedia of technical chemistry); 4th Edition Vol. 16, p. 289, V.C. 1978).
Come Esempi per i componenti di supporto T-M sisaio citati metilmetacrilato, metilacrilato, etilmetacrilato, nbutiImetacrilato e simili. As Examples for the cited T-M support components methyl methacrylate, methyl acrylate, ethyl methacrylate, nbutiI methacrylate and the like.
Come Esempi per il componenti di supporto T—L siano citati il butilacetato, etossietilacetato e simili, e idrocarburi come ad esempio Shellsol . Come conveniente ai é dimostra ta una combinazione di T-L T-M. As Examples for the support components T-L butyl acetate, ethoxyethyl acetate and the like, and hydrocarbons such as Shellsol are mentioned. A combination of T-L T-M is shown as convenient.
La quota di componenti di supporto T sulla vernice L sta in generale nell'intervallo 40 - 90 % in peso, la quota del legante polimero B-P a 0 - 20, preferibilmente 0,5 a 10, in particolare 1 - 10 % in peso. The share of support components T on the paint L generally lies in the range 40 - 90% by weight, the share of the polymer binder B-P at 0 - 20, preferably 0.5 to 10, in particular 1 - 10% by weight.
La quota di pigmento a lucentezza perlacea su vernice L sprezzabile é usualmente nell'intervallo 1 — 20 % in peso preferibilmente 2 - 15 % in peso. The percentage of pearly luster pigment on despicable paint L is usually in the range of 1 - 20% by weight, preferably 2 - 15% by weight.
Una composizione tipica per la vernice L può quindi essere A typical composition for L paint can therefore be
ca. 70 parti in peso metilmetacrilato ca. 70 parts by weight methyl methacrylate
5 parti in peso PMMA 5 parts by weight PMMA
20 parti in peso pigmento a lucentezza perlacea 20 parts by weight pearly luster pigment
5 parti in peso resina alchidica, ad esempio Alkydal <® >F26 5 parts by weight of alkyd resin, for example Alkydal <®> F26
Come solvente per la formulazione della vernice spruz zabile vengono impiegati quelli citati a T, ad esempio butilacetato, etilacetato e/o monomeri come MMA e/o Shellsol <® >A. Essi vengono ad esempio elaborati alla vernice sprezzabile con la formulazione della ricetta di vernice che pre cede nel rapporto in peso di 1 : 2 e per aggiunta di circa 1 a 2 parti in peso per 100 parti in peso di vernice spruzza bile di iniziatore che avvia la polimerizzazione radicalica. As solvent for the formulation of the sprayable paint, those mentioned in T are used, for example butyl acetate, ethyl acetate and / or monomers such as MMA and / or Shellsol <®> A. For example, they are processed to the despicable paint with the formulation of the paint recipe that precedes in the ratio by weight of 1: 2 and by adding about 1 to 2 parts by weight per 100 parts by weight of sprayable paint of initiator which initiates radical polymerization.
Per la produzione della vernice L si può ad esempio procedere in modo che si sciolgono tutti i componenti con eccezione del legante B-R nel componente di supporto T all'agitatore ad alette, quindi si aggiunge l'Iriodin e si ripartisce intensamente con l'agitatore ad alette. Alla fine viene aggiunto il legante B-R e disciolto. For the production of the paint L, for example, it is possible to proceed in such a way that all the components with the exception of the binder B-R in the support component T are dissolved in the fin stirrer, then the Iriodin is added and intensively distributed with the stirrer. fins. Finally the B-R binder is added and dissolved.
Come resine per colata secondo la presente invenzione in accordo con il livello della tecnica, vengono intese re sine sintetiche fluide, colabili in stampi, induribili, As casting resins according to the present invention in accordance with the state of the art, fluid, moldable, hardenable,
nel cui indurimento vengono formati gli articoli sagomati polimerici. Resine per colata G del genere molto ben utiliz zabili ovvero corrispondenti prepolimeri possono venire ri levati al brevetto europeo 218866 ovvero al US-A 4786660 o ai US—A 4221697 ovvero US—A 4251576. Preferibilmente le resine per colata G appartengono alla classe delle resine acriliche, particolarmente di preferenza si tratta di polimeri a base di metilmetacrilato, giungendo all'impiego con venientemente una miscela di un prepolimero ed i monomeri. Preferibilmente si tratta di resine per colata contenenti carica "caricate", specialmente di quelle, nelle quali le cariche costituiscono una quota di 50 - 80 % in peso riferì ta alla resina per colata. in the hardening of which the polymeric shaped articles are formed. Casting resins G of the kind that are very well usable or corresponding prepolymers can be found in European patent 218866 or in US-A 4786660 or in US-A 4221697 or US-A 4251576. Preferably the casting resins G belong to the class of resins acrylics, particularly preferably polymers based on methylmethacrylate, with a mixture of a prepolymer and the monomers being conveniently used. Preferably they are casting resins containing "filled" fillers, especially those, in which the fillers constitute a share of 50 - 80% by weight referred to the casting resin.
Come cariche P sono adatti i materiali impiegati in modo pertinente per resine per colata, a particelle fini inorga nici od organici. Opportunamente non viene superata una di mensione di grana media di 100μm di diametro. Vengono pre ferite particelle granulari. Occasionalmente può essere con veniente liberare le particelle mediante riscaldamento, circa a 250° gradi C, da umidità legata per adsorbimento. Le cariche P possono essere prodotti naturali o preparati per sintesi. Le proprietà meccaniche come durezza, modulo elastico di taglio si dimensionano secondo lo scopo d'impie go previsto delle resine sintetiche. Quivi può essere conveniente la regolazione di un modulo elastico di taglio di almeno 5 GNm<2 >· Sono adatti ad esempio minerali come os sidi d'alluminio, idrossidi d'alluminio e derivati ad esem pio ossidi doppi alcalini e alcalìnoterrosi-e idrossidi al calinoterrosi, argille, diossido di silicio in sue diverse modificazioni, silicati, allumosilicati, carbonati,fosfati, solfuri, ossidi, carbone, metalli e leghe metalliche. Suitable P fillers are the materials used appropriately for casting resins, fine inorganic or organic particles. Conveniently, an average grain size of 100μm in diameter is not exceeded. Granular particles are preferred. Occasionally it may be desirable to free the particles by heating, to approximately 250 ° C, from adsorbed moisture. The fillers P can be natural products or prepared by synthesis. The mechanical properties such as hardness, shear modulus of elasticity are sized according to the intended purpose of use of the synthetic resins. Here it can be convenient to adjust an elastic shear modulus of at least 5 GNm <2>. calinoterrosi, clays, silicon dioxide in its various modifications, silicates, alumosilicates, carbonates, phosphates, sulphides, oxides, carbon, metals and metal alloys.
Inoltre sono adatti materiali sintetici come farina di vetro, ceramica, porcellana, scorie, SiO2 sintetica finemente suddivisa. Siano citate modificazioni di silice come quarzo (farina di quarzo) tridimite e cristobalite, nonché caolino, talco, mica, feldspato, apatite, barite, gesso, creta, pietra calcarea, dolomite. Eventualmente possono an che venire impiegate miscele di cariche. La quota di carica sulle resine per colata ammonta di norma almeno a 20 % in peso. In generale non viene superata una quota di 80 % in peso. Come valore orientativo sia indicato un contenuto di carica delle resine per colata di 50 - 80 % in peso. La produzione di cariche nelle dimensioni di grana opportu ne può avvenire secondo i procedimenti noti, ad esempio me diante frantumazione e macinazione. Particolarmente preferite sono cristobalite ed idrossido d'alluminio. Also suitable are synthetic materials such as glass flour, ceramic, porcelain, slag, finely divided synthetic SiO2. Modifications of silica such as quartz (quartz flour) tridymite and cristobalite, as well as kaolin, talc, mica, feldspar, apatite, barite, gypsum, clay, limestone, dolomite are mentioned. Optionally, blends of fillers can also be used. The amount of filler on the casting resins usually amounts to at least 20% by weight. In general, a share of 80% by weight is not exceeded. As a guideline value, a filler content of the casting resins of 50 - 80% by weight is indicated. The production of fillers in the appropriate grain size can take place according to known processes, for example by crushing and grinding. Particularly preferred are cristobalite and aluminum hydroxide.
Attuazione del procedimento Implementation of the procedure
L'attuazione del procedimento secondo la presente invenzione presuppone gli stampi di formatura e dispositivi di spruzzatura usuali. Le modalità d'applicazione si possono dimostrare convenientemente su una lastra di metallo (ad esempio su una lastra d'ottone nichelato lucidata a specchio). Come temperatura di scelta per le superfici di metallo pre viste per l'applicazione siano indicati 85 gradi C. Si raccomanda di scaldare in precedenza circa 30 minuti, ad esem pio nella stufa d'essiccazione a questa temperatura. The implementation of the process according to the present invention presupposes the usual forming molds and spraying devices. The methods of application can be conveniently demonstrated on a metal plate (for example on a mirror-polished nickel-plated brass plate). 85 degrees C is indicated as the temperature of choice for the metal surfaces intended for application. It is recommended to pre-heat approximately 30 minutes, eg in the drying oven to this temperature.
L'applicazione può venire effettuata con una pistola per spruzzatura (ad esempio marca SAIA Minijet), ad esempio con ugello da 0,8 mm ed una pressione di 2,5 bar. The application can be carried out with a spray gun (for example SAIA Minijet brand), for example with a 0.8 mm nozzle and a pressure of 2.5 bar.
Convenientemente si producono i singoli strati di vernice mediante ogni volta doppia spruzzatura della vernice L'e L sull'intera superficie della lastra di metallo. La dura ta della verniciatura ammonta in generale a 2 - 2,5 minuti. Direttamente dopo l'ultima verniciatura si pone l'oggetto ancora una volta nella camera di riscaldamento (stufa di essiccazione) a 85 gradi C. Entro "breve tempo, ad esempio al disotto di 5 minuti avviene poi opportunamente il riempi mento con la resina per colata G. Il modo di procedere sia illustrato in maggior dettaglio in base ad una resina per colata PMMA/MMA contenente carica. Si prepara ad esempio en tro circa 3 minuti dalla lastra di metallo munita della ver niciatura., una seconda lastra di metallo adatta, non verniciata (come punto d'appoggio 350 x 350 x 4 mm ) ed uno spago di tenuta, (ad esempio spago-FVC con 4 mm diametro), una ca mera di formatura, nella quale s'introduce la resina per co lata molto caricata, eventualmente colorata (degasata) con ad esempio PMMA/MMA.come resina sintetica induribile e con almeno un iniziatore che provoca la polimerizzazione radica lica, ad esempio un perestere come bis-(4-tert.butilciclo esil)perossidicarbonato in quantità usuali (ad esempio 0,5 -5 % in peso riferito ai monomeri) entro breve tempo, ad esem pio circa 1,5 minuti. Dopo la chiusura della camera di formatura anzitutto a temperatura aumentata - ad esempio a cir ca 65 gradi C e nel bagno d’acqua opportunamente a posizione orizzontale della camera di formatura e convenientemente con la parte rivestita da vernice verso il basso - per uno spazio di tempo di - come punto d’appoggio - 20 minuti e quindi a temperatura ancora più elevata, ad esempio a 105 gradi C, preferibilmente nella stufa d'essiccazione per 15 minuti si tempera. Quindi l'articolo sagomato polimerico a circa 60 - 70 gradi C viene estratto dalla camera di formatura The individual layers of paint are conveniently produced by double spraying the paint L and L each time on the entire surface of the metal plate. The duration of the coating is generally 2 - 2.5 minutes. Directly after the last painting, the object is once again placed in the heating chamber (drying oven) at 85 degrees C. Within "a short time, for example under 5 minutes, the filling with resin takes place appropriately. casting G. The procedure is illustrated in greater detail on the basis of a filler-containing PMMA / MMA casting resin. For example, a second suitable metal sheet is prepared within about 3 minutes from the coated metal plate. , unpainted (as a base 350 x 350 x 4 mm) and a sealing cord, (for example twine-FVC with a 4 mm diameter), a molding chamber, in which the resin is introduced by casting heavily loaded, possibly colored (degassed) with for example PMMA / MMA as a hardenable synthetic resin and with at least one initiator that causes radical polymerization, for example a perester such as bis- (4-tert.butylcyclohexyl) peroxidicarbonate in usual quantities (for example or 0.5 -5% by weight referred to the monomers) within a short time, for example about 1.5 minutes. After closing the molding chamber first of all at increased temperature - for example at about 65 degrees C and in the water bath suitably in the horizontal position of the molding chamber and conveniently with the part coated with paint downwards - for a space of time of - as a base - 20 minutes and then at an even higher temperature, for example at 105 degrees C, preferably in the drying oven for 15 minutes it is tempered. Then the polymer shaped article at about 60 - 70 degrees C is taken out of the forming chamber
Effetti convenienti Convenient effects
Secondo il procedimento secondo la presente invenzione vengono ottenuti nuovi articoli sagomati polimerici di resi ne per colata con effetto metallico di superficie, a lucentezza metallica, eventualmente colorato e molto uniforme. According to the process according to the present invention, new shaped polymeric articles of resinous casting are obtained with a metallic surface effect, with metallic luster, possibly colored and very uniform.
Essi mostrano anche per immagazzinamento prolungato in test in acqua : 24 ore in acqua calda a 90 gradi C - nessuna colorazione bianca superficiale, il cosiddetto "Water-Whitening" (imbianchimento da acqua). They also show for prolonged storage in water tests: 24 hours in hot water at 90 degrees C - no surface white coloring, the so-called "Water-Whitening".
I seguenti Esempi e dati per la produzione degli articoli sagomati polimerici servono ad illustrare la presente invenzione. The following Examples and data for manufacturing the polymeric shaped articles serve to illustrate the present invention.
ESEMPI EXAMPLES
A) Preparazione della vernice di spruzzatura L A) Preparation of the spray paint L
Esempio 1: Example 1:
In 71 parti in peso di metilmetacrilato vengono sciolte 5,0 parti in peso di un polimetilmetacrilato con un con tenuto di 10 % in peso di metilacrilato (PM = circa 350000). A questa soluzione vengono aggiunti 1 parte in peso di glicoldimetacrilato , 3 parti in peso di Alkydal (H) F26 (60 % in xilolo, un prodotto della Ditta BAKER AG) e sciolte. In 71 parts by weight of methyl methacrylate 5.0 parts by weight of a polymethyl methacrylate with a content of 10% by weight of methyl acrylate (MW = about 350,000) are dissolved. To this solution are added 1 part by weight of glycoldimethacrylate, 3 parts by weight of Alkydal (H) F26 (60% in xylene, a product of BAKER AG) and dissolved.
Sotto agitazione con un agitatore ad alette a questo scirop po vengono aggiunte 20 parti in peso di Iriodin <® >911 Rutil Peinsatin WR (Ditta Merck). Il tempo di agitazione ammonta a circa 30 minuti. 20 parts by weight of Iriodin <®> 911 Rutil Peinsatin WR (Merck Company) are added to this syrup while stirring with a fin stirrer. The stirring time amounts to about 30 minutes.
A 50 parti in peso di questa vernice contenente Iriodin ven gono aggiunte e sciolte 12,5 parti in peso di Shellsol A (Ditta Shell), 12,5 parti in peso di n-butilacetato e 1 par te in peso Interox BCHPC = Bis-(4-t-butilcicloesilperossidicarbonato, della Ditta Peroxid-Chemie GmbH. To 50 parts by weight of this paint containing Iriodin, 12.5 parts by weight of Shellsol A (Company Shell), 12.5 parts by weight of n-butyl acetate and 1 part by weight of Interox BCHPC = Bis- are added and dissolved. (4-t-butylcyclohexylperoxydicarbonate, of the company Peroxid-Chemie GmbH.
Esempio 2: Example 2:
Procedimento come in Esempio 1, in luogo di Iriodin 9111 Rutil Pteinsatin WR venne impiegata la stessa quantità di Iriodin 9514 Silkrot WRII. Procedure as in Example 1, the same quantity of Iriodin 9514 Silkrot WRII was used instead of Iriodin 9111 Rutil Pteinsatin WR.
B) Preparazione della vernice di spruzzatura L' B) Preparation of the spray paint
In 75 parti in peso di metiImetacrilato vengono aggiun te e disciolte 5,0 parti in peso di un poiimetilmetaorilato con un contenuto di 10 $ in peso di metilacrilato (PM = cir ca 350000) e 45 parti in peso di cristobalite silanizzata (prodotto SILBOND <® >6000 JET di Quarzwerke Erechen) disperse al dissolutone con circa 10,0 m/sec per 15 minuti. A que sta sospensione vengono aggiunte e disciolte 1 parte in peso di glicoldimetilacrilato e 3 parti in peso Alkydal <® >F26 (60 % in xilolo, un prodotto della Ditta BATER AG). In 75 parts by weight of methyl methacrylate, 5.0 parts by weight of a polyimethyl methacrylate with a content of 10% by weight of methyl acrylate (MW = about 350,000) and 45 parts by weight of silanized cristobalite are added and dissolved (product SILBOND < ®> 6000 JET by Quarzwerke Erechen) dispersed in dissolutone with about 10.0 m / sec for 15 minutes. To this suspension are added and dissolved 1 part by weight of glycoldimethylacrylate and 3 parts by weight Alkydal <®> F26 (60% in xylene, a product of the company BATER AG).
C) La resina per colata molto caricata C) The heavily loaded casting resin
Ad una soluzione preliminare prepolimerica, ad esempio 40 parti in peso di una soluzione MMA/PMMA (Rapporto in peso 35 ' 5), che contiene ancora agente di reticolazione ed even tualmente un silano con un catalizzatore di silanizzazione, vengono disperse 50 - 80 parti in peso di una carica inorganica. Preferibilmente vengono impiegati cristobalite 0 idros sido d'alluminio. Oltre ad agenti distaccanti come acido stearico la resina per colata contiene ancora un iniziatore di polimerizzazione come ad esempio bis-(4—tert.butilciclo— e sii )perossidi carbonato o un sistema-Redox usuale . To a preliminary prepolymer solution, for example 40 parts by weight of an MMA / PMMA solution (ratio by weight 35 '5), which still contains crosslinking agent and possibly a silane with a silanization catalyst, 50 - 80 parts are dispersed by weight of an inorganic filler. Cristobalite or aluminum hydroxide are preferably used. In addition to release agents such as stearic acid, the casting resin still contains a polymerization initiator such as bis- (4-tert.butylcyclo- e sii) peroxide carbonate or a usual Redox system.
D) Preparazione degli articoli sagomati polimerici D) Preparation of the polymeric shaped articles
La produzione degli articoli sagomati polimerici é descritta in maggior dettaglio in quanto precede nel paragrafo attuazione del procedimento. The production of the polymeric shaped articles is described in greater detail in the preceding paragraph in the paragraph on carrying out the procedure.
E) Controllo degli articoli sagomati al "Water-Whitening" Da provini di colatura di lastre vengono ritagliati pro vini di 50 x 50 mm. E) Control of the shaped articles at "Water-Whitening" 50 x 50 mm pro wines are cut from specimens of casting plates.
I provini vengono collocati 24 ore in acqua con una temperatura di 90 gradi C. Dopo un ulteriore tempo d'immagazzinamen to di 24 ore a temperatura ambiente, in aria, i campioni ven gono comparati con un campione come fornito. The specimens are placed 24 hours in water at a temperature of 90 degrees C. After an additional 24 hour storage time at room temperature, in air, the samples are compared with a sample as supplied.
Risultato: Result:
Gli articoli sagomati secondo la presente invenzione dopo il trattamento in acqua non mostrano praticamente alcun schiarimento rispetto ai campioni come fomiti. The shaped articles according to the present invention after water treatment show practically no lightening compared to the samples as supplied.
Resine per colata indurite senza rivestimento di pigmento a lucentezza perlacea mostrano dopo il test "Water-Whitening" (imbianchimento all'acqua)uno schiarimento sensibile. Hardened casting resins without pearly luster pigment coating show noticeable lightening after the "Water-Whitening" test.
Claims (13)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4313925A DE4313925A1 (en) | 1993-04-28 | 1993-04-28 | Polymer moldings made of casting resins with shiny metallic, possibly colored surfaces |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| ITTO940338A0 ITTO940338A0 (en) | 1994-04-27 |
| ITTO940338A1 true ITTO940338A1 (en) | 1995-10-27 |
| IT1273162B IT1273162B (en) | 1997-07-07 |
Family
ID=6486609
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| ITTO940338A IT1273162B (en) | 1993-04-28 | 1994-04-27 | POLYMER SHAPED ARTICLES OF RESINS FOR CASTING WITH SURFACES OF METALLIC GLOSS, EVENTUALLY COLORED |
Country Status (8)
| Country | Link |
|---|---|
| AT (1) | ATA55994A (en) |
| CH (1) | CH686498A5 (en) |
| DE (1) | DE4313925A1 (en) |
| ES (1) | ES2094683B1 (en) |
| FR (1) | FR2704551B1 (en) |
| GB (1) | GB2277477B (en) |
| IT (1) | IT1273162B (en) |
| NL (1) | NL9400692A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10004449A1 (en) * | 2000-02-03 | 2001-08-09 | Roehm Gmbh | Self-reinforced, thermoplastic moldable sheet made of poly (meth) acrylate, process for its production and sanitary articles made from the sheet |
| FR2826904A1 (en) * | 2001-07-06 | 2003-01-10 | Extreme Decors | METHOD FOR MANUFACTURING FLOOR COVERING PLATES |
| DE102004045295A1 (en) * | 2004-09-16 | 2006-03-23 | Röhm GmbH & Co. KG | Plastic body with inorganic coating, method of manufacture and uses |
| DE202016005744U1 (en) * | 2016-09-20 | 2017-01-10 | FR Bayern Technology GmbH | Moldings made of composite materials with an artificial optical surface patina similar to a natural copper patina |
| DE102017116306A1 (en) * | 2017-07-19 | 2019-01-24 | Blanco Gmbh + Co Kg | Process for producing a plastic molding with an optically structured surface area and produced plastic molding |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB457986A (en) * | 1934-11-03 | 1936-12-10 | Albert Products Ltd | A process for preparing and forming the surface of moulded articles from synthetic resins capable of being hardened |
| GB915011A (en) * | 1958-03-28 | 1963-01-09 | Heinz Hunsdiecker | Production of synthetic resin articles with pearl and mother of pearl iridescence |
| GB1076167A (en) * | 1963-05-21 | 1967-07-19 | Mecmax Ltd | Improvements in and relating to the manufacture of artificial materials |
| GB1138477A (en) * | 1965-05-13 | 1969-01-01 | Monsanto Co | Improvements in and relating to blow moulded containers |
| SE366521B (en) * | 1973-02-02 | 1974-04-29 | Tetra Pak Int | |
| DE2544245C3 (en) * | 1975-10-03 | 1981-12-17 | Röhm GmbH, 6100 Darmstadt | Infrared reflective glazing material |
| DE2861961D1 (en) * | 1977-11-14 | 1982-09-09 | Ici Plc | Decorative acrylic sheets and articles formed therefrom |
| EP0061245B1 (en) * | 1981-03-20 | 1988-05-11 | Imperial Chemical Industries Plc | Process for providing colour contrast on surface of moulded article |
| DE3140316C2 (en) * | 1981-10-10 | 1983-10-13 | Basf Farben + Fasern Ag, 2000 Hamburg | Process for the production of plastic composite material parts |
| DE3317882A1 (en) * | 1983-05-17 | 1984-11-22 | Merck Patent Gmbh, 6100 Darmstadt | RADIATION-curable BINDING SYSTEMS, METHOD FOR THEIR USE AND COVERS PRODUCED THEREOF |
| GB8411824D0 (en) * | 1984-05-09 | 1984-06-13 | Ici Plc | Producing shaped articles |
| US4598020A (en) * | 1985-08-16 | 1986-07-01 | Inmont Corporation | Automotive paint compositions containing pearlescent pigments and dyes |
| GB8521652D0 (en) * | 1985-08-30 | 1985-10-02 | Ici Plc | Moulding articles & composition |
| EP0362129B1 (en) * | 1988-09-09 | 1994-06-22 | Ciba-Geigy Ag | Paint containing molybdenum disulfide |
| US4959189A (en) * | 1988-09-26 | 1990-09-25 | E. I. Du Pont De Nemours And Company | Process for forming a composite structure of thermoplastic polymer and sheet molding compound |
| DE4126024A1 (en) * | 1991-08-06 | 1993-02-11 | Roehm Gmbh | METHOD FOR PRODUCING POLYMERIZED MOLDING PIECES FROM HIGHLY FILLED CAST RESIN WITH COLOR-DIFFERENTIATED SURFACE AREAS |
| EP0662032A1 (en) * | 1992-09-24 | 1995-07-12 | H.B. Fuller Company | Thermoplastic coated substrates |
-
1993
- 1993-04-28 DE DE4313925A patent/DE4313925A1/en not_active Withdrawn
-
1994
- 1994-03-16 AT AT0055994A patent/ATA55994A/en not_active Application Discontinuation
- 1994-04-19 CH CH118694A patent/CH686498A5/en not_active IP Right Cessation
- 1994-04-25 FR FR9404939A patent/FR2704551B1/en not_active Expired - Fee Related
- 1994-04-26 ES ES09400872A patent/ES2094683B1/en not_active Expired - Fee Related
- 1994-04-27 IT ITTO940338A patent/IT1273162B/en active IP Right Grant
- 1994-04-28 NL NL9400692A patent/NL9400692A/en not_active Application Discontinuation
- 1994-04-28 GB GB9408426A patent/GB2277477B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| DE4313925A1 (en) | 1994-11-03 |
| GB2277477B (en) | 1997-03-26 |
| ITTO940338A0 (en) | 1994-04-27 |
| ES2094683A1 (en) | 1997-01-16 |
| FR2704551B1 (en) | 1997-04-18 |
| GB9408426D0 (en) | 1994-06-22 |
| FR2704551A1 (en) | 1994-11-04 |
| GB2277477A (en) | 1994-11-02 |
| CH686498A5 (en) | 1996-04-15 |
| NL9400692A (en) | 1994-11-16 |
| IT1273162B (en) | 1997-07-07 |
| ATA55994A (en) | 1998-11-15 |
| ES2094683B1 (en) | 1997-12-16 |
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